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WO2018078001A1 - Procédé de prévention de la corrosion d'articles métalliques - Google Patents

Procédé de prévention de la corrosion d'articles métalliques Download PDF

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Publication number
WO2018078001A1
WO2018078001A1 PCT/EP2017/077413 EP2017077413W WO2018078001A1 WO 2018078001 A1 WO2018078001 A1 WO 2018078001A1 EP 2017077413 W EP2017077413 W EP 2017077413W WO 2018078001 A1 WO2018078001 A1 WO 2018078001A1
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Prior art keywords
chain
polymer
ionisable
polymers
group
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Inventor
Claudio Adolfo Pietro Tonelli
Giuseppe Marchionni
Solange BARBIERI
Evgeny Denisov
Gabriella Carignano
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Solvay Specialty Polymers Italy SpA
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Solvay Specialty Polymers Italy SpA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
    • C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups

Definitions

  • the present invention relates to a method for preventing the corrosion of metal articles and to compositions for carrying out such method.
  • electrochemical oxidation by contact with an oxidant, like oxygen or sulfur and convert to more stable forms, such as their oxides, hydroxides or sulfides.
  • an oxidant like oxygen or sulfur
  • electrochemical oxidation is rusting, which consists in the formation of iron oxides or salts on a metal surface and imparts a typical orange coloration.
  • One of the methods used to prevent the oxidation of metals and metal alloys is to apply a polymeric film on their surface.
  • US 2004265603 (SCHLENOFF, JOSEF B) 30/12/2004 discloses an anticorrosion polymer coating to be applied on a metallic surface, said coating comprising a positively-charged polyelectrolyte and a negatively-charged polyelectrolyte forming a complex.
  • the polyelectrolytes used for making the coating are copolymers having a combination of charged and neutral repeat units. There is no disclosure or suggestion of polymers comprising a neutral polymer chain and one charged unity at each end of the chain.
  • the coating disclosed in this document can be formed either by exposing a surface to alternating oppositely charged polyelectrolyte solutions or using a pre-formed polyelectrolyte complex, which can be obtained by mixing the oppositely-charged polyelectrolytes.
  • the pre-formed complex precipitates and is then dissolved or resuspended in a suitable solvent/liquid to form a polyelectrolyte complex solution/dispersion.
  • Such solution or dispersion is then applied to the substrate surface and the solvent/liquid is evaporated, leaving behind a film comprising the polyelectrolyte complex.
  • PFPEs fully or partially fluorinated polyethers
  • HFPO hexafluoropropylene oxide
  • 2,2,3,3-tetrafluorooxetane the photooxidation of
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • PFPEs comprises a fully or partially fluorinated polyoxyalkylene chain (PFPE chain) that contains recurring units having at least one catenary ether bond and at least one fluorocarbon moiety.
  • PFPEs can be divided into non-functional and functional; the former comprise a PFPE chain having at least two ends, wherein such ends bear (per)haloalkyl groups, while the latter comprise a PFPE chain having at least two ends, wherein at least one end comprises a functional group.
  • Functional PFPEs can be used as starting materials for the manufacture of other functional PFPEs that are used as such for a variety of industrial applications, e.g. as additives for lubricant compositions, or as building blocks for the manufacture of block copolymers.
  • the lubricating film layer comprises a fluoropolyether lubricant having at least two acidic functional groups in one molecule and a fluoropolyether lubricant having at least two basic functional groups in one molecule.
  • This document teaches that the two fluoropolyether lubricants form a stable network structure on the medium surface by an appropriate combination of the lubricant having the acidic groups and the one having the basic groups.
  • magnetic recording media typically comprise a substrate, a magnetic layer and a protective carbon overcoat laid on the magnetic layer and lubricants are applied onto the carbon overcoat in order to prevent wear by contact with a magnetic head floating over the surface of the medium during recording and reproduction, or by contact with dust generated during such contact.
  • Magnetic materials used in the manufacture of recording media are metal oxides, such as ferromagnetic oxides, in admixture with a binder and further additives.
  • EP 1231297 A1 (AUSIMONT SPA) 14/08/2002 discloses the use of mono- and bi-functional PFPE having phosphate or silane terminal groups for the treatment of metals or metal alloys in order to confer anti- calcar properties and prevent corrosion.
  • This document neither discloses nor suggests the use of functional PFPEs other than phosphates and silanes and also neither discloses nor suggest to combine PFPE derivatives having ionisable anionic and cationic groups able to interact or form supramolecular structures.
  • WO 2013/017470 SOLVAY SPECIALTY POLYMERS ITALY SPA 07/02/2013 discloses compositions comprising two ionisable
  • fluoropolymers each comprising recurring fluorinated blocks and recurring blocks comprising at least one ionisable anionic or cationic group, wherein at least one ionizable recurring block is comprised between two fluorinated blocks.
  • the two fluoropolymers in the composition are present at an ionic ratio ranging from 1.1 to 0.9.
  • Such compositions are able to form elastomeric materials which, in certain instances, advantageously show a self-repairing behaviour.
  • compositions comprising fluoropolymers having a chain of recurring fluorinated blocks, said chain having two ends, each end comprising one ionisable anionic or cationic group.
  • anti-corrosion properties There is also no hint to anti-corrosion properties.
  • WO 2014/090646 SOLVAY SPECIALTY POLYMERS ITALY SPA discloses compositions comprising:
  • compositions are stable even after addition of a cross-linking
  • compositions comprising fluoropolymers having a chain of recurring fluorinated blocks, said chain having two ends, each end comprising one ionisable anionic or cationic group. There is also no hint to anti-corrosion properties.
  • composition (FC) comprising:
  • polymer (A) comprising recurring (per)fluorinated blocks [blocks (F)], recurring functional blocks [blocks (B a )] and at least one curable group [group (C)], said blocks (B a ) comprising at least one ionisable anionic group [group (I-)];
  • polymer (B) comprising recurring (per)fluorinated blocks [blocks (F)], recurring functional blocks [blocks (Bb)] and at least one curable group [group (C)], said blocks (Bb) comprising at least one ionisable cationic group [group (l + )];
  • Composition can be used for example for preparing polymeric articles, preferably amorphous articles, endowed with elastic properties.
