MX2008008631A - Copolymers, method for producing them and their use for treating surfaces - Google Patents

Abstract

The invention relates to copolymers that contain, polymerized into them, as comonomers (a) ethylene, (b) one or more compounds of general formula (I), (c) optionally one or more alkenylphosphonic diesters, (d) optionally one or more additional radically copolymerizable comonomers, the variables being defined as follows:R1is selected from hydrogen and unbranched or branched C1-C10alkyl, R2is selected from hydrogen and unbranched or branched C1-C10alkyl, R3is selected from hydrogen, phenyl, benzyl and unbranched or branched C1-C10alkyl and unbranched or branched hydroxy-C2-C10alkyl, as a free acid or partially or completely neutralized with alkali metal, alkaline earth metal, ammonia or organic amine.

Description

COPOLYMERS. METHOD TO PRODUCE AND USE TO TREAT SURFACES The present invention relates to copolymers comprising as comonomers in copolymerized form: (a) ethylene, (b) one or more compounds of the general formula I (c) if appropriate, one or more alkenyl phosphonic diesters, (d) if appropriate, one or more other radically free copolymerizable comonomers, whose variables are defined as follows: R1 is selected from hydrogen and unbranched and branched d-C10 alkyl, R2 is selected from hydrogen and unbranched and branched dC? 0 alkyl, R3 is selected from hydrogen, phenyl, benzyl and unbranched and branched d-Cio alkyl and C2-C? or unbranched and branched hydroxyalkyl, as free or neutralized acid partially or completely with alkali metal, alkaline earth metal, ammonia or organic amine.

The present invention also relates to a process for preparing copolymers of the invention. The present invention further relates to the use of the copolymers of the invention for the purpose, for example, of treating surfaces. The present invention further relates to surfaces coated with the copolymer of the invention. The surface treatment of, for example, metal surfaces or polymer surfaces is a field of great economic importance. The surface treatment, for example, may be a treatment for the purpose of coating material adhesion, for the purpose of protecting a coating material under corrosive exposure of expanded sub-film oxidation, for the purpose of improving the coefficient of friction. with other surfaces, in particular in the case of cold forming, such as by deep drawing, folding, bending or bending, for the purpose of obtaining a decorative appearance, gloss and roughness, for example, or for the purpose of enhancing the skill of bending, swirling and, in particular, corrosion protection. It is known to impart corrosion resistance to surfaces by treating them with compounds such as, for example, 1,12-dodecanedi (dimethyl phosphonic acid ester). However, said treatment has the disadvantage of acting exclusively as protection against sub-film corrosion for combinations of particular metals with particular coating materials, and when used alone does not accumulate a corrosion protection layer.

Therefore, the object was to provide a method of treating metal or polymer surfaces, for example, and thus achieve an overall improvement in properties and in particular enhanced corrosion protection. Another object was to provide coated surfaces. Still another object was to find suitable materials with particular adaptation to treat surfaces. In particular, the object was to provide compounds that are capable of acting not only in aqueous solution as a corrosion inhibitor, but also after drying on a metal surface as a protective layer of corrosion. Accordingly, the invention provides the copolymers defined above and the method defined at the beginning. The copolymers of the invention comprise in copolymerized form: (a) ethylene, (b) one or more compounds of the general formula I whose variables are defined as follows: R1 is selected from branched and preferably unbranched C?-C alquilo alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, ter -butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; more preferably C 1 -C 4 alkyl such as methyl, ethyl, n-propyl or n-butyl, especially methyl, and very particularly preferably hydrogen, R 2 is selected from branched and preferably unbranched d-Cι alkyl, such such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl , sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; more preferably Ci-C4 alkyl such as methyl, ethyl, n-propyl or n-butyl, especially methyl, and very particularly preferably hydrogen, R3 is different or, preferably, identical and is selected from hydrogen; phenyl, unsubstituted or substituted one to three times, for example, by halogen, chlorine, for example, or by unbranched C 1 -C 4 alkyl such as methyl, ethyl, n-propyl or n-butyl, especially methyl, benzyl , and branched and preferably unbranched CrC10 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, , 2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n- octyl, 2-ethylhexyl, n-nonyl, n-decyl; more preferably C 1 -C 4 alkyl such as methyl, ethyl, n-propyl or n-butyl, especially methyl, and branched and preferably unbranched C 2 -C 10 hydroxyalkyl, preferably 2-hydroxy-C 2 -C 6 alkyl or α- hydroxy-C2-C6 alkyl. Examples of 2-hydroxy-C2-C6 alkyl are 2-hydroxyethyl, 2-hydroxy-n-propyl, 2-hydroxy-n-butyl, 2-hydroxy-n-hexyl, 2-hydroxy-n-hexyl, and -hydroxy-isopropyl. Examples of α-hydroxy-C2-C6 alkyl are 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, and, in particular, 2-hydroxyethyl. (c) if appropriate, one or more alkenyl phosphonic diesters, alkenylphosphonic diester (c) preferably being a compound of formula II whose variables are defined below: R 4 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, , 2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; more preferably d-d alkyl such as methyl, ethyl, n-propyl or n-butyl, especially methyl, and very particularly preferably hydrogen, R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; more preferably C 1 -C 4 alkyl such as methyl, ethyl, n-propyl or n-butyl, especially methyl, and very particularly preferably hydrogen, R 6 is different or, preferably, identical and is selected from phenyl, unsubstituted or substituted two to three times, for example, by hydrogen, chlorine, or, for example, by unbranched C 1 -C 4 alkyl such as methyl, ethyl, n-propyl or n-butyl, especially methyl, benzyl, and alkyl of branched and preferably unbranched C? -C10, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, , 2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; more preferably C 1 -C 4 alkyl such as methyl, ethyl, n-propyl or n-butyl, especially methyl.

The radicals R6 can be brought together to form a ring of five to 10 members. In this way, the group P (O) (OR6) 2 can be, for example: (c) if appropriate, one or more other radically free copolymerizable comonomers. In one embodiment of the present invention, one or more other radically free copolymerizable comonomers (d) are selected from ethylenically unsaturated carboxylic acids, such as crotonic acid and especially (meth) acrylic acid, dC? 0 alkyl esters. of (meth) acrylic acid, especially methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, vinyl formate, vinyl esters of C? -C10 alkylcarboxylic acid, such as vinyl acetate or vinyl propionate, ethylenically unsaturated C-C 10 dicarboxylic acids and their anhydrides, C 1 -C 20 alkyl vinyl ethers and allyl alkyl ethers of α-olefins having 3 to 40 carbon atoms, such as isobutene, 1-butene, diisobutene, 1-hexene and 1-dodecene, for example. Preferred comonomers (d) are selected from ethylenically unsaturated carboxylic acids, such as acid crotonic and in particular (meth) acrylic acid, and C4-C10 ethylenically unsaturated dicarboxylic acids and their anhydrides, especially itaconic anhydride and very particularly maleic anhydride. In one embodiment of the present invention, the copolymers of the invention comprise no other comonomer (d) in copolymerized form. In the context of the present invention, "comprises in copolymerized form" in connection with compounds of the general formula I does not necessarily mean that a compound of the general formula I as such is reacted with ethylene and, if appropriate, one or more alkenyl phosphonic diesters (c) and / or one or more comonomers (d).

Instead, the copolymers of the invention formally comprise at least one compound of the general formula I in copolymerized form; that is, they comprise units that formally derive from one or more compounds of the general formula I as a comonomer. In one embodiment of the present invention, the two radicals R6 are different, one radical R6 being methyl and the other ethyl or n-propyl or isopropyl, for example. In another preferred embodiment of the present invention, the two radicals R6 are identical and in particular are selected from methyl and ethyl. In one embodiment of the present invention, R1 and R2 are each hydrogen and R3 is selected from C1-C alkyl, particular is selected from methyl and ethyl. In one embodiment of the present invention, R 4 and R 5 are each hydrogen and the radicals R 6 are each identical and selected from C 1 -C alkyl, in particular selected from methyl and ethyl. In one embodiment of the present invention, R3 and R1 are each in each case identical. In one embodiment of the present invention, R1 and R4, R2 and R5, and R3 and R6, in each case in pairs, are identical; in other words, R1 and R4 are each identical, R2 and R5 are each identical, and R3 and R6 are each identical. Preferably, R1, R2, R4 and R5 are each identical and with particular preference are each hydrogen. In one embodiment of the present invention, the copolymers of the invention comprise two different compounds of the formula I in copolymerized form, of which R1 and R4 and also R2 and R5, in each case in pairs, are identical, and of which one R3 is hydrogen and the other R3 is selected from phenyl, benzyl, d-C10 alkyl, and C2-C10 hydroxyalkyl, especially linear d-C4 alkyl, and, very particularly preferably, methyl. In one embodiment of the present invention, the copolymer of the invention comprises copolymer having an average molecular weight Mw in the range of 1000 to 500,000 g / mol, preferably 1000 to 200000 g / mol, and most preferably 1500 to 150000 g / mol. In one embodiment of the present invention, the copolymer of the invention has a melt flow rate (MFR) in the range of 1 to 50 g / 10 minutes, preferably 5 to 20 g / 10 minutes, more preferably 7 to 15 g / 10 minutes, measured at 160 ° C under a load of 325 g in accordance with EN ISO 1133. In one embodiment of the present invention, the copolymer of the invention has a viscosity v of kinematic melt at 120 ° C of 60 mm2 / s at 100 000 mm2 / s, preferably 100 mm2 / s at 50 000 mm2 / s. In one embodiment of the present invention, the casting scale of copolymer of the invention is placed on the scale of 50 to 120 ° C, preferably on the scale of 60 to 110 ° C, determined by DSC in accordance with DIN 51007. In one embodiment of the present invention, the copolymer casting scale of the invention can be broad and can be related to a temperature scale of at least 7 to no more than ° C, preferably at least 10 ° C and not more than 15 ° C. In another embodiment of the present invention, the copolymer casting point of the invention is remarkably defined and is within a temperature range of less than 2 ° C, preferably less than 1 ° C, determined in accordance with DIN 53479. In one embodiment of the present invention, the acid number of copolymer of the invention is in the range of 10 to 250 mg KOH / g of copolymer, preferably 20 to 200 mg KOH / g of copolymer, determined in accordance with DIN 53402.

