FR2868423A1 - POLYMERIZABLE PHOSPHONIC AMINOALKYLENE COMPOUNDS AND COPOLYMERS OF AT LEAST ONE COMPOUND WITH AT LEAST ONE ETHYLENE-UNSATURATED COMONOMER, AND THE USE OF SUCH COPOLYMERS - Google Patents

Abstract

The invention relates to polymerizable aminoalkylene phosphonic compounds and the copolymers obtained by polymerizing at least one of said compounds with at least one ethylenically unsaturated comonomer. The invention also relates to the use of the copolymers obtained as anticorrosive agents, adhesion promoters on metal supports or flame retardants in many fields of application such as, for example, the field of metals, plastics.

Description

POLYMERIZABLE PHOSPHONIC AMINOALKYLENE COMPOUNDS AND

  COPOLYMERS OF AT LEAST ONE OF SAID COMPOUNDS WITH AT LEAST ONE ETHYLENE UNSATURATED COMONOMER, AND USE OF SUCH COPOLYMERS.

  The invention relates to novel unsaturated aminoalkylene phosphonic compounds (I) capable of polymerizing and copolymerizing, as well as the copolymers obtained by polymerizing at least one of said compounds (I) with at least one ethylenically unsaturated comonomer.

  The invention also relates to the use of the copolymers resulting from the polymerization of unsaturated aminoalkylene phosphonic compounds (I) with at least one ethylenically unsaturated comonomer, as anticorrosive agents, adhesion promoters or flameproofing agents according to the intended application. .

  It is known to use polymers resulting from the polymerization of polymerizable compounds comprising phosphorus for their anticorrosive properties and / or for their adhesion properties, for example in the field of metals. Indeed, the use of such phosphorus products has proved particularly interesting in the field of metal surface coating formulations because of their adhesion and anticorrosion properties.

  Moreover, various polymers derived from polymerizable compounds containing phosphorus have been used as flame retardants for example in plastic formulations. Indeed, it seems that in the presence of flames the phosphorus products act by forming, for example, phosphoric and polyphosphoric acids of low volatility which catalyze the decomposition of organic compounds into coal and water.

  Polymers resulting from the polymerization of polymerizable compounds phosphorus by the presence of phosphorus atoms covalently bonded to the polymer chain have been found to be effective flame retardants resulting in an improvement of the mechanical and physical properties of fireproof plastics containing them, including with respect to flame retardants usually used such as mineral additives such as Mg (OH) 2 and Al (OH) 3 physically mixed with plastics for the purpose of fireproofing but whose use has many drawbacks as per examples of compatibility problems between the mineral additive and the polymer to which it must be mixed, modifications of the mechanical and physical properties of the polymers due to physical mixing with this type of additive, phenomena of color change, migration (effect "blooming") that may hinder the use of this type e additives for coating type applications.

  A great deal of research has therefore been undertaken on the synthesis of polymerizable monomers carrying a phosphorus group.

  Thus, phosphorus-containing monomers have been described for use as flame retardants, such as, for example, bis (2-chloroethyl) vinyl phosphonate, in "Stauffer Chemicals" [Kabachnick M.I., Izv. Akab Nauk. Otd. Khim., 2, 233 (1947)].

  The publication of Boutevin et al., Published in "Polymer Bulletin 30", pages 243-248 (1993) describes the preparation of phosphonated (meth) acrylate according to a three-step process whose first step leads to the synthesis of a dialkyl allylphosphonate which after two successive reactions with mercaptoethanol and then with (meth) acryloyl chloride leads to the phosphonated (meth) acrylate.