  • the articles are endowed with self-healing properties.
  • compositions comprising definite amounts of ionisable polymers having a defined glass transition temperature (Tg) are able to form particularly effective anti-corrosion coatings on metals and alloys.
  • Tg glass transition temperature
  • the present invention relates to a method [method (M)] for preventing the corrosion of metals and alloys, said method comprising applying to a metallic or alloy substrate a composition
  • composition (C) comprising, preferably consisting of:
  • chain (R) consisting of a plurality of non-ionisable recurring units [units (U)], said chain having two ends, each end comprising at least one ionisable acid group;
  • chain (R) consisting of a plurality of non-ionisable recurring units [units (U)], said chain (R) being equal to or different from that of polymer (P1 ) and having two ends, each end comprising at least one ionisable amino group
  • - polymers (P1 ) and (P2) are amorphous and have a Tg lower than - 35°C, preferably ranging from -35 to -120°C and wherein
  • the ratio between the equivalents of polymer (P1 ) and the equivalents of polymer (P2) in composition (C) ranges from 1.1 to 0.9.
  • Tg is typically measured at midpoint by differential scanning calorimetry (DSC) with a scan rate of 20 °C/min.
  • polymer (P1 ) and the equivalents of polymer (P2) is referred to the acid/base reaction between the at least one ionisable amino group in each end group of polymer (P1 ) and the at least one ionisable acid group in each end of polymer (P2).
  • polymer (P1 ) and polymer (P2) form a supramolecular ionic network which shows a significantly higher experimental viscosity than the theoretical viscosity and which is able to form coatings that are highly resistant to corrosion even at very low thicknesses.
  • the invention relates to certain compositions (C) for performing method (M).
  • the invention relates to a metallic article [article
  • PFPE perfluoropolyether
  • PFPEs perfluoropolyether
  • (per)haloalkyl denotes a fully or partially halogenated
  • halogen includes fluorine
  • a "cycloalkyl group” is a univalent group derived from a cycloalkane by removal of an atom of hydrogen; the cycloalkyl group thus comprises one end which is a free electron of a carbon atom contained in the cycle, which able to form a linkage with another chemical group;
  • divalent cycloalkyl group or "cycloalkylene group” is a divalent radical derived from a cycloalkane by removal of two atoms of hydrogen from two different carbons in the cycle; a divalent cycloalkyl group thus comprises two ends, each being able to form a linkage with another chemical group;
  • aromatic denotes any mono- or polynuclear cyclic group (or moiety) having a number of ⁇ electrons equal to 4n+2, wherein n is 0 or any positive integer; an aromatic group (or moiety) can be an aryl or an arylene group (or moiety);
  • an "aryl group” is a hydrocarbon monovalent group consisting of one core composed of one benzenic ring or of a plurality of benzenic rings fused together by sharing two or more neighboring ring carbon atoms, and of one end.
  • Non limitative examples of aryl groups are phenyl, naphthyl, anthryl, phenanthryl, tetracenyl, triphenylyl, pyrenyl, and perylenyl groups.
  • the end of an aryl group is a free electron of a carbon atom contained in a (or the) benzenic ring of the aryl group, wherein an hydrogen atom linked to said carbon atom has been removed.
  • the end of an aryl group is capable of forming a linkage with another chemical group;
  • an "arylene group” is a hydrocarbon divalent group consisting of one core composed of one benzenic ring or of a plurality of benzenic rings fused together by sharing two or more neighboring ring carbon atoms, and of two ends.
  • arylene groups are phenylenes, naphthylenes, anthrylenes, phenanthrylenes,
  • An end of an arylene group is a free electron of a carbon atom contained in a (or the) benzenic ring of the arylene group, wherein an hydrogen atom linked to said carbon atom has been removed.
  • Each end of an arylene group is capable of forming a linkage with another chemical group.
  • CycloalkyI, cycloalkylene, aryl and arylene groups can be substituted with one or more straight or branched alkyl or alkoxy groups and/or halogen atoms and/or can comprise one or more heteroatoms, like nitrogen, oxygen and sulfur, in the ring.
  • average functionality (F) denotes the average number of functional groups per polymer molecule and can be calculated according to methods known in the art.
  • the average functionality (F) of PFPE alcohols can be calculated following the method reported in EP 1810987 B (SOLVAY SOLEXIS SPA) 7/25/2007 or in S.Turri, E. Barchiesi, M. Levi Macromolecules 28, 7271 , (1995).
  • the average functionality of polymers (P1) and (P2) according to the present invention was determined following the teaching of the latter reference.
  • corrosion means the conversion of a metal into its corresponding oxide(s), hydroxide(s) or sulphide(s) or mixtures thereof.
  • An alloy is a mixture of metals or a mixture of a metal with another element wherein the metal is the main component.
  • ionisable amino group and "ionisable acid groups” identify amino or acid groups able to form ionic groups, namely cationic and anionic groups respectively.
  • an ionisable amino group identifies a primary, secondary or tertiary amino group
  • an ionisable acid group identifies an acid group comprising at least one hydroxyl function in its protonated form, i.e. a protic acid group.
  • non-ionisable recurring unit identifies a chemical moiety that is not able to form an ionic group with the at least one ionisable amino group or the at least one ionisable acid group in each end of polymers (P1 ) and (P2).
  • Polymer (P1 ) can be represented with formula (P1 ) here below:
  • - R is a polymer chain consisting of a plurality of non-ionisable recurring units [units (U)], equal to or different from one another and
  • Recurring units (U) are hydrocarbon units, which can further comprise non-ionisable atoms or non-ionisable functional groups, including one or more of halogen atoms, preferably fluorine atoms, ethereal oxygen atoms, alkyl or alkoxy silane groups, carbonate, ester, urethane and acrylate groups.