The copolymers of the invention may be alternating copolymers or block copolymers or, preferably, random copolymers. In a specific embodiment of the present invention, the copolymer of the invention comprises substantially random copolymers which may have one or more alternating comonomer sequences or one or more comonomer sequences with block character, in copolymerized form. The copolymers of the invention can be present as free or partially or completely neutralized acid, with, for example, divalent or polyvalent cations, such as alkaline earth metal cations, Zn2 +, Zr4 +, ZrO +, Cr3 +, Mn2 \ Fe2 +, Fe3 +, Co +, Ni2 +, Cu2 +, Al3 +, Ce3 +, V2 +, V3 +, preferably Mg2 +, Ca2 +, Zn2 + or Mn2 + and Cr3 +, preferably with monovalent cations such as alkali metal, such as Na + or K +, or with ammonia or amine organic, especially C 1 -C 4 monoalkylamine, C 1 -C 4 di-alkylamine, C 1 -C 4 tri-alkylamine or C 1 -C 4 tetra-alkyl-ammonium. In one embodiment of the present invention, all or up to 90 mole%, preferably up to 75 mole%, of the carboxylic acid groups and / or P (O) -OH groups of the copolymers of the invention are neutralized with hydroxyalkylammonium, in particular from the formula (alkyl of d-C) x (hydroxy alkyl of C2-C -?) and NH-xy) where x is an integer on the scale from zero to three, preferably zero or one, and is an integer on the scale of one to four, with the systemic inflammatory condition that the sum of x and y does not exceed a value of four.

Preferred examples of hydroxyalkyl of d-C -? they are 3-hydroxypropyl, 4-hydroxybutyl, and, in particular, 2-hydroxyethyl, hereinafter referred to as hydroxyethyl. Particularly preferred examples of hydroxyalkylammonium are N, N-dihydroxyethylammonium, N-methyl-N-hydroxyethylammonium, N, N-dimethyl-N-hydroxyethylammonium, N-methyl-N, N-dihydroxyethylammonium, Nn-butyl-hydroxyethylammonium, and N-butyl -N, N-dihydroxyethylammonium. Amines particularly suitable for neutralizing are trialkylamines and alkanolamines having less than 30, more preferably less than 10 carbon atoms. Especially preferred amines to neutralize are (3-aminopropyl) amino-2-ethanol, 1,1-dimethylpropin-2-ylamine, 1,2-ethanediamine, 1,2-propylenediamine, 1,3-propanediamine, 1,6-hexanediamine, 1-amino-2 -propanol, 2- (dimethylamino) ethanol, 2-phenylaminoethanol, 6-amino-1-hexanol, cyclohexyl-amine, diethanolamine, diisopropanolamine, dimethylamine, dimethylamidoethoxy-ethanol, ethanolamine, ethylamine, amine coconut fat, triethanolamine, cyclohexylamine and N, N-dimethylaminocyclohexane. More organic amines suitable for neutralization are, for example, morpholine, imidazole, imidazolines, oxazolines, triazoles, and fatty amines. Suitable neutralizing agents are, in addition, KOH, NaOH, Ca (OH) 2, NaHCO 3 > Na2CO3, K2CO3 and KHCO3. In one embodiment of the present invention, the neutralization can be carried out using stoichiometric amounts or an excess of transition metal complexes, such as one or more transition metal amines or transition metal ammonium complexes, preferably one or more zinc-amine and / or zinc-ammonia complexes, examples being Zn (NH3) 4 (H2O) 2] 2+ salts such as sulfates or nitrates, for example. In particular, the use of zinc-ammonia complexes has the advantage that, after drying, a film is formed which is entangled via zinc ions, which does not readily dissolve even in aggressive medium and which therefore offers improved corrosion protection . The present invention further provides a process for preparing copolymers of the invention. The copolymers of the invention can be prepared, for example, by subjecting ethylene (a), one or more compounds of the general formula I (b), and, if appropriate, one or more alkenyl phosphonic diesters (c), and, to be appropriate, one or more copolymerizable comonomers radically free (d) to copolymerization with each other.

The copolymers of the invention can be prepared, especially when R.sup.1 and R.sup.4, R.sup.2 and R.sup.5, and R.sup.3 and R.sup.6, in each case in pairs, are identical, by means of preferably radically ethylene-free (ethylene-free) copolymerization, so minus one diester alkenyl phosphonic (c), and, if appropriate, one or more other radically free copolymerizable comonomers (d) under high pressure conditions, such as in stirred high pressure autoclaves or in high pressure tube reactors, for example, followed by at least partial hydrolysis of copolymerized alkenylphosphonic diester (c). The present invention further provides a process for preparing copolymers of the invention comprising subjecting (a) ethylene, (c) if appropriate, one or more alkenyl phosphonic diesters, (d) if appropriate, one or more copolymerizable, free radical comonomers to copolymerization with each other at 500 to 4000 bar and reaction temperatures in the range of 150 to 300 ° C, preferably with free radical initiation, and subsequently at least partial hydrolysis. The radically free initiated copolymerization, also referred to for short as copolymerization below, is preferably performed in stirred high pressure autoclaves. Agitated high pressure autoclaves are known per se: a description is found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, key: Waxes, vol. A 28, p. 146 ff., Verlag Chemie Weinheim, Basle, Cambridge, New York, Tokyo, 1996. The length / diameter ratio of said autoclaves is predominantly at the scales of 5: 1 to 30: 1, preferably 10: 1 to 20: 1. . The high pressure tube reactors that is equally possible to employ are also found in Ullmann's Encyclopedia of Industrial Chemistry, 5a. edition, key: Waxes, vol. A 28, p. 146 ff., Verlag Chemie Weinheim, Basle, Cambridge, New York, Tokyo, 1996. Suitable pressure conditions for copolymerization are 500 to 4000 bar, preferably 1500 to 2500 bar. The conditions of this class are also referred to later as high pressure. The reaction temperatures are in the range of 150 to 300 ° C, preferably in the range of 195 to 280 ° C. The copolymerization can be carried out in the presence of a regulator. Regulators used include, for example, hydrogen or at least one aliphatic aldehyde or at least one aliphatic ketone of the general formula III or mixtures thereof. The radicals R7 and R8 are identical or different and are selected from hydrogen; d-Ce alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, more preferably C 1 -C 4 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; C3-C10 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preference is given to cyclopentyl, cyclohexyl and cycloheptyl. In a particular embodiment, the radicals R7 and R8 are covalently linked together to form a ring of 4 to 13 members. In this way, for example, R7 and R8 can be together - (CH2) 4-, - (CH2) 5-, - (CH2) 6-, - (CH2) 7-, -CH (CH3) -CH2-CH2 -CH (CH3) - or -CH (CH3) -CH2-CH2-CH2-CH (CH3) -. Particularly preferred regulators are propionaldehyde, acetone, and ethyl methyl ketone. Examples of suitable regulators further include alkylaromatic compounds, examples being toluene, ethylbenzene or one or more xylene isomers. Examples of highly suitable regulators further include paraffins such as, for example, isododecane (2,2,4,6,6-pentamethylheptane) or isooctane. The initiators that can be used for the free radical copolymerization are the typical free radical initiators such as organic peroxides, oxygen or azo compounds, for example. Mixtures of two or more free radical initiators are also suitable. The suitable peroxides, selected from commercially available substances, are didecanoyl peroxide, 2,5-dimethyl-2,5-di (2- ethylhexanoylperoxy) hexane, ter-amyl peroxypivalate, tert-butyl peroxypivate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-ethylacetate, tert-butyl peroxydiethylisobutyrate, 1,4- di (tert-butylperoxycarbonyl) cyclohexane as a mixture of isomer, tert-butyl perisononanoate, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (tert-butylperoxy) - cyclohexane, methyl isobutyl ketone peroxide, tert-butyl peroxyisopropyl carbonate, 2,2-di (tert-butylperoxy) butane or tert-butyl peroxyacetate; tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, the isomeric di (tert-butylperoxyisopropyl) benzenes, 2,5-dimethyl-2,5-di-tert-butylperoxy-hexane, tert-butyl peroxide cumyl, 2,5-dimethyl-2,5-di (tert-butylperoxy) hex-3-ina, di-tert-butyl peroxide, 1,3-diisopropylbenzene monohydroperoxide, eumenohydroperoxide or tert-butylhydroperoxide; or peroxides of dimeric or trimeric ketone, as is known from EP-A 0813550.