  The subject of the present invention is novel unsaturated aminoalkylene phosphonic compounds (I) capable of polymerizing and copolymerizing, corresponding to the following general formula: ## STR2 ## in which: R1 represents a hydrogen atom or a methyl group, the R, which are identical to or different from each other, may be chosen from: * a hydrogen atom, * a linear or branched alkyl group containing from 1 to 22 carbon atoms, * an aryl group, and a phenyl group, the R ', which may be identical or different, may be chosen from: * a hydrogen atom, and * a linear or branched alkyl group containing from 1 to 8 carbon atoms, A represents a NN group or a group -NR2- in CII 0 which R2 represents a hydrogen atom, a linear or branched alkyl group having 1 to 22 carbon atoms, an aryl group, a phenyl group or a group C (R) 2 PO (OR ') 2 in which the R and R' have the significati Y is -C (O) O-, -OC (O) -, C (O) NHC (O) O- or benzyl, Z is selected from: * a linear or branched alkyl group having 1 to 22 carbon atoms, a CH 2 CH (OH) CH 2 OCH 2 CH 2 group, a CH 2 CH (OH) CH 2 OC (O) CH 2 group, a CH 2 CH 2 SC 3 H 6 group, a CH 2 CH (OH) CH 2 O CH 2 CH 2 SC 3 H 6 group, and a CH 2 CH (OH) CH 2 OC group. 0) CH2SC3H6, * CH2CH2NHC (O) OCH2CH2, * C (CH3) (CH3) NHC (O) OCH2CH2, * (CH2) tOC (O) (CH2) t, wherein t and t ' Are an integer from 1 to 12; and the group: CH (X) wherein X is selected from the group consisting of linear or branched alkyl having 1 to 22 carbon atoms, phenyl, a group ( CH 2) 2SCH 3, a group (CH 2) 4 N (R 2) 2 r and a group corresponding to the formula or formula in which the R 2 have the abovementioned meaning, excluding the compounds (I) for which: R 1 represents a hydrogen atom or a methyl, - the R, identi the same or different R 'are alkyl groups of 1 to 8 carbon atoms, Y is a group -C (O) O- or, and - A represents a group -NR2- in which R2 is either a hydrogen atom or a tert-alkyl group having from 4 to 22 carbon atoms.

  The compounds (I) of the invention as defined above have the advantage of being particularly stable. Indeed, the compounds (I) of the invention contain a carbon-phosphorus bond (CP bond) which is stable to hydrolysis, unlike the usual phosphate monomers in which the phosphorus atom is bonded to four oxygen atoms forming a COP bond which is particularly sensitive to hydrolysis. Furthermore, the compounds (I) of the invention do not contain any phosphate group, groups that are at the root of many disturbances of the ecosystem, including water eutrophication.

  Thus, the copolymers of the invention resulting from the polymerization of compounds (I) of the following formula:

H R Z H>

  YZAC (R) 2-PO (OR ') 2 in which R 1 R, R', Y, Z and A have the meanings previously specified in the description, with at least one ethylenically unsaturated comonomer, have proved particularly effective as anticorrosive agents, adhesion promoters on metal or as flame retardants according to the intended application. Therefore, the subject of the invention is also the copolymers resulting from the polymerization of at least one of the compounds (I) with at least one ethylenically unsaturated comonomer.

  The invention finally relates to the use of the aforementioned copolymers as anticorrosive agents, adhesion promoters on metal or as flame retardants in many fields of application such as the field of metals, plastics.

  The preparation of the compounds (I) according to the invention can be carried out according to two different preparation methods.

  For example, the compounds (I) of the invention may be synthesized according to a preparation process consisting of the chemical conversion of an ethylenically unsaturated monomer comprising an amine function to an unsaturated monomer comprising at least one phosphonated function.

  According to this method of preparation, the compounds (I) of the invention of formula as defined above for which R, R ', A have the aforementioned meanings and R1 is a methyl, Y is a group C (O) O and Z is a CH2CH2, are obtained by reaction of a monomer (II) corresponding to the following formula:

H R 1

  Wherein R 1 represents a methyl, A represents a group NN or a group -NR 2 - in CII 0 where R 2 represents a hydrogen atom, a linear or branched alkyl group comprising 1 to 22 carbon atoms, an aryl group, a phenyl group or a C (R) 2 PO (OR ') 2 group in which the R and R' have the abovementioned meanings, with paraformaldehyde of formula (CH 2 O),, followed by a reaction with a dialkyl (III) hydrogenophosphonate corresponding to the following formula: in which the R ', which are identical, are chosen from a hydrogen atom and a linear or branched alkyl group containing from 1 to 8 carbon atoms; carbon.

  This process for the preparation of the compounds (I) defined above consists of a chemical reaction of the Kabashnick-Field type which takes place under standard operating conditions of the Kabashnick-Field type reactions with a temperature of the order of 25 to 100 C. preferably between 50 and 80 ° C.

  The molar ratio of monomer (II) / paraformaldehyde is between 0.5 and 2, preferably between 0.8 and 1.2. Similarly, the molar ratio of monomer (II) / dialkyl hydrogenphosphonate (III) is between 0.5 and 2, preferably between 0.8 and 1.2.