  • Non limiting examples of polymers (P1 ) are those wherein chain (R) is independently selected from a fully or partially fluorinated polyoxyalkylene chain, a polyalkylsiloxane chain, a polyoxyalkylene chain, a polycarbonate chain, a polyester chain, a polyacrylate chain and a polybutadiene chain, as described in greater detail here below.
  • chain (R) is independently selected from a fully or partially fluorinated polyoxyalkylene chain, a polyalkylsiloxane chain, a polyoxyalkylene chain, a polycarbonate chain, a polyester chain, a polyacrylate chain and a polybutadiene chain, as described in greater detail here below.
  • chains (R) are those wherein chain (R) is independently selected from a fully or partially fluorinated polyoxyalkylene chain, a polyalkylsiloxane chain, a polyoxyalkylene chain, a polycarbonate chain, a polyester chain, a polyacryl
  • chain (RF) comprises recurring units [units (UF)] having at least one catenary ether bond and at least one fluorocarbon moiety; typically, chain (RF) comprises repeating units (UF) selected from:
  • chain (RF) complies with formula (RF-I):
  • - Xi is independently selected from -F and -CF3;
  • - X2, X3, equal or different from each other and at each occurrence, are independently -F, -CF3, with the proviso that at least one of X is -F;
  • chain (RF-I) is selected from chains of formulae (RF-
  • - a1 and a2 are independently integers ⁇ 0 such that the number average molecular weight (M n ) ranges from 400 to 10,000, preferably from 400 to 5,000; both a1 and a2 are preferably different from zero, with the ratio a1/a2 being preferably ranging from between 0.1 to 10;
  • b1 - b1 , b2, b3, b4, are independently integers ⁇ 0 such that the number average molecular weight (M n ) ranges from 400 to 10,000, preferably from 400 to 5,000; preferably b1 is 0, b2, b3, b4 are > 0, with the ratio b4/(b2+b3) being >1 ;
  • c1 , c2, and c3 are independently integers ⁇ 0 such that the number average molecular weight (M n ) ranges from 400 to 10,000, preferably from 400 to 5,000; preferably c1 , c2 and c3 are all > 0, with the ratio c3/(c1 +c2) being generally lower than 0.2;
  • M n the number average molecular weight ranges from 400 to 10,000, preferably from 400 to 5,000;
  • Hal is a halogen selected from fluorine and chlorine atoms, preferably a fluorine atom;
  • chain (RF) complies with formula (RF-I I I) here
  • M n number average molecular weight
  • a2/a1 generally ranging from 0.2 to 5.
  • a polyalkylsiloxane chain [herein after otherwise referred to as chain (Rs)] comprises recurring units [units (Us)] of formula:
  • Ra s and Rb s are independently selected from hydrogen, straight or branched (halo)alkyl and aryl, with the proviso that at least one of Ra s and Rb s is not hydrogen.
  • Preferred Ra s and Rb s groups are straight or branched alkyl groups comprising from 1 to 4 carbon atoms; more preferably, both Ra s and Rb s are methyl, i.e. chain (Rs) is a polydimethylsiloxane chain [chain (Rs-I), which comprises recurring units of formula (Us-i) here below:
  • Chain (Rs) has a number average molecular weight (M n ) typically
  • ROA Polyoxyalkylene chains
  • a polyoxyalkylene chain is a straight or branched polymer chain consisting of repeating hydrocarbon units comprising at least one catenary ether bond [units (UOA)]; non-limiting examples of chain (ROA) are polyoxyethylene chains and polyoxypropylene chains, respectively comprising recurring units of formulae (UoA-i) - (UoA-iv) here below:
  • Chain (ROA) has a number average molecular weight (M n ) typically ranging from 500 to 10,000, preferably from 500 to 5,000.
  • chain (Rpc)] consists of repeating units [units (Upc)] of formula:
  • R°PC represents:
  • - a straight or branched alkylene chain, optionally comprising one or more cycloalkyl, divalent cycloalkyl group, aryl or arylene groups as defined above.
  • the polycarbonate chain has a number average molecular weight (M n ) typically ranging from 500 to 10,000, preferably from 500 to 5,000.
  • Polyester chains (RPE) RPE
  • a polyester chain [herein after otherwise referred to as chain (RPE)] comprises recurring units [units (UE)] of formula:
  • R°PE and R°'PE equal to or different from one another, represent a straight or branched alkylene chain, optionally comprising one or more cycloalkyl, divalent cycloalkyl group, aryl or arylene groups as defined above.
  • Chain (RPE) has a number average molecular weight (M n ) typically
  • chain (R) of polymer (P1) is a chain (RF) as defined above, preferably a chain of formula (RF-I), more preferably a chain of formula (RF-I 11).
  • chain (R) of polymer (P1) is a chain (Rs) as defined above, preferably a chain (Rs-I).
  • End groups E1 and E1 ' typically comprise at least one carboxylic acid group, phosphonic acid group or sulfonic acid group, said at least one acid group comprising at least one hydroxyl group in its protonated form, so that it is capable to form an anionic group via acid/base reaction with the at least one ionisable amino group at one of the ends of polymer (P2).
  • E1 and E1 ' can be equal to or different from one another.
  • E1 and E1 ' are equal to one another.
  • groups E1 and E1 ' comply with formula (E1 -A) here below:
  • - B1 represents a chemical bond or a straight or branched alkylene
  • alkylene chain preferably comprising from 1 to 20 carbon atoms, and optionally bearing one or more halogen atoms, one or more further -EA groups and/or optionally comprising i one or more heteroatoms or moieties independently selected from:
  • - cycloalkylene and arylene groups as defined above, -O-, -S-, - OC(O)O-, -OC(O)NH-, -OC(O)S-, -SC(O)S-, -NHC(O)NH- and - NHC(S)NH- and - EA represents a -COOH, a -P(O)(OREA)2 or a -S(O)2OH group, wherein one of REA is hydrogen and the other one is hydrogen or straight or branched alkyl, preferably Ci-C 4 alkyl.