Particularly suitable peroxides are di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxy-isononanoate or dibenzoyl peroxide or mixtures thereof. As an example of an azo compound, mention may be made of azobiisobutyronitrile (AIBN). Free radical initiators are measured in typical amounts for polymerizations.

Numerous commercially available organic peroxides are mixed with what are called phlegmatizers before being sold, in order to improve their handling qualities. Examples of suitable phlegmatizers include soft oil or hydrocarbons such as isododecane in particular. Under the conditions of high pressure polymerization it is possible that said phlegmatizers may have a molecular weight regulating effect. For the purposes of the present invention, the use of molecular weight regulators should involve the additional use of more molecular weight regulators beyond the use of phlegmatizers. The proportion of the comonomers in the case of measured addition typically does not correspond to the proportion of the units in the copolymers of the invention, since the alkenyl phosphonic diesters (c) are generally more readily incorporated into copolymers than ethylene. The comonomers (a), (c), and, if appropriate, (d) are typically identified together or separately. The comonomers (a), (c), and, if appropriate, (d) can be brought to the polymerization pressure using a high pressure pump. In another embodiment, the comonomers (a), (c), and, if appropriate, (d) are first brought to an increased pressure of 150 to 400 bar, for example, preferably 200 to 300 bar, and in particular 260 bar , using a compressor, and then brought to the actual polymerization pressure using another compressor. In another embodiment, the comonomers (a) are first brought to an increased pressure of 150 at 400 bar, for example, preferably 200 to 300 bar, and in particular 260 bar, by means of a compressor, and then brought to the actual polymerization pressure with another compressor, and the comonomers (c) and, if appropriate , (d) at the same time they are brought to the polymerization pressure with a high pressure pump. The copolymerization can alternatively be carried out in the absence and in the presence of solvents - mineral oils, white oil, and other solvents present during polymerization in the reactor and used for the purpose of phleizing the free radical initiator or initiators are not considered. solvents for the purposes of the present invention. Examples of suitable solvents include toluene, isododecane, and isomers of xylene, acetone, and methyl ethyl ketone. Then, copolymerization was possible, for example, to remove the non-copolymerized comonomer (a), (c) and / or, if appropriate, (d). The copolymerization described above produces a copolymer which in the context of the present invention is also referred to as a precursor copolymer. The copolymerization of (a), (c), and, if appropriate, (d) is followed by at least partial hydrolysis of copolymerized alkenylphosphonic diester (c). In one embodiment of the present invention, the at least partial hydrolysis is carried out such that the precursor copolymer is reacted with one or more inorganic hydroxides, preferably alkali metal hydroxides, in particular sodium hydroxide or potassium hydroxide, by volume or, preferably, in organic solvent or water, or in a mixture of organic solvent and water. In one embodiment of the present invention, the at least partial hydrolysis is carried out so that the precursor polymer is reacted with ammonia or an organic amine in a mixture of organic solvent and water, or in water. In one embodiment of the present invention, the at least partial hydrolysis is carried out so that the precursor copolymer is reacted with ammonia or an organic amine by volume or an organic solvent and then treated with water. In another embodiment of the present invention, the at least partial hydrolysis is carried out so that the precursor copolymer is reacted with one or more acids, preferably hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, and acid methanesulfonic acid, in the presence of water and, if appropriate, an organic solvent. In one embodiment of the present invention, the precursor copolymer is reacted at a temperature in the range of 60 to 150 ° C, more preferably 75 to 120 ° C. In one embodiment of the present invention, the precursor copolymer is reacted under atmospheric pressure. In another embodiment of the present invention, the precursor copolymer is reacted at a pressure in the range of 1.1 to 20 bar, in an autoclave, for example.

In one embodiment of the present invention, the precursor copolymer is reacted in an organic solvent selected from alcohols, diols such as ethylene glycol, ethers, toluene, xylene, and dimethyl sulfoxide; Preference is given to Cr C 4 alkanols such as, for example, methanol, ethanol, n-propanol, and n-butanol, and particularly preferably isopropanol. The weight ratio of precursor copolymer to organic solvent can be 20: 1 to 1:20. The weight ratio of precursor copolymer to water can be 1: 1 to 1: 100. The reaction time for the partial hydrolysis can be, for example, 30 minutes to 30 hours. In one embodiment of the present invention, based on alkenylphosphonic ester (c) copolymerized in precursor copolymer, 0.1 equivalent to 100 equivalents, preferably 1 equivalent to 10 equivalents, of hydroxide, ammonia or organic amine are employed. In one embodiment of the present invention, the inorganic hydroxide simultaneously serves as a neutralizing agent. Without wanting to adhere to any particular theory, the authors are unable to rule out the formation, in those cases where ammonia or a primary amine is used in the hydrolysis, of compounds containing P-N bonds as intermediates. The present invention further provides the use of copolymer of the invention to treat surfaces. Additionally the present invention provides a method of coating surfaces using copolymer of the invention, also referred to below as the method of treatment of the invention. The method of treatment of the invention is carried out starting from one or more surfaces, which may be of any desired material. The preferred material comprises plastics, more preferably one-phase or multiple-phase polymer blends or compound formulations, in particular with design of thermoplastic fractions such as, for example, polyethylene, polypropylene, polystyrene, polyamides, polyacrylonitrile, PMMA, and metals, the term "metals" for the purpose of the present invention also comprises alloys. Particularly suitable alloys are those with predominantly iron, aluminum, nickel, chromium, copper, titanium, zinc, tin, magnesium and cobalt, a particularly suitable alloy being steel, such as chrome-nickel steel, stainless steel or otherwise steel galvanized, for example. The composite surfaces of one or more of the foregoing metals may be a coating covering completely or in part a surface of another metal, wood or plastic. The surfaces for the inventive treatment can take any desired form: they can be flat or curved, and can be interior or exterior surfaces of one or more articles. The surfaces for the inventive treatment can be smooth, and in particular they can have a smooth appearance to the naked human eye, or else they can be textured - for example, they can have elevations or depressions, in dot format or in the form of slots, for example. The method of treatment of the invention can be implemented for example in the following manner: In one embodiment of the present invention, a possible method is to moisten a metal surface or polymeric surface with a copolymer solution of the invention. For this purpose, a possible method, for example, is to dissolve or disperse or emulsify the copolymer of the invention in a liquid, such as in an organic solvent or in water, for example, and then contact it with the surface to be treated. In this embodiment, the subsequent drying of the inventively treated surface is omitted. In one embodiment, the surface to be treated is the interior surface of an installation that serves as a freezing circuit, in automobiles or power stations, for example. If it is desired to treat inventively surfaces of installations that serve as freezing circuits, then the copolymer of the invention can be dissolved, dispersed or emulsified in a liquid, which can serve both as a constituent of the freezer or freezers, salt, for example, and the solution, dispersion or emulsions can be fed into the freezing circuit. Suitable concentrations of copolymer of the invention in the overall liquid serving as a freezer are, for example, 0.05% to 30%, preferably 0.1 to 10% by weight. The copolymer of the invention can be fed once or continuously or periodically Where the surfaces of facilities serving as freezing circuits are treated inventively, an effect of corrosion inhibition is observed. In one embodiment of the present invention, the freezing circuits in question are constituents of refrigerators or freezers. In one embodiment of the present invention, a metal surface or plastic surface is wetted in the course of drilling, milling, rotating, cutting, abrading, threading or entangling and / or extracting with copolymer solution of the invention. In another embodiment of the present invention, a metal surface or polymer surface, which may be untreated or pretreated, is provided with an inventive copolymer layer. For this purpose, a possible method, for example, is to apply inventive copolymer in the form of a film to the surface to be treated., and then dry it. In the course of drying, the copolymer film of the invention can be cured. The inventively pretreated or untreated metallic or polymeric surfaces are preferably base metal surfaces, such as iron surfaces, steel, zinc or zinc alloys, aluminum or aluminum alloys, tin or tin alloys, magnesium or magnesium alloys, for example. The steels can be low alloy steels or high alloy steels.