  For example, the compounds (I) of the invention for which R 1, Y, Z, R and R 'have the meanings defined above and for which A represents a group -NR 2 - in which R 2 represents a hydrogen atom, a group linear or branched alkyl comprising from 1 to 22 carbon atoms, an aryl group, a phenyl group or a C (R) 2 PO (OR ') 2 group in which the R and R' have the meanings mentioned above, are preferably prepared according to a preparation process consisting of the reaction between an ethylenically unsaturated functional monomer (IV) and a phosphonated tertiary amine V) According to this preparation method, the compounds (I) of the invention as defined above in which A represents a group -NR2- where R2 has the abovementioned meanings are obtained by reaction between a functional monomer (IV) of the following formula: H \ \ R1 (IV)

HEY

  in which: R1 represents a hydrogen atom or a methyl, and - E is chosen from: * a -C (O) O-CnH2n + 1 group with n ranging from 1 to 8, a -C (0) group; ), A -C (O) NCO group, a -C (O) O group, a -C (O) O-C 2 H 4 -NCO group, a -CO-OCH 2 -CH-CH 2 group, a -C (O) O- (CH 2) t-OH group with t between 1 and 4, a - (O) C (O) - CH 3 r group and a phosphonated tertiary amine (V) of the following formula: Wherein R 2 are the same or different from each other and may be chosen from: a hydrogen atom, a linear or branched alkyl group having from 1 to 22; carbon atoms, an aryl group, and a phenyl group; the R ', which are similar to or different from one another, may be chosen from: * a hydrogen atom, and * a linear or branched alkyl group containing from 1 to 8 carbon atoms, R2 represents a hydrogen atom, an alkyl group linear or branched chain comprising from 1 to 22 carbon atoms, an aryl group, a phenyl group or a C (R) 2 PO (OR ') 2 group in which the R and R' have the abovementioned meanings; G is selected from: an HO (CH 2) n group with n between 1 and 16, an HO 2 C (CH 2) n group with n between 1 and 16, an HOCH 2 CH 2 SC 3 H 6 group, a HO 2 CCH 2 SC 3 H 6 group, and group: HO2CC (X) H wherein X is selected from the group consisting of a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a phenyl group, a (CH 2) 2SCH 3 group, a group (CH 2) 4 N (R 2) 2 in which R 2 has the abovementioned meaning, and a group corresponding to the formula CH 2 R 2 or to the formula / R 2 in which the R 2 are as defined above.

  The ethylenically unsaturated functional monomer (IV) may be, for example, (meth) acrylic acid, (meth) acryloyl chloride, chloromethylstyrene, hydroxyalkyl (meth) acrylate, 3-isopropenyl dimethylbenzyl isocyanate or 2-isocyanatoethylmethacrylate. or else glycidyl (meth) acrylate.

  In addition, the tertiary phosphonated amine (V) as defined above can be obtained according to the method of preparation 5 described below.

  In fact, according to the Kabachnik-Fields reaction, the tertiary phosphonated amine (V) can be obtained by reaction between an alkyl hydrogenphosphonate (VI) corresponding to the following formula:

GOLD

  I (VI) HP = 0 OR 'in which: - R and R' identical may be chosen from the group consisting of a hydrogen atom and a linear or branched alkyl group having 1 to 22 carbon atoms, with the para formaldehyde (CH2O) n and an amine (VII) having the following formula: ## STR2 ## wherein: G 'is selected from: * HO (CH2) n with n between 1 and 16 a group HO2C (CH2) n with n between 1 and 16, a group HOCH2CH2SC3H6, a group HO2CCH2SC3H6i * and the group: HO2CC (X) H wherein X is selected from the group consisting of hydrogen, a linear or branched alkyl group having from 1 to 5 carbon atoms, a phenyl group, the - (CH2) 2 -S-CH3r the (CH2) 4N (R2) 2 in which R2 represents a hydrogen atom , a linear or branched alkyl group having from 1 to 22 carbon atoms, an aryl group, a phenyl group or a group C (R) 2 PO (OR ') 2 in which the R and R' have the the above-mentioned meanings, and a group corresponding to the formula: R2 in which the R2s have the abovementioned meanings, and R3 represents a hydrogen atom or a linear or branched alkyl group containing from 1 to 18 carbon atoms.