  • EA is a -COOH group.
  • Polymer (P2) can be represented with formula (P2) here below:
  • - R is a polymer chain as defined above and
  • E2 and E2' are end groups each comprising at least one ionisable amino group.
  • Chain (R) of polymer (P2) can be the same or different from chain (R) of polymer (P1 ).
  • End groups E2 and E2' typically comprise at least one ionisable
  • Groups E2 and E2' can be equal to or different from one another; preferably, groups E2 and E2' are equal to one another, "lonisable primary, secondary or tertiary amino group” means that the amino group is in its free form, so that it is capable to form a cationic group via acid/base reaction with the at least one a ionisable acid group at one of the ends of polymer (P1 ).
  • groups E2 and E2' comply with formula (E2-A) here below:
  • - B2 represents a chemical bond or a straight or branched alkylene
  • alkylene chain preferably comprising from 1 to 20 and optionally bearing one or more halogen atoms, one or more further - N(Rp2)2 groups and optionally comprising one or more heteroatoms or moieties independently selected from:
  • RP2* represents hydrogen or straight or branched alkyl, preferably Ci-C 4 alkyl, more preferably methyl; - ⁇ -, -S-, -OC(0)0-, -OC(O)NH-, -OC(0)S-, -SC(0)S-, -NHC(O)NH- and -NHC(S)NH- and
  • RP2 represents hydrogen or straight or branched alkyl, preferably Ci- C 4 alkyl.
  • Polymers (PF1 ) and (PF2) can be prepared according to methods known in the art for the synthesis of PFPEs.
  • the synthesis of polymers (PF1 ) and (PF2) wherein chain (RF) is a chain of formula (RF-I) can be carried out by oxypolymerization of fluoroolefins, followed by conversion of a resulting -CFXC(O)F terminated polymer ("acyl fluoride- terminated polymer", wherein X is as defined above) into the
  • Ester (EF1 ) can be either hydrolyzed to provide an acid polymer (PF1 ) wherein E and E' represent -CFXC(O)OH [herein after (PF1 -A)] or reduced to the corresponding PFPE diol ["diol (DF1 )] of formula (RF-I)- (CFXCH 2 OH) 2 [herein after "PFPE diol (D F 1 -A)"].
  • ester (EF1 ) can be carried out according to methods known in the art, using reducing agents such as NaBH 4 , or by catalytic hydrogenation, as disclosed, for example, in US 6509509 A (AUSIMONT S.P.A) 7/5/2001 , US 657341 1 (AUSIMONT S.P.A.) 1 1/21/2002, WO 2008/122639 A (SOLVAY SOLEXIS S.P.A.) 10/16/2008.
  • reducing agents such as NaBH 4
  • catalytic hydrogenation as disclosed, for example, in US 6509509 A (AUSIMONT S.P.A) 7/5/2001 , US 657341 1 (AUSIMONT S.P.A.) 1 1/21/2002, WO 2008/122639 A (SOLVAY SOLEXIS S.P.A.) 10/16/2008.
  • Polymer (PF1 -A) can be used as such in the manufacture of
  • Diols (DF1 -A) can be reacted with alkylene oxides, typically ethylene oxide and propylene oxide, in the presence of a base, to provide further diols (DF1 -B) - (DF1 -D) of formulae:
  • n°D is a positive number, preferably ranging from 1 to 10, more preferably ranging from 1 to 5.
  • Diols (DF1 -B) - (DF1 -D) can also be used as precursors for polymers (PF1 ) and (PF2), as explained below in greater detail.
  • Diols (DF1 -A) and (D F 1 -B) with a chain (RF-I I I) and wherein in (D F 1 -B) n°D ranges from 1 to 2 are available from Solvay Specialty Polymers Italy S.p.A. with the tradename Fomblin ® Z DOL.
  • Other diols (D F 1 -B) - (D F 1 -D) can be obtained following the teaching of WO2014090649 (SOLVAY SPECIALTY POLYMERS ITALY SPA).
  • ester EF1
  • diols DF1
  • DF1 diols
  • ester (EF1 ) and diols (DF1 ) are always obtained as mixtures comprising the corresponding mono-functional and neutral esters or alcohols which form in the oxypolymerization reaction, i.e. compounds terminating with (per)haloalkyl groups at one or both ends, typically C1 -C3 perfluoroalkyl groups.
  • Ester (EF1 ) and diols (DF1 ) are thus characterized by an average functionality (F) as defined above; the higher the average functionality, the higher the number of bifunctional species.
  • polymers (PF1 ) and (PF2) obtained from ester (EF1 ) or from diols (DF1 ) are also in admixture with corresponding polymers wherein one end of chain (RF) bears a (per)haloalkyl group and with neutral compounds present in the (EF1 ) or diol (DF1 ) used as starting material.
  • neutral compounds that comprise (per)haloalkyl groups at both ends are present in an amount lower than 0.04% on a molar basis.
  • ester (EF1 ), diols (DF1 ) having an average functionality (F) higher than 1 , preferably of at least 1.5 can be used.
  • PFPE ester (EF1 ) and diols (DF1 ) can be used as precursors for the synthesis of polymers (PF1 ) and (PF2) with suitable reaction partners, according to methods known in the art for the manufacture of PFPE derivatives.
  • PFPE ester (EF1 ) can be used as precursor for polymers (PF1 ) or (PF2) wherein groups (E1 -A) and (E2-A) respectively comply with formulae (E1 -Aa), (E1 -Ab), (E2-Aa), (E2-Ab) here below :
  • B1 * and B2 * represent straight or branched alkylene chains, said alkylene chain preferably comprising from 1 to 10 carbon atoms and optionally bearing one or more halogen atoms, and/or optionally comprising one or more heteroatoms or moieties independently selected from:
  • B1 * may also comprise one or more further EA groups, while B2 * may also comprise one or more further -N(Rp 2 ) 2 groups.
  • B2 * may also comprise one or more -N(Rp 2 *)- moieties.