The method of the invention is particularly suitable for passivating surfaces of zinc, zinc alloys, aluminum or aluminum alloys. These may be workpiece surfaces or elements composed entirely of the aforementioned metals and / or the alloy mentioned above. Alternatively, they can be surfaces of workpieces or elements coated with zinc, zinc alloys, aluminum or aluminum alloys, the elements or workpieces in question being composed of other materials, such as other metals, alloys, polymers or mixed bodies. , for example. The surface in question can be, in particular, that of steel or galvanized iron. The term "galvanized" also covers coating with a zinc alloy, especially hot dip galvanizing with ZnAl alloys and electrolytic galvanizing with ZnNi, ZnFe, ZnMn alloys and ZnCo alloys. Alloys of Zn or Al alloys are known to the person skilled in the art. Typical constituents of zinc alloys comprise, in particular, Al, Mg, Pb, Si, Mg, Sn, Cu or Cd. The alloys in question can also be Al / Zn alloys where Al and Zn are present in approximately amounts same. The coatings may be largely homogenous coatings or otherwise coatings exhibiting concentration gradients. By way of example, the substrate in question may comprise galvanized steel which has received an additional vapor coating with Mg. By this means, it is possible for a Zn / Mg alloy to be produced on the surface. Typical constituents of aluminum alloys comprise, in particular, Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti. In a preferred embodiment of the method of the invention, the surface in question is that of a coil metal, preferably of aluminum or aluminum alloys or iron or steel, especially coils of electrolytically galvanized steel or hot-dip galvanized. The surface is desired to be treated inventively with the copolymer of the invention, in particular a metal surface, first pretreated, for example, cleaned, in particular degreasing and / or de-oiling. In many embodiments, degreasing or de-oiling also comprises one or more preliminary cleaning steps. After carrying out the preliminary cleaning step, if appropriate, the contaminating grease or oil, which may have been formed, for example, in the form of spots or a layer of oil or grease, is removed in the step of actual cleaning by means of at least one cleaning bath, by immersion, for example, or by means of at least one cleaning agent for application to the surface to be cleaned, being possible to apply said agent by spraying, when pouring on the surface to be cleaned, or to run using, for example, a hose. The residues of the cleaning bath or cleaning agent can be removed later, with one or more successive rinsing baths, for example, and finally the surface is dried. Degreasing and de-oiling baths must be disposed of regular intervals For the arrangement, the grease or oil accumulated in the degreasing or de-oiling bath is separated from the aqueous phase in another operation. Due to the presence of surfactants in the degreasing or de-oiling bath, more chemicals (demulsifiers, breakers) are required as auxiliaries for the disposal. Details of the degreasing and de-oiling of metals and also of useful formulations and apparatus for the purposes are established for example under the keyword "Metals, Surface Treatment" in the Ullmann Encyclopedia of Industrial Chemistry, 6a. edition, 2000, Wiley-VCH-Verlag GmbH, Weinheim, Germany. In one embodiment, degreasing or de-oiling is carried out with an aqueous cleaning or degreasing bath, preferably in an alkaline cleaning bath or an alkaline degreasing bath comprising as surfactant one or more sulfated polyalkoxylated fatty alcohols or one or more phenols sulfated polyalkoxylates, having in each case, for example, a molecular weight Mn in the range of 800 to 3000 g / mol, in a concentration which can be, for example, in the range of 0.01% to 20%, preferably 0.02% to 10% , and more preferably at least 0.1% by weight. The alkaline cleaning or degreasing bath employed can have, for example, a pH in the range of 8 to 14, preferably at least 9, and more preferably 11 to 13. The cleaning and degreasing baths, especially cleaning baths or degreasing alkaline, can have a temperature in the scale from 10 to 80 ° C. Cleaning or degreasing or de-oiling can be carried out, for example, over a period in the range of 0.1 to 30 seconds. Following any pretreatment carried out, if appropriate, the copolymer of the invention is applied to the surface to be treated inventively. This can be done using common techniques. By way of example, it is possible to apply a formulation, selected from solutions, dispersions or emulsions of the copolymer of the invention, or a casting of the copolymer of the invention, but preferably a dispersion, to a surface that has been pretreated, if necessary. appropriate, and thus produce a layer of the copolymer of the invention. According to the invention, a non-uniform or, preferably, uniform layer thickness of the copolymer of the invention can be provided. In one embodiment of the present invention, the application can be carried out as a jet, aspersion, dip, knife coating, winding, brushing or electrophoretic coating. The layer thickness of the copolymer of the invention can be, for example, in the range of 10 nm to 100 μm, preferably 100 nm to 10 μm. The layer thickness of the copolymer of the invention can be influenced, for example, by the nature and amount of the components applied and also the exposure time. It is preferred to adjust the layer thickness of the copolymer of the invention by means of the concentration of the copolymer of the invention in the preferably aqueous formulation that is used to coat. Additionally it can be influenced by technical parameters, such as by eliminating over-applied formulation using sheets or rollers, for example. The layer thickness in the context of the present invention is measured after drying, and can be determined gravimetrically or by means of X-ray fluorescence (phosphorus). The copolymer of the invention for the purpose of coating is preferably applied as a formulation in a suitable solvent or a mixture of different solvents. Particular preference is given to using water as the sole solvent. More components of a mixture of different solvents comprise, in particular, miscible solvents in water. The following may be mentioned by way of example: monoalcohols such as methanol, ethanol or propanol, higher alcohols such as ethylene glycol or polyether polyols and ether alcohols such as n-butyl glycol or methoxypropanol. A preferred mixture of water with organic solvents comprises at least 75%, more preferably at least 85%, and most preferably at least 95% by weight of water. The figures refer in each case to the total amount of solvents used to prepare the formulation in question. The copolymer of the invention can be dissolved, emulsified or dispersed in solvent or solvent mixture. The method of the invention is preferably carried out using a dispersion of the copolymer of the invention, which is likewise provided by the present invention. The copolymer concentration of the invention can be, for example, 0.1 to 40%, preferably 1% to 30%, and more preferably 3% to 25% by weight. The aforementioned quantity figures refer to the sum of all the components of the formulation. The copolymer of the invention is preferably formulated in water as the sole solvent, and the concentration of the copolymer of the invention is preferably in the range of 0.5% to 40% by weight. It is also possible to use mixtures of two or more copolymers of the invention. As well as the aforementioned solvent and the inventive copolymer components, the formulation of the invention may further comprise additional components, which in the context of the present invention are also referred to as adjuvants. The adjuvants can be, for example, organic or inorganic acids which can serve as neutralizing agents or as a regulator. Other adjuvants optionally used comprise active surface (dispersants, emulsifiers, surfactants), corrosion inhibitors such as antioxidants, for example, hydrotropic agents, frost preventives, biocides, complexing agents, carriers, waxes, metal salts, bases, and other polymers other than the copolymer of the invention. An adjuvant may have more than only one function in said formulation. Active surface compounds to name by way of example include surfactants, emulsifiers and / or dispersants, which may be cationic, nonionic, zwitterionic or non-ionic Suitable surfactants are, for example, alkoxylates and alkenyl alkoxylates of the type R9-EOv / POw, wherein the radicals R9 are generally straight or branched C6-C30 alkyl or alkenyl radicals, preferably alkyl radicals of C8-C20, and EO is a unit of ethylene oxide and PO is a propylene oxide unit, it being possible for EO and PO to be arranged in any order, including randomly, and v and v may be identical or different or, preferably, different and they are preferably = 100, with the proviso that v and w are not simultaneously zero; preferably v or w is in the range of 3 to 50. Examples of commercially available nonionic surfactants are Emulan®, Lutensol® and Plurafac® from BASF Aktiengesellschaft. Other examples are alkylphenol ethoxylates, EO / PO block copolymers such as EO7PO8EO7, for example. Examples of suitable anionic surfactants are R EOvSO3Na and R9EOvSO3K. Examples of suitable cationic surfactants are alkylammonium salts, such as sulfates or halides of R9N (CH3) 3, known as quarts. Exemplary corrosion inhibitors include butynediol, benzotriazole, aldehydes, amine carboxylates, benzotriazoles, benzotriazole derivatives such as methylenebenzotriazole and 2-mercaptobenzotriazole, aminophenols and nitrophenols, amino alcohols such as, for example, triethanolamine, aminobenzimidazole , imidazolines, aminoimidazolinas, aminotriazol, benzimidazolaminas, benzotiazoles, boric esters with alkanolamines, such as diethanolamine ester boric acid, carboxylic acids and their esters, quinoline derivatives, dibenzyl sulfoxide, dicarboxylic acids and their esters, diisobutenylsuccinic acid, dithiophosphonic acid, fatty amines and fatty acid amides, guanidine and guanidine derivatives , urea and urea derivatives, laurylpyridinium chloride, maleamides, mercaptobenzimidazole, N-2-ethylhexyl-3-aminosulfopropionic acid, salts of phosphonium, phthalamides, monoesters and phosphoric diesters neutralized with amine and sodium of C 1 -C 20 alkyl alcohols and also the corresponding phosphoric esters themselves, phosphoric esters of polyalkoxylates and especially of polyethylene glycol, polyetheramines, sulfonium salts, sulphonic acids such as, for example, methanesulfonic acid, thioethers, thioureas, sulfides of thiuramide, cinnamic acid and their derivatives , zinc phosphates and zinc silicates, zirconium phosphates and zircon silicates io Corrosion inhibitors - if used in the compositions of the invention - are employed in an amount generally of 0.01 to 50 g / l, preferably 0.1 to 20 g / l, more preferably 1 to 10 g / l. Dispersants can be used in unstabilized form and stabilized with one or more thickeners. Examples of suitable thickeners include unmodified or modified polysaccharides of the xanthan, alginate, guar or cellulose type. Particularly suitable modified polysaccharides are methylcellulose and carboxymethylcellulose.