  As preferred compounds (I) of the invention, there may be mentioned for example the compounds (I) for which R 1 is a methyl, R is a hydrogen atom, R 'is a hydrogen atom or a linear alkyl or branched having from 1 to 3 carbon atoms, preferably methyl, ethyl or isopropyl, Y is -C (O) O-, Z is CH2CH2, A is -NR2 wherein R2 is a group C (R) 2 P (O) (OR ') 2 where R is hydrogen and R' is a hydrogen atom or a linear or branched alkyl having 1 to 3 carbon atoms, preferably a methyl, an ethyl or an isopropyl, which correspond to the following formula: ## STR1 ## Similarly, mention may be made of the compounds (I) for which R 1 is a methyl, R is a hydrogen atom, R 'is a hydrogen atom or a linear or branched alkyl having 1 to 3 carbon atoms, preferably a methyl, an ethyl or an isopropyl, Y is a groupbenzyl, Z is C (CH3) 2NHC (O) OCH2CH2r A is -NR2 where R2 is / R2 N CH2 N R2 or the formula is C (R) 2P (O) (OR Where R and R 'have the meaning specified above, compounds (I) having the following formula: CH 2 P (O) (OR') 2 / NCO CH 2 CH 2 -N HO \ CH 2 P (O) ( As compounds (I) of the invention, there may also be mentioned in particular compounds (I) for which R 1 is a methyl, Y is a group C (O) O-n Z is a CH 2 CH 2 group, A is a group NNCII O 15, R is a hydrogen atom and R 'is a hydrogen atom or a linear alkyl having from 1 to 3 carbon atoms, preferably a methyl, an ethyl or an isopropyl compounds (I) of the following formula: ## STR2 ##

O

  The novel compounds (I) of the invention, which are polymerizable monomers bearing at least one phosphonated group, are used as starting material in the preparation of the copolymers according to the invention which result from the polymerization of compounds (I) with at least one ethylenically unsaturated comonomer.

  According to the invention, said copolymers result from the polymerization of from 0.5% to 50% by weight, preferably from 1 to 10% by weight, of at least one compound (I) of the invention as defined previously with 50% to 99.5% by weight, preferably 90% to 99% by weight, of at least one ethylenically unsaturated comonomer.

  Suitable comonomers may be selected from the group consisting of the family of acrylic and methacrylic acids and esters. Preferably, the comonomer of the family of acrylic and methacrylic acids and esters may be chosen from the group consisting of acrylic acid, methacrylic acid, methyl acrylate and ethyl acrylate. butyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate.

  The ethylenically unsaturated comonomers may also be selected from crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, diethyl maleate, acrylonitrile and the like. methacrylonitrile.

  The ethylenically unsaturated comonomers may also be chosen from the group consisting of the family of vinyl esters such as, for example, vinyl acetate, vinyl propionate, vinyl butyrate, by the family of alkyl vinyl ethers, for example methyl vinyl ether, ethyl vinyl ether, isobutylvinyl ether, olefins such as ethylene, propylene, and the diene family such as butadiene, isoprene, chloroprene, and styrene and its derivatives such as methylstyrene, chloromethylstyrene.

  The aforementioned comonomers can be used alone or in admixture. Thus, one or more comonomers can be used simultaneously.

  The copolymers according to the invention may be prepared by bulk polymerization, in solution, in suspension or in emulsion. Preferably, the copolymers according to the invention are prepared by solution polymerization.

  The copolymerization is generally carried out in the presence of polymerization initiators such as, for example, in the presence of peroxides, hydroperoxides, persulfates, diazo compounds or redox catalysts.

  Suitable polymerization solvents are aqueous and / or organic media well known to those skilled in the art. The polymerization temperatures are of the order of 20 C to 140 C, preferably 40 to 90 C.

  As mentioned above, the copolymers of the invention can be used in many fields of application. Thus, the copolymers according to the invention are preferably used as anticorrosive agents for example in the field of metals (in particular the protection of metals), as adhesion promoters for example in the latexes to which they confer particularly advantageous adhesion properties when they are intended for solid supports such as for example metals and glass, and as flame retardants for example in plastics. The copolymers of the invention in phosphonic acid form, that is to say having two functions P (O) (OH) 2r are used as anticorrosive agents and / or adhesion promoters on metals for applications in the field of metals.

  The copolymers of the invention in the phosphonic ester form, that is to say having a P (O) (OR ') 2 function with R' representing an alkyl, are especially used as flameproofing agents for materials such as, for example, plastics. .

  Moreover, the copolymers of the invention carrying two phosphonated functional groups, that is to say two P (O) (OH) 2 groups or two P (O) (OR ') 2 groups in which R' is alkyl , have in their application fireproofing properties or adhesion properties and / or anticorrosion higher than copolymers carrying a single phosphonated function.

  The examples below are given for illustrative purposes only and therefore have no limiting character of the present invention.