  • Polymers (P F 1 ) or (P F 2) wherein groups (E1 -A) and (E2-A) comply with formulae (E1 -Aa), (E1 -Ab), (E2-Aa), (E2-Ab) as defined above can be manufactured by reacting ester (EF1 ) with compounds of formulae NH 2 - B1 * -E A and HO-B2 * -N(R P2 ) 2 , wherein B1 * , EA, B2 * and N(R P2 ) 2 are as defined above.
  • end groups (E1 -Aa), (E1 -Ab), (E2-Aa), (E2-Ab) can also be build up by subsequent reactions of ester (EF1 ) with suitable reaction partners.
  • a polymer (PF1 ) wherein group (E1 -Aa) comprises a -NHC(O) moiety can be obtained by reacting ester (EF1 ) first with a diamine and then with an acid comprising two EA groups.
  • a polymer (PF1 ) wherein group (E1 -Ab) comprises one or more -O-C(O)-NH moieties can be obtained by reacting ester (EF1 ) first with a diol and the with a diisocyanate.
  • PFPE diols can be used, for example, as precursors of polymers (PF1 ) and (PF2) wherein groups (E1 -A) and (E2-A) respectively comply with the formulae listed below:
  • X, EA and Rp 2 are as defined above and nD is 0 or a positive number, preferably from 1 to 10, more preferably from 1 to 5, while B1 ** and B2 ** represent a chemical bond or straight or branched alkylene chains, said alkylene chains preferably comprising from 1 to 10 carbon atoms and optionally bearing one or more halogen atoms, and/or comprising one or more heteroatoms or moieties independently selected from:
  • B1 ** may also comprise one or more further EA groups, while B2 ** may also comprise one or more further -N(Rp 2 ) 2 groups.
  • B2 ** may also comprise one or more -N(Rp 2 *)- moieties.
  • RF-I, X, Rp 2 and nD are as defined above.
  • polymers (PF2-A) can be obtained by converting a PFPE diol (DF1 -A) or (DF1 -B) into the corresponding sulfonic ester (like the trifluoromethanesulfonyl, perfluorobutylsulfonyl or p-toluenesulfonyl ester) and then reacting the sulfonic ester with an amine of formula HN(R P2 ) 2 , following the procedure disclosed in US 6984759 B (SOLVAY SOLEXIS SPA).
  • Amines (PF2-A) can be used as such in the manufacture of
  • compositions (C) or can be used as precursors of other polymers (PF1 ) or (PF2) by reaction with suitable reaction partners according to methods known in the art.
  • suitable reaction partners for example, convenient polymers (PF1 ) can be obtained by reaction of an amine(Pp2-A) with an aromatic compound (PF2).
  • polycarboxylic acid or a derivative thereof able to form amido bonds for example with trimellitic acid or a derivative thereof, such as trimellitic anhydride.
  • trimellitic acid or a derivative thereof such as trimellitic anhydride.
  • Good results were obtained using a polymer (PF1 ) obtained by reacting an amine (PF2-A) of formula (RF-I I I)-(CF2CH 2 N H2)2 with trimellitic anhydride.
  • a further example of polymer which can be obtained from a PFPE diol (DF1 ) is a polymer (PF1 ) complying with formula (PF1 -B):
  • Polymer (PF1 -B) can be used as such in the manufacture of
  • compositions (C) or it can in turn be used as precursor for the
  • RF-I , X and nD are as defined above and RBI is C1-C10 straight or branched alkylene, C 4 -C6 cyloalkylene as defined above or C5-C6 arylene as defined above, optionally comprising one or more -COOH groups.
  • chain (RF-I) is a chain (RF-I I I) as defined above, X is F, nD is 0 or ranges from 1 to 5 and RBI is selected from 0-, m-, p- cyclohexylene and 0-, m-, p-phenylene.
  • Polymers (PF1 -C) and (PF1 -D) can be obtained from diols (D F 1 -A), (D F 1 -B) and from (PF2-A) by reaction with a diacid of formula HOOC-RBI -COOH wherein RBI is as defined above or with a reactive derivative thereof, like a halide or an anhydride.
  • PF1 -C complies with formula (PF1 -Ca) here below:
  • polymers (P2) for the preparation of compositions (C) are those complying with the following formulae (PF2- B) and (P F 2-C)
  • RF-I , X, nD and N(RP2)2 and RBI are as defined above.
  • RB2 is straight or branched C1-C6 alkylene chain optionally comprising a C 4 -C6 cyloalkylene group as defined above or a C5-C6 arylene group as defined above and RB3 is C2-C10 straight or branched alkylene, optionally interrupted by one or more -N(RP2*)- groups as defined above.
  • Polymers (P F 2-B) can be obtained by reaction of a diol (D F 1-A) or (D F 1 - B) with an amidoacid or with a reactive derivative thereof, such as an halide or anhydride.
  • Polymers (PF2-C) can be obtained by reaction of a diol (D F 1-A) or (D F 1 -
  • Polymers (Ps1 ) and (Ps2) are available on the market, or can be
  • polymers (Ps1 ) and (Ps2) wherein Ra s and Rb s are both methyl can be obtained by hydrolysis of dimethyl chlorosilane to provide a dihydroxy-terminated poly(dimethylsiloxane) and derivatization of the same according to methods known in the art for the manufacture of amines and acids.
  • Ps2 polydimethyl siloxane of formula (Ps2-A) here below:
  • ns is a positive number selected in such a way that the number average molecular weight (M n ) of the [Si(CH3)2O] ns chain ranges from 500 to 10,000, preferably from 500 to 5,000 and ns* is 0 or a positive number equal to or higher than 1 , preferably ranging from 1 to 10.
  • M n number average molecular weight of the [Si(CH3)2O] ns chain ranges from 500 to 10,000, preferably from 500 to 5,000 and ns* is 0 or a positive number equal to or higher than 1 , preferably ranging from 1 to 10.
  • a polymer (Ps2-A) wherein ns* is 3 is available from Aldrich®.