Hydrotropic agents that may be named by way of example include urea and sodium xylene sulfonate. Frost preventives to name by way of example include ethylene glycol, propylene glycol, diethylene glycol, glycerol and sorbitol. Exemplary biocides include 2-bromo-2-nitropropane-1,3-diol, glutaraldehyde, phenoxyethanol and phenoxypropanol, glyoxal, 2,4-dichlorobenzyl alcohol, chloroacetamide, formalin, 1,2-benzisothiazolin-3. -one, silver, and polyvinylpyrrolidone-iodine. Exemplary complexing agents include, for example, nitriloacetic acid, ethylenediaminetetraacetic acid, methyl glycine diacetic acid, diethylenepentaminepentaacetic acid, and also their respective salts, especially alkali metal salts. Suitable carriers are polycarboxylic acids, such as poly (meth) acrylic acid or polymaleic acid, if appropriate in partially or completely neutralized form, partially or completely hydrolyzed polyacrylonitrile, polyacrylamide, polyacrylamide copolymers, lignosulfonic acid and its salts, starch, derivatives starch (for example, oxidized starch), cellulose, d-C10 alkyl phosphonic acid >; and 1-aminoalkyl-1,1-diphosphonic acid. The metal salts to be mentioned by way of example include phosphates. These can be dissolved or particle phosphates. For example, they can be orthophosphates, hydrogen phosphates, phosphates of dihydrogen, or diphosphates (pyrophosphates). Examples of suitable phosphates include Zn3 (PO4) 2, Zn (H2PO), Mg3 (PO4) 2 or Ca (H2PO4) 2 and corresponding hydrates thereof. Acids to be named by way of example include phosphoric acid, phosphorous acids, methane phosphonic acid and phosphonic acid. Polymers other than the copolymer of the invention that may be named by way of example include polyacrylates, polyurethanes, and polyamides, each preferably in aqueous solution or in the form of an aqueous dispersion. In a particularly preferred embodiment, a formulation of the invention comprises at least one dispersed wax. The term "wax" is known to the person skilled in the art and is defined, for example, in Rompp Lexikon der Chemie, key "Paints and Printing Inks", Georg Thieme Verlag, Stuttgart, New York 1998, pp. 615/616 or Ullmann's Encyclopedia, 6th edition, code "Waxes: 1.2. Definition", and the term comprises substances of the fluorinated wax type such as those known as PTFE waxes, for example (see, for example, Roppp, op. cit., pages 466/467). Preferred waxes are oligomeric or polymeric substances having a molecular weight Mw of 1000 to 100 000 g / mol, more preferably 2000 to 30000 g / mol. In one embodiment of the present invention, preferred waxes have a weight fraction that adds at least 50% by weight of structural elements selected from the group that consists of (-CH2-CH2-), (-CH2-CH <), (-CH2-CH (CH3) -), (CH3), [C (R8) 2-C (R8) 2], and [ C (R8) 2-C (R8) (C (R8) 3)], it being possible for R8 to be identical or different, and R8 being H or F, and with the proviso that the aforementioned structural elements are joined together in such a way that they predominantly comprise units of at least 12 carbon atoms directly linked to each other. It will be appreciated that a mixture of different waxes can be used. The waxes may also have acidic functions, especially carboxylic acid groups, which may be in neutralized or unneutralized form. Waxes having an acid number = 200 mg KOH / g, determined in accordance with DIN 53402 are preferred. Particularly preferred waxes are those having an acid number on the scale of 10 to 190 mg KOH / g. Waxes having a melting point are preferred. Particular preference is given to waxes having a melting point of 40 to 150 ° C. Especially preferred are waxes having a melting point in the range of 50 to 120 ° C. Examples of waxes particularly suitable for carrying out the present invention include [CAS numbers in square brackets]: polyethylene wax [9002-88-4], paraffin wax [8002-74-2], montan wax and montan raffinates, for example [8002-53-7], polyethylene-polypropylene waxes, polybutene waxes, Fischer-Tropsch waxes, carnauba waxes, oxidized waxes, such as oxidized polyethylene wax corresponding to [68441-17-8], copolymer polyethylene waxes, examples being copolymers of ethylene with acrylic acid, methacrylic acid, maleic anhydride, vinyl acetate, vinyl alcohol, for example [38531-18-9], [104912-80-3], [219843-86-4] or copolymers of ethylene with two or more of the aforementioned monomers, waxes of polar modified polypropylene, for example [25722-45-6], microcrystalline waxes, examples being microcrystalline paraffin waxes [63231-60-7], montanic acids, for example [68476-03-9], metal salts of montanic acid, such as sodium salts [93334-05-5] and calcium salts [68308-22-5], esters of long chain carboxylic acids with long chain alcohols, one example being n-octadecyl stearate [2778-96-3] ], monastic esters of polyhydric alcohols, examples being glycerides of montan wax [ 98476-38-0], including those with partial hydrolysis, montanic esters of trimethylolpropane [73138-48-4], montanic esters of 1,3-butanediol [73138-44-0], including those with partial hydrolysis, montanic esters of ethylene glycol [73138-45-1], including those with partial hydrolysis, montan wax ethoxylates, for example [68476-04-0], fatty acid amides, examples being Erucamid [112-84-5], oleamide [301-02-0], and 1, 2-ethylenebi (stearamide) [110-30-5] long chain ethers, n-octadecyl phenyl ether, for example. Mixtures of waxes are additionally suitable, examples being • mixtures of n-octadecyl stearate and partly hydrolyzed montanic esters of polyhydric alcohols • mixtures of paraffin waxes and partly hydrolyzed montanic esters of polyhydric alcohols and / or montanic acids • mixtures of polyethylene wax and polyethylene glycol.