  Preparation of compounds (I) of the invention 1. Synthesis of tetraethyl [N, 2-hydroxyethyl] dimethylene diphosphonate.

  In a two-necked flask equipped with a condenser and a dropping funnel, 8.6 g (0.1408 mol) of ethanolamine, 8.42 g (0.283 mol) of paraformaldehyde, 100 ml of methanol are introduced. The reaction mixture is mechanically stirred at 65 ° C. for one hour.

  Then, 31 g of dimethyl hydrogen phosphonate (0.2805 mol) are added slowly through the dropping funnel.

  The reaction mixture is maintained at 65 ° C. for 6 hours.

  At the end of the reaction, the excess paraformaldehyde is filtered and the crude reaction product is distilled under water (20 mmHg) to remove the reaction solvent.

  Tetraethyl [N, 2-hydroxyethyl] dimethylene diphosphonate is obtained in a yield of 80 and has the following characteristics: 31 P NMR (CDCl3): 8: 29 ppm (s, 1 P).

  1H NMR (CDCl3): δ: 2.9 ppm (t, 3H, HOCH2CH2N); 3.3 ppm (d, 4H, NCH 2 P (O) (OCH 3) 2); 3.7 ppm (t, 2H, HOCH2CH2N); 3.8 ppm (d, 12H, CH 2 P (O) (OCH 3) 2). 2- Synthesis of tetraethyl N, ethyldimethylene diphosphonate methacrylate.

  In a two-necked flask equipped with a condenser and a dropping funnel, 3 g (ie 0.0108 mol.) Of tetraethyl (N, 2-hydroxyethyl) dimethylene diphosphonate, 1.5 g (0.0150 g) are introduced. mol.) of triethylamine, 0.05 g of hydroquinone and 40 ml of perfectly anhydrous DMF.

  1.25 g (0.0120 mol) of methacryloyl chloride are introduced dropwise through the dropping funnel. After the addition is complete, the reaction is allowed to proceed at room temperature for 12 hours.

  At the end of this addition, the reaction solvent is evaporated off under reduced pressure.

  Tetraethyl N, ethyldimethylene diphosphonate methacrylate is obtained in a yield of 80 and has the following characteristics: 31 P NMR (CDCl 3): 8: 29 ppm (s, 1 P).

  1H NMR (CDCl3): 8: 1 ppm (s, 3H, CH2 = C (CH3)); 2.9 ppm (t, 3H, OCH 2 CH 2 N); 3.3 ppm (d, 4H, NCH 2 P (O) (OCH 3) 2); 3.9 ppm (t, 2H, COOCH2CH2N); 3.8 ppm (d, 12H, CH 2 P (O) (OCH 3) 2); 5.5 ppm (s, H, CH 2 = C (CH 3); 6 ppm (s, H, CH 2 = C (CH 3)) Preparation of copolymers of the invention Copolymerization reaction: Methyl methacrylate (MMA) / Acrylate Butyl (ABu) / tetraethyl diphosphonate methacrylate (molar proportions 50/45/5) In a 200 ml flask equipped with a condenser and an inlet of argon, 10 g of tetraethyl diphosphonate methacrylate ( 0.023 mol), 23 g of methyl methacrylate (0.23 mol) and 27.32 g of butyl acrylate (0.207 mol) in 200 ml of acetonitrile. argon for 15 minutes and brought to 70 ° C., 0.75 g of azobis-isobutyronitrile (AIBN) (4.6 × 10 -3 mol) are then introduced.

  After 16 hours of reaction, the acetonitrile is evaporated off under reduced pressure and the copolymer is solubilized in 200 ml of tetrahydrofuran. This solution is then precipitated in 1 liter of pentane.

  After filtration and drying, the desired copolymer is obtained with a yield of 90

Claims (14)