  • Polymer (Ps2-A) can be used as such in the manufacture of
  • Ps1 polymers
  • Ps2 polymers
  • convenient polymers (Ps1 ) complying with the following formula (Ps1 -A) here below: (Ps1 -A) Rs-[(CH 2 )ns*N HC(O)- R B i-COOH] 2
  • ns* and RBI are as defined above and Rs is a chain of formula Si(CH3)2O[Si(CH3)2O]nsSi(CH3)2 can be obtained by reaction of polymer (Ps2-A) with an acid of formula HOOC-RBI -COOH, wherein RBI is as defined above, or with a reactive derivative thereof, such as an halide or anhydride.
  • Ps1 -A A convenient example of polymer (Ps1 -A) is one complying with formula (Ps1 -Aa) here below:
  • polymer (Ps1 ) is a polymer complying with formula (Ps1 -B):
  • ns* and RBI are as defined above and Rs is a chain of formula Si(CH3)2O[Si(CH 3 )2O]nsSi(CH 3 )2.
  • Polymer (Ps1 -B) can be obtained by reaction of a dihydroxy-terminated silane precursor of formula:
  • Preferred examples of polymers (P 1OA) and (P2OA) are those comprising a polyoxyethylene chain, a polyoxypropylene chain or a polytetramethylene glycole chain.
  • R*OA is a straight or branched alkylene chain, typically an ethylene, propylene or a tetramethylene chain, and ⁇ * ⁇ is an integer selected in such a way as the number average molecular way ranges from 500 to 5,000
  • polymers (POA1 ) and (POA2) can be obtained by methods know in in the art by reaction with suitable reaction partners.
  • a diol (DOA-1 ) wherein R*OA is an ethylene chain is commercially available from Aldrich ® .
  • polymers (P1 OA) complying with formula (P1 OA-A):
  • RBI , R * oA and ⁇ * ⁇ are as defined above, can be obtained by reaction of a diol (DOA1 ) with a halo-alkyl or haloalkylene acid X°-RBI- COOH wherein X° iis halogen and RBI is as defined above or with a corresponding halide or ester.
  • a polymer (P1 OA-A) wherein RBI is -Chb- can be obtained by reaction of diol (DOA1 ) with a 2- halo acetic acid or halide or ester thereof, such as with 2-chloroacetic acid ethyl ester.
  • a polymer (P1 OA-A) wherein R*OA is an ethylene chain and RBI is -Chb- is available from Aldrich ® .
  • HOOC-RBI- C(O)-(OR * oA) n *oA-O-C(O)R B i-COOH can be obtained by reaction of a diol (DOA-1 ) with a diacid of formula HOC(O)-RBI-COOH, wherein RBI is as defined above, or with a reactive derivative thereof, such as an halide or anhydride.
  • a polymer (P2OA-A) wherein R*OA IS ethylene is available on the market from Aldrich ® .
  • Polymers (Pipe) and (P2PC) can be manufactured by reaction of a diol of formula (D° PC 1 ):
  • (R° PC ) is a straight or branched alkylene chain, preferably a C2 - C10 alkylene chain, optionally comprising ethereal oxygen atoms and a carbonate, typically diphenylcarbonate,
  • DPC1 Dihydroxy-terminated polycarbonates having an average number molecular weight (M n ) ranging from 500 to 3,000 are commercially available, for example, from UBE as Ethernacoll ® PH.
  • polymers can be obtained by reaction of (DPC1 ) with a halo-alkyl or haloalkylene acid ester, preferably with an acid of formula X°-RBI-COOH wherein X° is halogen and RBI is as defined above, or an ester thereof, for example with 2-chloro acetic acid ethyl ester.
  • D°PC1 diol
  • Polymers (P2PC-A) wherein at least one of Rp2 is hydrogen can be used as precursors of further polymers (Pi pe) and (P2PC).
  • Polymers (P1PE) and (P2PE) can be prepared according to methods known in the art starting from a polyester diol [diol (DPE1 )].
  • Diols (DPE1 ) can be obtained by polycondensation of dicarboxylic acids or lactams and diols.
  • Polyester diols are commercially available; for example, polycaprolactone diols are available from Perstop under the tradename CapaTM.
  • Convenient polymers can be obtained by reaction of a diol (DPE1 ) with a halo-alkyl or haloalkylene acid ester, preferably with an acid of formula X°-RBI-COOH wherein X° is halogen and RBI is as defined above, or an ester thereof, for example with 2-chloro acetic acid ethyl ester.
  • Further convenient polymers (PPE1 ) can be obtained by reaction of a diol (DPE1 ) with an acid of formula HOOC- RBI-COOH wherein RBI is as defined above, or with a reactive derivative thereof, such as a halide or anhydride
  • Polymers (PPE2) with -N(RP2)2 end groups can be obtained from diols (DPE1 ) according to methods known in the art for the replacement of the hydroxyl group with an amino group. Polymers (PPE2) thereby obtained can be in turn used as precursors for other polymers (PPE1 ) or (PPE2) by reaction with suitable precursors according to methods known in the art.
  • Polymers (PPBD1 ) and (PPBD2) can be obtained from dihydroxy
  • polybutadienes terminated polybutadienes according to methods disclosed in the art.
  • Such polybutadienes are available, for example, from Cray Valley; one of them is marketed as Poly bd ® R-45HTLO.
  • Convenient polymers (PPBD1 ) can be obtained by reaction of a
  • dihydroxy terminated polybutadiene [diol (DPBDI)] with a halo-alkyl or haloalkylene acid ester, preferably with an acid of formula X°-RBI- COOH wherein X° is halogen and RBI is as defined above, or an ester thereof, for example with 2-chloro acetic acid ethyl ester.
  • Further convenient polymers PPBD1
  • PPBD1 can be obtained by reaction of a dihydroxy terminated polybutadiene with an acid of formula HOOC- RBI-COOH wherein RBI is as defined above, or a reactive derivative thereof.