Particularly preferred waxes are those that can be incorporated with particular ease into a formulation of the invention, such as micronized waxes and / or wax dispersions, for example. Micronized waxes for the purpose of the present invention are particularly fine particle powders having an average particle diameter preferably less than 20 μm, more preferably 2 to 15 μm. Wax dispersions are aqueous preparations of waxes comprising water, optionally more miscible solvents in water, spherical wax particles, and, generally, one or more auxiliaries. Preferred wax dispersions for use in the context of the present invention have an average particle diameter of less than 1 μm, preferably 20 to 500 nm, more preferably 50 to 200 nm. The Micronized waxes and wax dispersions are commercially available. Auxiliaries are used in wax dispersions in order, for example, to ensure the dispersion ability of the wax and its stability in storage. The auxiliaries can be, for example, bases for complete or partial neutralization of acid functions in the wax, examples being alkali metal hydroxides, ammonia, amines or alkanolamines. The acid groups can also be completely or partially neutralized with cations, examples being Ca + + or Zn + +. More possible auxiliaries are active surface substances, preferably nonionic or anionic surfactants. Examples of nonionic surfactants include ethoxylates and propoxylates based on alcohols and hydroxyaromatics and also their sulfation and sulphonation products. Examples of anionic surfactants include alkylsulfonates, arylsulfonates and alkylarylsulfonates. Wax dispersions are particularly suitable for carrying out the present invention having a pH in the range of 8 to 11. According to the invention, wax is used in an amount from 0.01% to 60%, preferably 0.1% to 40%, more preferably 0.25% to 20%, most preferably 0.5% to 10%, and for example 1% to 5% by weight, based in each case on the formulation of the invention as an integer. In one embodiment of the invention, the formulations of the invention comprise in total in the range of 0.01 to 600 g / l, preferably 0.1 to 100 g / l, of adjuvant (s). The duration of the copolymer treatment of the invention can be on the scale of significantly less than one second up to a number of minutes: for example, on the scale from 0.1 second to 10 minutes. In the case of a continuous method, it has been found particularly appropriate to contact the surface under treatment with the copolymer of the invention for a duration of 1 to 60 seconds. In a specific embodiment of the present invention, the copolymer of the invention is formulated in a powder coating material and applied to the surface to be treated inventively in accordance with a powder coating process. In one version of the method of the invention, a metal surface or polymer surface, which may be unpretreated or pretreated, is provided with a copolymer layer of the invention and then with another coating material, such as a paint, in particular a powder coating material. In a specific version, a metal surface or plastic surface is first coated with copolymer of the invention and a powder coating is subsequently applied. If it is desired to perform the coating of the invention by immersion, then the coating occurs at a relevant dip bath temperature in the range of 15 to 90 ° C, preferably 25 to 80 ° C, and more preferably 30 to 60 ° C. For For this purpose, the immersion bath comprising the formulation comprising the copolymer of the invention can be heated. If desired, according to the invention for coating articles having a metal surface, a high temperature can also arise automatically by immersion of the hot metal in question in the immersion bath comprising the formulation comprising the copolymer of the invention. If it is desired to carry out the method of the invention by spraying, blasting, brushing, knife coating, winding or electrophoretic coating, then it is possible to operate preferably at a temperature in the range of 15 to 40 ° C, preferably 20 to 30 ° C. The method of the invention can be carried out in batch form or, preferably, continuously. A discontinuous method can be related, for example, to an immersion method for piece goods, where the piece goods can be suspended from the shelves or they can be present as a loose product inside perforated drums. A continuous method is especially suitable for treating coil metals. The coil metal in this case is passed through a tank or a spray apparatus with a formulation comprising the copolymer of the invention, and also, optionally, through pretreatment stations or after treatment. In one version of the method of the invention, the metal surface or polymer surface is treated in accordance with a continuous coil process. The actual application of the copolymer of the invention is followed by drying. Drying can occur at room temperature by simple evaporation in air at room temperature. Drying can also be assisted by means of suitable auxiliary means and / or auxiliary measures, such as by heating and / or passing gas jets, especially air jets, on the drying systems, in particular by means of drying a tunnel dryer. Drying can also be assisted by means of IR lamps. It has been found appropriate to carry out the drying at a temperature of 40 ° C to 160 ° C, preferably 50 ° C to 150 ° C, and more preferably 70 ° C to 130 ° C. The temperature referred to is that on the polymer or metal surface; It may be necessary to set a higher dryer temperature. The drying itself can be preceded by allowing the article with the surface coated with the copolymer of the invention to drip dry, in order to remove the excess formulation. When the article with surfaces coated with the polymer of the invention comprises metal foils or aluminum foil, the excess formulation can be removed when draining or cutting with foil, for example. It is possible to rinse the surface with a cleaning liquid, in particular with water, after the treatment of the invention but before drying, in order to remove excess residues of the formulation employed from the inventively treated surface. After drying occurs.

It is also possible to carry out drying in the manner of what is called a "do not rinse" operation. The formulation comprising the copolymer of the invention is dried immediately after its application, without previous rinsing, in a drying oven. Through the inventive treatment of surfaces with the copolymer of the invention, at least fractions of the copolymer of the invention, and also, if appropriate, more components of the formulation, are quimoabsorbed by the surface of the polymer or metal and / or react with the surface, so that a firm bond occurs between the surface and the copolymer of the invention. The coated surfaces according to the invention can be provided, in a manner that is known in principle, with one or more coating films applied on each. These can be, for example, color or effect coating films. Typical coating materials, their composition, and typical film sequences in the case of two or more coating films, they are known by themselves. The inventively applied coating is in many cases readily observed as overcoat with commercially common coating materials. In one embodiment of the present invention, the surface to be coated, which may or may not have been pretreated, is coated with what is called a base paint prior to the coating operation. Base paints to name by way of example include polyamines and polyethyleneimines. This is followed by coating with the copolymer of the invention, as described above. In this case, a layer thickness of the copolymer of the invention is preferably set on the scale of = 4 μm to 100 μm. After that, it is possible to provide one or more coating films. In another embodiment of the present invention, the copolymer of the invention is applied as a base paint, with a layer thickness, for example, in the range of 50 nm to 50 μm, preferably 100 nm to 10 μm, and with very particular preference of 300 nm to 3 μm. After that, it is possible to apply one or more coating films. In another embodiment of the present invention, the copolymer of the invention is applied as a coating material or constituent of a coating material, preferably to a non-pretreated metal surface. In this embodiment, a copolymer of the layer thickness of the invention in the range of 100 nm to 3 μm is preferred. The present invention further provides polymer surfaces or metal surfaces coated with the copolymer of the invention comprising as comonomers in copolymerized form: (a) ethylene, (b) one or more compounds of the general formula I, as defined above, ( c) one or more alkenyl phosphonic diesters, (d) if appropriate, one or more copolymerizable comonomers radically free. The present invention further provides articles having at least one surface in accordance with the invention. The surfaces of the invention and, consequently, articles with surfaces according to the invention, show particularly good corrosion protection, having, for example, improved oxidative corrosion stability with respect to solid, liquid and gaseous oxidizing media. The present invention further provides aqueous formulations, such as aqueous solutions, aqueous emulsions, and, in particular, aqueous dispersions, comprising 0.01% to 40% by weight of the copolymer of the invention comprising as comonomers in copolymerized form: (a) ethylene, ( b) one or more compounds of the general formula I, as defined above, (c) if appropriate, one or more alkenyl phosphonic diesters, (d) if appropriate, one or more other radically free copolymerizable comonomers. In one embodiment of the present invention, it is possible for aqueous formulations of the invention to comprise at least one adjuvant selected from dispersants, surfactants, corrosion inhibitors, antioxidants, biocides, waxes, complexing agents, salts, acids and bases metallic EJ EMPLOS I. Preparation of precursor copolymers 1.1 Preparation of precursor copolymer (A.1) to (A.5) and also (A.1 1) to (A.12) A high pressure autoclave as described in the literature (M Buback et al., Chem. Ing. Tech. 1994, 66, 51 0) was used to copolymerize ethylene, the amount of dimethyl vinylphosphonate 11. 1 ft ^^ P-OMe OMe Me = CH, specified in table 1, either in volume or as a solution in toluene (for concentration see table 1), and methacrylic acid (table 1). For this purpose, ethylene (10.0 or 12.0 kg / h) was continuously fed into the autoclave at high pressure under a pressure of 1700 bar. Dimethyl vinylphosphonate was continuously measured in the autoclave at high pressure using a high pressure pump under a pressure of 1700 bar. Separately, the amount of methacrylic acid specified in Table 1 was first compressed at an intermediate pressure of 260 bar, using a compressor, and then continuously fed into the autoclave at high pressure, using another compressor, under the reaction pressure from 1700 bar. Separately, the The amount of initiator solution specified in Table 1, consisting of ter-amyl peroxypivalate (in isododecane, for concentration see taota 1), was continuously fed into the autoclave at high pressure under the reaction pressure of 1700 bar. Separately, the amount of propionaldehyde specified in Table 1 (in volume or as a solution in isododecane); for concentration see table 1) it was first compressed at an intermediate pressure of 260 bar, using a compressor, and then continuously fed into the autoclave at high pressure, using another compressor, under the reaction pressure of 1700 bar. The reaction temperature was approximately 220 ° C. This gave precursor copolymer having the apparent analytical data from Table 2. Examples (A.11) and (A.12) were carried out using a tube reactor as described in EP 0 101 343 (length: 595 m, internal diameter: 15/21 mm) having a length / diameter ratio of approximately 35,000 and including three positions for the measured addition of ter-amyl peroxypivalate. The course of the reaction is characterized by the descending maximum temperatures of the positions at which ter-amyl peroxypivalate is measured. T11: 228/225/224 ° C, T12: 219/226/225 ° C. .2 Preparation of precursor copolymers (A.6) to (A.10) A high pressure autoclave as described in the literature (M. Buback et al., Chem. Ing. Tech. 1994, 66, 510) was used for copolymerize ethylene, the amount of dimethyl vinylphosphonate 11.1 ff ^^ P-OMe OMe Me = CH, specified in table 1, either in volume or as a solution in toluene (for concentration see table 1), and methacrylic acid (table 1). For this purpose, ethylene (10.0 or 12.0 kg / h) was continuously fed into the autoclave at high pressure under a pressure of 1700 bar. Dimethyl vinylphosphonate was continuously measured in the autoclave at high pressure using a high pressure pump under a pressure of 1700 bar. Separately, the amount of methacrylic acid specified in Table 1 was first compressed at an intermediate pressure of 260 bar, using a compressor, and then continuously fed into the autoclave at high pressure, using another compressor, under the reaction pressure of 1700 bar. Separately, the amount of initiator solution specified in Table 1, consisting of ter-amyl peroxipivalate (in isododecane, for concentration see Table 1), was continuously fed into the autoclave at high pressure under the reaction pressure of 1700 bar. Separately, the amount of propionaldehyde specified in Table 1 (in volume or as a solution in isododecane, for concentration see Table 1) was first compressed at an intermediate pressure of 260 bar, using a compressor, and then fed continuously in the autoclave at high pressure, using another compressor, under the reaction pressure of 1700 bar. The reaction temperature was approximately 220 ° C. This gave copolymer precursor to the apparent analytical data of Table 2.