1. Compounds (I) of formula: H R1   Wherein R 1 represents a hydrogen atom or a methyl group, the R, which are identical to or different from each other, are chosen from: a hydrogen atom; a linear or branched alkyl group comprising from 1 to 22 carbon atoms, an aryl group and a phenyl group; the R ', which are identical to or different from each other, are chosen from: a hydrogen atom a linear or branched alkyl group having 1 to 8 carbon atoms, or a -NR 2 - group in 25 - A is a group C I I   which R2 represents a hydrogen atom, a linear or branched alkyl group having from 1 to 22 carbon atoms, an aryl group, a phenyl group or a C (R) 2 PO (OR ') 2 group in which the R and R 'have the abovementioned meanings, - Y is a group -C (O) O-, a group -OC (O) -, a group -C (O) NHC (O) O- or a benzyl, - Z is chosen among: a linear or branched alkyl group having 1 to 22 carbon atoms, a CH 2 CH (OH) CH 2 OCH 2 CH 2 group, a CH 2 CH (OH) CH 2 OC (O) CH 2 group, a CH 2 CH 2 SC 3 H 6 group, a CH 2 CH (OH) group; ) CH2OCH2CH2SC3H6i * a group CH2CH2NHC (O) CH2OC (O) CH2SC3H6, * a group CH2CH2NHC (O) OCH2CH2, a group C (CH3) (CH3) NHC (O) OCH2CH2, a group (CH2) tOC (0) (CH2) t. wherein t and t 'are an integer from 1 to 12; and the group: CH (X) wherein X is selected from the group consisting of linear or branched alkyl having from 1 to 22 carbon atoms, phenyl, a (CH2) 2SCH3 group, a (OH2) 4N (R2) 2 group, and a group corresponding to the formula or formula wherein R2 is as defined above, with the exception of compounds (I) for which R 1 is a hydrogen atom or a methyl, the R, which are identical or different, are a hydrogen atom or an alkyl having from 1 to 8 carbon atoms, the R ', which are identical or different, are an alkyl group Of 1 to 8 carbon atoms, Z is CH 2 CH 2, Y is -C (O) O-, A is -NR 2 - in which R 2 is either hydrogen or tert-group; alkyl having from 4 to 40 carbon atoms.   2. Compounds (I) according to claim 1, characterized in that R1 is a methyl, Y is a -C (O) O- group, Z is a CH2CH2 group, A is a -NR2 group in which R2 is a grouping. C (R) 2 P (O) (OR ') 2 where R is a hydrogen atom and R' is a hydrogen atom or a linear or branched alkyl having 1 to 8 carbon atoms, preferably a methyl, an ethyl or an isopropyl.   Compounds (I) according to claim 1, characterized in that R1 is methyl, Y is benzyl, Z is C (CH3) 2NHC (O) OCH2CH2r A is -NR2 wherein R2 is a group C (R) 2 P (O) (OR ') 2 where R is a hydrogen atom and R' is a hydrogen atom or an alkyl having 1 to 3 carbon atoms, preferably a methyl, an ethyl or isopropyl.   4. Compounds (I) according to claim 1, characterized in that R1 is a methyl, Y is a -C (O) O- group, Z is a CH2CH2 group, A is a nN group, R is a d hydrogen, R 1 and R 'is a hydrogen atom or an alkyl having 1 to 3 carbon atoms, preferably methyl, ethyl or isopropyl.   5. Copolymers resulting from the polymerization of at least one compound (I) as defined in claim 1 with at least one ethylenically unsaturated comonomer.   6. Copolymers according to claim 5, characterized in that the at least one ethylenically unsaturated comonomer is selected from the group consisting of crotonic acid, maleic acid, maleic anhydride, fumaric acid and itaconic acid. , itaconic anhydride, diethyl maleate, acrylonitrile and methacrylonitrile.   7.Copolymers according to claim 5, characterized in that the at least one ethylenically unsaturated comonomer is selected from the group consisting of the family of acids and acrylic and methacrylic esters, from the family of vinyl esters and alkyl vinyl ethers, by olefins, by the family of dienes, by the family of styrenics.   8.Copolymers according to claim 7, characterized in that the at least one comonomer of the family of acids and acrylic and methacrylic esters is chosen from the group consisting of acrylic acid, methacrylic acid and methyl acrylate. ethyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.   9. Copolymers according to claim 7, characterized in that the at least one comonomer of the family of vinyl esters and alkyl vinyl ethers is selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate. , methyl vinyl ether, ethyl vinyl ether and isobutylvinyl ether.   10. Copolymers according to claim 5, characterized in that they result from the polymerization of 0.5% to 50% by weight, preferably 1 to 10% by weight, of at least one compound (I) such as defined in claim 1 with 50% to 99.5% by weight, preferably 90% to 99% by weight, of at least one ethylenically unsaturated comonomer.   11. Use of the copolymers as defined in claim 5, in applications requiring anti-corrosion effects, adhesion or fireproofing.   12. Use of the copolymers as defined in claim 5 as flame retardants in plastics.   13. Use of the copolymers as defined in claim 5, as adhesion promoting agents on metal supports.   14. Use of the copolymers as defined in claim 5 as anticorrosive agents for metals.