  • Polymers (PPBD2) with -N(RP2)2 end groups can be obtained from a dihydroxy terminated polybutadiene (DPBDI) according to methods known in the art for the replacement of the hydroxyl groups with an amino group.
  • Polymers (PPBD2) thereby obtained can be in turn used as precursors for other polymers (PPBD1 ) or (PPBD2) by reaction with suitable precursors according to methods known in the art.
  • Composition (C) and its manufacture
  • Composition (C) for carrying out method (M) can be prepared by mixing a polymer (P1 ) and a polymer (P2) according to conventional mixing techniques at an equivalent ratio between polymer (P1) and polymer (P2) ranging from 1.1 to 0.9. Mixing can be carried out with or without solvents, using appropriate mixing equipment.
  • One or more polymers (P1 ) can be used in the manufacture of
  • composition (C) "More polymers” means that polymers (P1 ) can be used which can differ from one another in the kind of units (U) of chain (R), in the kind of end groups (E1 ) and ( ⁇ 1 ') or both.
  • One or more polymers (P2) can also be used in the manufacture of composition (C).
  • "More polymers” means that polymers (P2) can differ from one another in the kind of chain (R), in the kind of end groups (E2) and ( ⁇ 2') or both.
  • polymer (P2) are used in the manufacture of composition (C); chains (R) of polymer (P1 ) can be the same or different from chain (R) of polymer (P2).
  • chain (R) in either (P1 ) or (P2) is a chain (RF) as defined above, preferably a chain of formula (RF-I) as defined above, more preferably a chain of formula (RFI-I I) as defined above, while chain (R) in the other polymer is a chain (Rs) as defined above, preferably a chain (Rs-I) as defined above.
  • chain (R) is the same in the polymers (P1 ) and (P2).
  • compositions (C) for carrying out method (M) comprise a polymer (P1 ) and a polymer (P2) wherein, in both polymers, chains (R) is a (per)fluoropolyether chain (RF) as defined above, preferably a chain of formula (RF-I) as defined above, more preferably a chain of formula (RFI-I I) as defined above.
  • RF perfluoropolyether chain
  • compositions for carrying out method (M) comprise a polymer (P1 ) and a polymer (P2) wherein chain (R) is a
  • compositions (C) per se represent a further embodiment of the
  • Composition (C) may further comprise one or more organic polar protic or aprotic solvents.
  • solvents are alcohols, ketones, acetates, dimethylacetamide (DMA) and hydrofluoroethers.
  • Preferred organic solvents are ketones, like methylethylketone (MEK) and acetates, like ethylacetate and butyl acetate).
  • the one or more organic solvent is comprised in
  • compositions (C) in an amount ranging from 1 % to 99.9%wt with respect to the overall weight of the composition.
  • the amount of solvent will be selected by the person skilled in the art according to the thickness of the coating (or film) obtained from the composition, being understood that the higher the amount of solvent, the lower the thickness of the film obtainable therefrom.
  • Method (M) can be carried out by applying composition (C) to a metal article or a part thereof, according to conventional techniques.
  • composition (C) can be applied by casting composition (C) and drying or evaporating of any solvent upon heating, or can be applied by means of a dip-coater followed and drying or evaporation of any solvent upon heating.
  • Composition (C) can also be applied by spray coating.
  • Metal articles obtained by method (M) represent a further aspect of the present invention.
  • a metal article is an article consisting of a metal or a metal alloy, without limitation in its dimension and shape.
  • magnetic means are not metallic articles for the purpose of the present application.
  • Films of composition (C) may have a thickness ranging from 0.1 to 100 ⁇ .
  • composition (C) are metallic articles used in architecture, industrial plants, in the automotive industry.
  • a metal article is an article made of iron, zinc, nickel and alloys thereof.
  • compositions (C) showed highly resistant to corrosion. Without being bound to theory, it is believed that this high resistance is due to the high viscosity of compositions (C), which is significantly higher than the sum of the viscosities of polymers (P1 ) and (P2).
  • Isophorone diisocyanate IPDI
  • DBTDL dibutyltindilaurate
  • DABCO 1 ,4- diazabicyclo[2.2.2]octane
  • Fascat 4100 ® butyltin hydroxide oxide hydrate
  • MEK methy-ethylketone
  • HFX hexafluoroxylene
  • DMEA ⁇ , ⁇ '- dimethyl-ethanolamine
  • DMEA hexahydrophthalic anhydride, trimellitic anhydride, adipic acid, ethyl chloroacetate, 2-propanol
  • IPA 2-propanol
  • Fomblin ZDOL TX ® PFPE Fomblin ZDOL TX ® PFPE:
  • Hydrofluoroether Novec ® HFE 7500 was purchased from 3M and was used as received.
  • Titrating agent tetramethylammonium hydroxide TMAI 0.1 M in CH3OH Electrode: DG1 15SC Mettler Toledo
  • a glass reactor was charged with IPDI (50 g, 450 meq), Fomblin ZDOL ® PFPE (1 12.8 g, 1 10 meq, containing 5 % on a molar base of monofunctional PFPE alcohol).
  • the reaction mass was warmed up to 50°C, under mechanical stirring, then dibutyltin dilaurate (DBTDL, 0.43 ml, 5% w/w solution in MEK) was added; a spontaneous increase of the internal temperature to 55°C was observed. Thereafter, the temperature was increased to 65°C and kept at this value for two hours.
  • the completion of the reaction was monitored by 19 F-NMR.
  • the excess of IPDI was removed by washing with n-hexane, separation of the bottom fluorinated layer and removal from this layer of the trace of residual solvent by vacuum distillation at 80°C.
  • the amine content measured by titration according to the procedure disclosed in the Methods section, was 0.74 eq/kg; the result of this analysis was in accordance with the 1 H-NMR and GPC analyses and confirmed the obtainment of the target product (I) with 95% purity.
  • This polymer was prepared following the same as in Example 1 , using the reagents and solvents indicated below:
  • DBTDL dibutyltin dilaurate
  • a glass reactor was charged with Fomblin ZDOL TX ® PFPE (103.1 g, 133 meq, with 6% on a molar base of monofunctional PFPE alcohol) and was warmed up to 70°C, under mechanical stirring, and dried under vacuum for 2 hours.