Table 1 Preparation of precursor copolymer (A.1) - (A.12) 4w ractor is the maximum internal temperature of the autoclave at high pressure. Abbreviations: DVP :: dimethyl vinyl phosphate, ID: isodcdecano (2,2,4,6,6-pentamethylheptane), PO: ter-amyl peroxypivalate c (PO): concentration of PO in ID in mol l, c (PA ): concentration of PO in ID in% by weight, c (DVP): concentration of DVP in toluene in% by weight PCP: copolymer precursor, MAA: methacrylic acid Table 2 Analytical data of precursor copolymer (A.1) - (A.11) I heard or The MAA content was determined by measuring the acid number according to DIN 53402. The ethylene and DVP content was determined by 1 H NMR spectroscopy. The phosphorus content was further determined for (A.6) and (A.10) by means of elemental analysis: (A.6): P = 1.1 g / 100 g of precursor copolymer, corresponding to 4.8% by weight (1.3%) molar) DVP; (A.10): P = 4.9 g / 100 g of precursor copolymer, corresponding to 21.6% by weight (6.0 mole%) DVP. The density was determined in accordance with DIN 53479. The melting point or melting scale was determined by DSC (differential selection calorimetry) according to DIN 51007.

Preparation of copolymers of the invention 1 Preparation of the inventive copolymer CP-4.1 In a 2 liter round bottom flask 200 g of precursor copolymer (A.4) were heated under reflux with 550 g of isopropanol (initial charge 1). 200 g of initial charge 1 were stirred under reflux with 58.2 g of NaOH (approximately 2 equivalents, based on the methoxy groups of (A.4)) and 500 g of isopropanol. After one hour, plus 200 g and after another 2 hours, the remainder of the initial charge 1 was added. The formation of a solid polymer precipitate was observed. After 8 hours boiling at reflux, the mixture was cooled to room temperature, the solvent was decanted from the solid polymeric precipitate, and in a 2 liter round bottom flask this precipitate was absorbed in 1.4 liters of water at 95 ° to 98 ° C. ° C. The formation of an emulsion was observed. It was stirred at room temperature for 3 hours. The precipitation was carried out by adding 10% by weight hydrochloric acid (to adjust a pH of about 3). The precipitated material was washed with water, isolated by filtration, and dried at 130 ° C. This gave 175 g of inventive copolymer CP-4.1, which according to 1 H NMR still comprised 16 mol% of the methoxy groups originally present. 11. 2 Preparation of the inventive copolymer CP-4.2 In a 2 liter cylindrical pressure glass vessel, 100 g of precursor copolymer (A.4) was heated at 126 ° C over 2 hours (3.5 bar) with 1 liter of isopropanol and 29.1 g of NaOH (approximately 2 equivalents, based on the methoxy groups of (A.4)), and the mixture was stirred at about 1700 revolutions per minute at 126 ° C (3.5 bar) for about 2 hours. After about another hour, the temperature had dropped to 114 ° C and the pressure to 2.3 bar. The contents of the vessel were cooled to room temperature, left at atmospheric pressure, and the precipitated solid was absorbed in 1000 ml of water, to form an emulsion. The precipitation was carried out by adding 10% by weight hydrochloric acid (to adjust a pH of about 3). The precipitated material was washed with water, isolated by filtration, and dried at 130 ° C. This gave 75 g of inventive copolymer CP-4.2, which according to 1 H NMR still comprised 5 mol% of the methoxy groups originally present.

II.3 Preparation of the inventive copolymer CP-6 In a 2-liter round bottom flask, 147.2 g of precursor copolymer (A.6) were heated at 95 ° C for 30 minutes with 25.7 g of NaOH (added in the form of 10% by weight of sodium hydroxide solution watery) and a total of 563 g of water.

The contents of the flask were stirred at 95 ° C for an additional 3.5 hours and then cooled to room temperature. After just one hour of agitation, the formation of an opaque emulsion was observed. Upon cooling to room temperature, a milky emulsion formed. The milky emulsion thus obtained was diluted with water twice its volume and acidified to a pH of 1.5 using 10% by weight of hydrochloric acid, to which a white solid was agglomerated and precipitated. The precipitated solid was mechanically ground, washed four times with water, separated by decantation, and dried at 130 ° C. This yielded 130 g of inventive copolymer CP-6. The recording of a 1 H NMR spectrum revealed that approximately 30 mol% of the methoxy groups of the precursor copolymer (A.6) had been hydrolysed.

II.4 Preparation of the inventive copolymer CP-7 In the same manner as in Example II.3, 211.2 g of the precursor copolymer (A.7) were hydrolysed with 36.9 g of NaOH and a total of 805 ml of water. Precipitation with 10% by weight hydrochloric acid and further reactions gave 206 g of the inventive copolymer CP-7. The recording of a H NMR spectrum revealed that approximately 38 mol% of the methoxy groups of the precursor copolymer (A.7) had been hydrolyzed. 1. Preparation of the inventive copolymer CP-10.1 In the same manner as in Example II.3, 173.9 g of precursor copolymer (A.10) were hydrolysed with 34.2 g of NaOH and 750 ml of water. Only after 4.5 hours an emulsion was formed, whose viscosity was higher than that of the emulsions of examples II.3 and II.4. It was diluted with an additional 200 ml of water and stirred at 95 ° C for one hour. Precipitation with dilute HCl (in the same manner as in Example II.3) and drying at 130 ° C gave 165 g of the inventive copolymer CP-10.1.

II.6 Preparation of the inventive copolymer CP-6.3 200 g of the precursor copolymer (A.6) were stirred for a total of 3.5 hours with 35.8 g of 25% by weight of aqueous ammonia solution and 764 ml of water at 95 ° C, forming an emulsion. The emulsion thus obtained was filtered to remove small amounts of residue. This gave approximately 20% by weight of emulsion of the inventive copolymer CP-6.3, for which a sample of 1H NMR was precipitated with dilute hydrochloric acid and developed in the same manner as in the preceding examples which revealed that approximately 8 mol% of the methoxy groups of the precursor copolymer (A.6) had been hydrolyzed. 11. 7 Preparation of the inventive copolymer CP-7.2 200 g of the precursor copolymer (A.7) were stirred for a total of 5 hours with 35.8 g of 25% by weight of aqueous ammonia solution and 764 ml of water at 95 ° C, forming an emulsion. The emulsion thus obtained was filtered to remove small amounts of residue. This gave about 20% by weight of emulsion of the inventive copolymer CP-7.2, for which a sample of 1H NMR was precipitated with dilute hydrochloric acid and developed in the same manner as in the preceding examples which revealed that approximately 8 mol% of the methoxy groups of the precursor copolymer (A.7) had been hydrolyzed. .8 Preparation of the inventive copolymer CP-10.2 200 g of the precursor copolymer (A.10) were stirred for a total of 4 hours in a 2 liter round bottom flask with 40.5 g of 25% by weight of aqueous ammonia solution and 1093 ml of water at 95 ° C, forming an emulsion. The emulsion thus obtained was filtered to remove small amounts of residue. This gave approximately 15% by weight of emulsion of the inventive copolymer CP-10.2, for which a sample of 1H NMR was precipitated with dilute hydrochloric acid and developed in the same manner as in the preceding examples which revealed that approximately 13 mol% of the methoxy groups of the precursor copolymer (A.10) had been hydrolyzed.

In another experiment, it was found that a corresponding 20% by weight of aqueous emulsion of the inventive copolymer CP-10.2 was made as a gel upon cooling to room temperature.