  • Hexahydro-phthalic anhydride (21.3 g, 135 meq) was melt at 40°C and was added in the glass reactor with Fascat 4100 ® butyltin hydroxide oxide hydrate.
  • the reaction mass was warmed up to 130°C and kept at this value for two hours.
  • the completion of the reaction was monitored by 1 H-NMR.
  • the acid content measured by titration as described in the Methods section, was 1.10 eq/kg. All analyses confirmed the obtainment of the target product.
  • This polymer (P1 ) was prepared from Fomblin ZDOL ® PFPE following the procedure described in Example 2 of US 7252740. NMR analyses confirmed the obtainment of a the target product. The Mn of this polymer (PF1 ) determined by NMR analyses was 1 ,950 (Ew 1063) and its purity was 95%.
  • a glass reactor was charged with 20 g (13 meq) poly(dimethylsiloxane), bis(3-aminopropyl) terminated (M n 3,000) and was warmed up to 70°C, under mechanical stirring, and dried under vacuum for two hours.
  • Trimellitic anhydride (3.0g 15 meq) was melt at 40°C and was added in the glass reactor. The reaction mass was warmed up to 130°C and kept at this temperature for two hours. The completion of the reaction was monitored by 1 H-NMR. The acid content, measured by titration according to the procedure described in the Methods section, was 1.19 eq/kg. All analyses confirmed the obtainment of the title product, with a purity higher than 98% and M n 3,350.
  • a glass reactor was charged with Fomblin ® diamine (30 g, 24 meq) and was warmed up to 70°C, under mechanical stirring, and dried under vacuum for two hours. Trimellitic anhydride was melt at 40°C and was added (4.9 g 25 meq) in the glass reactor. The reaction mass was warmed up to 130°C and kept at this temperature for two hours. The completion of the reaction was monitored by 1 H-NMR. The acid content, measured by titration as described in the Methods section, was 1 .38 eq/kg. All analysesconformed the obtainment of the title product with a purity higher than 97% and M n 2,900.
  • Table 2 below reports the ingredients of the compositions and their viscosity.
  • Table 3 compares the actual viscosity value of the compositions with the theoretical values.
  • Theoretical viscosity vas calculated as average of the viscosities of the single polymers, taking into account their reciprocal volume fractions in the composition, according to the following calculation:
  • Theorethical viscosity [Viscosity of (P1 ) x volume fraction of (P1 ) in the composition + viscosity of (P2) x volume fraction of (P2) in the composition]/2
  • Composition (C-3) was added with a mixture of HFE 7500 and IPA at a 10: 1 volume ratio until reaching a solid content of 90% wt (90% wt polymers with respect to the overall weight of the composition).
  • the resulting composition was cast on an iron slab and the solvents were evaporated at 80-100°C for 3 hours. The thickness of the coating was about 50 microns.
  • Composition (C-3) was added with a mixture of Novec® HFE 7500 and IPA at a 10: 1 volume ratio until reaching a solid content of 1 % wt (1 % wt polymers with respect to the overall weight of the composition).
  • the resulting composition was applied by dipping with a dip-coater onto an iron slab and the solvents were evaporated at 80-100°C for 3 hours.
  • the thickness of the coating was lower than 1 micron.
  • Corrosion test 3 Composition (C-5) was added with a mixture of HFE 7500 and IPA at a 10: 1 volume ratio until reaching a solid content of 80% wt. The resulting composition was cast on an iron slab and the solvents were evaporated at 80-100°C for 3 hours. The thickness of the coating was about 40 microns.
  • Composition (C-5) was dissolved in MEK until reaching a solid content of 1 % wt and applied by dipping with a dip-coated onto an iron slab; the solvent was evaporated at 80-100°C for 3 hours. The thickness of the coating was lower than 1 micron.
  • the coated iron slab was immersed in sea water and no corrosion was observed after 24 hours.
  • Test 4 was repeated with the difference that the solid content of the composition dissolved in MEK was 0.1 %wt.

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Abstract

L'invention concerne un procédé de prévention de la corrosion de métaux et d'alliages et des compositions pour la mise en oeuvre du procédé. Le procédé comprend l'application à un métal ou un alliage d'une composition comprenant deux polymères amorphes ionisables ayant une Tg faible. Un premier polymère comprend une chaîne polymère non ionisable ayant deux extrémités, chaque extrémité portant au moins un groupe acide ionisable tandis qu'un second polymère comprend une chaîne polymère non ionisable ayant deux extrémités, chaque extrémité portant au moins un groupe amino ionisable.
PCT/EP2017/077413 2016-10-28 2017-10-26 Procédé de prévention de la corrosion d'articles métalliques Ceased WO2018078001A1 (fr)

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WO2019229187A1 (fr) 2018-05-30 2019-12-05 Solvay Specialty Polymers Italy S.P.A. Composition réversiblement réticulable de polymères ioniques
WO2020030678A1 (fr) 2018-08-10 2020-02-13 Solvay Specialty Polymers Italy S.P.A. Compositions de polymères d'organosiloxane ionisables
EP3685913A1 (fr) * 2019-01-23 2020-07-29 Solvay Specialty Polymers Italy S.p.A. Composition contenant des microcapsules
WO2021105239A1 (fr) * 2019-11-29 2021-06-03 Solvay Specialty Polymers Italy S.P.A. Vêtement auto-réparable

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CN110359035A (zh) * 2019-06-05 2019-10-22 山东青洁能环保有限公司 蒸发式冷凝器用换热列管超分子覆膜方法
CN110359035B (zh) * 2019-06-05 2021-06-08 山东青洁能环保有限公司 蒸发式冷凝器用换热列管超分子覆膜方法
WO2021105239A1 (fr) * 2019-11-29 2021-06-03 Solvay Specialty Polymers Italy S.P.A. Vêtement auto-réparable

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