III. Surface treatment, general experimental description The inventive and comparative examples were carried out using test panels of Al 99.9 metal, CuZn 37, Zn 99.8, galvanized steel (20 μm zinc finish on one side) or steel of construction grade St 1.0037. In each case, an aqueous solution of 5% by weight of the respective copolymer of the invention was used. The aqueous solution of the respective copolymer of the invention was homogenized and charged to an immersion bath. The previously cleaned metal test panels were submerged for the aforementioned time and then dried to constant weight at 80 ° C. Finally, the edges of the coated panels were covered in order to rule out edge effects in the evaluation context. The thickness of the passivation layer was determined by differential weight before and after exposure to the metal surface to the inventively used composition and on the assumption that the layer has a density of 1 kg / l. "Layer thickness" below always refers to a parameter determined in this way, irrespective of the actual density of the layer. The effect of corrosion inhibition was determined by means of a salt spray test in a salt spray fog atmosphere in accordance with DIN 5002. The corrosion test resistance time is defined differently depending on the nature of the corrosion damage. Where white spots with a diameter of generally more than 1 mm (Zn oxide or Al oxide, referred to as white oxidation) were formed, the resistance time recorded was the time after the apparent damage corresponds to the rating 8 in DIN EN ISO 10289 of April 2001, Annex B, page 19. In the examples below, the following metal panel pretreatments were selected if appropriate in order to ensure a chromium free surface.

III.1 Pretreatment of metal test panels, general instructions The metal test panels were pretreated in accordance with ISO 8407 for the specific material, the pretreatment being given here explicitly for St 1.0037.

III.1.1 Degreasing and de-oiling at acid pH Electrolytically galvanized non-passivated metal test panels measuring 50 mm • 20 mm • 1 mm were immersed in an aqueous cleaning solution of 0.5% by weight of HCI and 0.1% by weight of ethoxylated saturated C13 oxo process alcohol with an average of 9 equivalents of ethylene oxide, then immediately rinsed with completely demineralized water, and then dried by blowing with nitrogen.

III.1.2 Degreasing at alkaline pH Preparation of an alkaline degreasing bath: In a plastic tray with two flat electrodes (stainless steel or graphite) having a larger surface area than the metal test panel in question, a solution of a degreasing bath was used, with the following composition: g NaOH 22 g Na2CO3 16 g Na3PO4 12 H2O 1 g EDTA-Na4 0.5 g ethoxylated saturated C13 oxo process alcohol with an average of 9 equivalents of ethylene oxide [C13 (EO) 9] 940 ml distilled water.

The alkaline degreasing bath was prepared by dissolving NaOH, Na2CO3 and NaPO4 in distilled water in succession and with agitation. In parallel with this, [C? 3 (EO9] and EDTA-Na were dissolved separately in distilled water, at a temperature of 50 ° C in the case of the EDTA-Na solution. Aqueous solutions of [C13 (EO) 9] and EDTA-Na4 were subsequently added to the solution of NaOH-Na2CO3-Na3PO4 in a graduated cylinder, cooled to room temperature, and constituted with up to 1000 ml with distilled water.

Procedure for degreasing at alkaline pH: A metal test panel measuring 50 mm • 20 mm • 1 mm was cleaned with a paper towel and immersed in the alkaline degreasing bath between the electrodes, at 10 volts, and connected as the cathode. The voltage was adjusted so that the current resistance was 1 A. After ten seconds, the metal test panel was removed from the alkaline degreasing bath and rinsed for five seconds under running water, completely demineralized.

III.2 Test instructions, general procedure First, the metal test panel in question was pretreated in each case in accordance with (Cu test panels) or III.1.2 (steel test panels). Then, the metal test panel was dipped in each case in a test solution at room temperature for 1 to 30 seconds, after which it was dried to constant weight at 80 ° C and The increase in mass per unit area was determined gravimetrically by means of differential weight. The recorded value was the average of individual measurements for 3 different test panels. The test panels were prepared and cleaned in accordance with ISO 8407 according to the specific material, and this preparation or cleaning is stated here explicitly for St 1.0037.

III.2.1 Coating of (CP-7) in St 1.0037 The metal test panels were immersed once for 10 seconds at room temperature in a 5% by weight solution of (CP-7).

Thickness of layer: 3μm.

The coated test panel showed no change in terms of color or metallic luster compared to the untreated test panel. Residence time to a rating of 8 in 5% mist atmosphere of salt spray at 30 ° C: 10 hours.

II.2.2 Coating of (CP-4.2) in St 1.0037 The metal test panels were submerged once for 10 seconds in an ethanolic solution of 5% by weight of (CP-4.2).

Layer thickness: 4 μm.

The coated test panel showed no change in terms of color or metallic luster compared to the untreated test panel. Residence time to a rating of 8 in 5% mist atmosphere of salt spray at 30 ° C: 15 hours.

III.2.3 Coating of (CP-6.3) in St 1.0037 The metal test panels were immersed once for 10 seconds in an aqueous solution of 5% by weight of (CP-4.2). Layer thickness: 2.9 μm. The coated test panel showed no change in terms of color or metallic luster compared to the untreated test panel. Residence time to a rating of 8 in 5% mist atmosphere of salt spray at 30 ° C: 10 hours.

Common example C 1"Blank" metal panel without coating The residence time at a rating of 8 in 5% mist atmosphere of salt spray at 30 ° C: less than 1 hour.

Comparative example C2: passivation layer with H3PO4 (phosphatizing agent) The metal test panels were immersed once for 10 seconds in aqueous 0.1% or 0.5% or 1% by weight of phosphoric acid. Residence time to a rating of 8 in 5% mist atmosphere of salt spray at 30 ° C: less than 2 hours in each case.

Claims (6)

1. - A copolymer comprising as comonomers in copolymerized form: (a) ethylene, (b) one or more compounds of the general formula I (c) if appropriate, one or more alkenyl phosphonic diesters, (d) if appropriate, one or more other radically free copolymerizable comonomers, whose variables are defined as follows: R1 is selected from hydrogen and an unbranched and branched C1-C10 alkyl, R2 is selected from hydrogen and an unbranched and branched C 1 -C 4 alkyl), R 3 is selected from hydrogen, phenyl, benzyl and unbranched and branched C 1 -C 0 alkyl, and unbranched and branched C 2 -C 6 hydroxy-alkyl, as free or partially or completely neutralized acid with alkali metal, alkaline earth metal, ammonia or organic amine.

2. The copolymer according to claim 1, which has an average molecular weight Mw on the scale of 1000 to 500 000 g / mol.

3. The copolymer according to any of claims 1 and 2, wherein the alkenyl phosphonic diester (c) is a compound of the general formula II whose variables are defined as follows: R4 is selected from hydrogen and unbranched and branched C1-C10 alkyl, R5 is selected from hydrogen and unbranched and branched CT-CKJ alkyl, R6 is identical or different in each occurrence and is selected from phenyl, benzyl and unbranched and branched CÍ-CIO alkyl, it being possible for the R6 radicals to join together to form a ring of five or ten members. 4 - The copolymer according to any of claims 1 to 3, wherein R1 and R4, R2 and Rs, in each case in pairs, are identical. 5. The copolymer according to any of claims 1 to 4, wherein R1 and R2 are each hydrogen and R3 and R6 are each identical and are selected from alkyl of C? -C

4. 6. The copolymer according to any of claims 1 to 5, wherein other radically free copolymerizable comonomers (d) are selected from (meth) acrylic acid, C 1 -C 10 alkyl esters of (meth) acrylic acid , vinyl format, C 1 -C 10 alkylcarboxylic acid vinyl esters, ethylenically unsaturated C 4 -C 10 dicarboxylic acids and their anhydrides, C 1 -C 20 alkyl vinyl ethers, C 1 -C 2 allyl alkyl ethers and α-olefins having 3 to 40 carbon atoms. 7. A process for preparing a copolymer according to any of claims 1 to 6, comprising subjecting (a) ethylene, (c) if appropriate, one or more alkenyl phosphonic diesters, (d) if appropriate, one or more radically free copolymerizable comonomers to copolymerization with each other at 500 to 4000 bar and reaction temperatures in the range of 150 to 300 ° C and subsequently to at least partial hydrolysis. 8. The use of a copolymer according to any of claims 1 to 6, for treating surfaces. 9. A method of treating surfaces using the copolymers according to any of claims 1 to 6. 10. The method according to claim 9, wherein a metal surface or polymer surface, which can is not pretreated or pretreated, it is provided with a copolymer layer according to any of claims 1 to

5. 11 - The method according to any of claims 9 and 10, wherein a metal surface or polymer surface is moisten with a copolymer solution according to any of claims 1 to

6. 12. The method according to any of claims 9 to 11, wherein a metal surface or polymer surface is treated by a coil process. continuous. 13. The method according to any of claims 9 to 12, wherein a metal surface or polymer surface, which may be pre-treated or pre-treated, it is provided with a copolymer layer according to any of claims 1 to 5 and then with another coating material. 14. A polymer surface or metal surface coated with at least one copolymer according to any of claims 1 to 6. 15. An article having at least one surface according to claim 14. 16.- An aqueous formulation comprising 0.01% to 40% by weight of the copolymer according to any of claims 1 to 6. 17 - The aqueous formulation according to claim 16, comprising at least one adjuvant selected from dispersants, surfactants, corrosion inhibitors, antioxidants, biocides, waxes, complexing agents, metal salts, acids and bases.