Classifications

• • 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
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D30/00—Producing pneumatic or solid tyres or parts thereof
  • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
  • B29D30/48—Bead-rings or bead-cores; Treatment thereof prior to building the tyre
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • 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
  • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
  • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
• • 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
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
• • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
  • C08G18/3228—Polyamines acyclic
• • 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
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
  • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
  • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
  • C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
• • 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
  • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
  • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
  • C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
• • 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
  • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
  • C08G18/6453—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having sulfur
• • 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
• • 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
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
  • C08G18/8074—Lactams
• • 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
  • C09D175/02—Polyureas
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/02—Polyureas
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D30/00—Producing pneumatic or solid tyres or parts thereof
  • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
  • B29D30/38—Textile inserts, e.g. cord or canvas layers, for tyres; Treatment of inserts prior to building the tyre
  • B29D2030/383—Chemical treatment of the reinforcing elements, e.g. cords, wires and filamentary materials, to increase the adhesion to the rubber
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D30/00—Producing pneumatic or solid tyres or parts thereof
  • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
  • B29D30/48—Bead-rings or bead-cores; Treatment thereof prior to building the tyre
  • B29D2030/483—Treating the bead cores to increase rubber adhesion
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
  • B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
  • B60C2009/0014—Surface treatments of steel cords
• • 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
  • C08G2115/00—Oligomerisation
  • C08G2115/02—Oligomerisation to isocyanurate groups
• • 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
  • C08G2150/00—Compositions for coatings
  • C08G2150/90—Compositions for anticorrosive coatings
• • 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
  • C08G2380/00—Tyres
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
  • Y10T428/12556—Organic component
  • Y10T428/12569—Synthetic resin
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide

Definitions

• the present invention relates to polymers with urea units, or polyurea, used in particular in adhesive systems intended in particular for bonding metal or glass to rubber.
• Metal / rubber composites in particular for tires, are well known. They generally consist of an unsaturated rubber matrix, generally diene, crosslinkable with sulfur, comprising reinforcing elements (or "reinforcements") of metal such as carbon steel wires, films or cables. Subject to very significant constraints during the rolling of the tires, in particular to repeated compressions, flexions or curvature variations, these composites must in a known manner satisfy a large number of technical criteria, sometimes contradictory, such as uniformity, flexibility, endurance in flexion and compression, tensile, wear and corrosion resistance, and maintain these performances at a very high level as long as possible.
• the traditional method of bonding the rubber compositions to carbon steel is to coat the surface of the steel with brass (copper-zinc alloy), the bond between the steel and the rubber matrix being provided by sulfurization brass when vulcanizing or baking rubber.
• organic rubber or metal complexes such as cobalt salts, as adhesion promoting additives, are generally also used in these rubber compositions.
• manufacturers of metal / rubber composites are looking for new adhesive solutions for bonding metal reinforcements to rubber compositions, while at the same time mitigating, at least in part , the aforementioned disadvantages.
• the invention relates to a polyurea comprising at least urea base units of formula -NH-CO-NH- and additional units, characterized in that these additional units comprise at least on the one hand a secondary alcohol function, on the other hand an ether, thioether or secondary amine function in the alpha position of the secondary alcohol function.
• the metal reinforcements thus coated with the polymer according to the invention, as adhesion primer, have the major advantage that they can then be bonded to unsaturated rubber matrices using simple textile adhesives such as "RFL” adhesives ( resorcinol-formaldehyde-latex) or other equivalent adhesive compositions, or directly (ie without use of such glues) to these unsaturated rubber matrices when the latter contain, for example, suitable functionalized unsaturated elastomers such as elastomers epoxides.
• the invention may be used metal reinforcements coated or not coated with adhesive metal layers such as brass, and surrounding rubber matrices devoid of metal salts, particularly cobalt salts.
• the invention also relates to the use of the polymer according to the invention as an adhesion primer for bonding any substrate, in particular metal such as iron or zinc, or glass, to an unsaturated rubber, such as in particular a diene elastomer. .
• the invention also relates to the use of this polymer as anticorrosive protective coating of a metal substrate or a substrate whose surface is at least partly metallic, in particular in any application where said metal substrate is susceptible to be used in a humid environment.
• the invention also relates per se to any substrate, in particular metal or glass (or at least whose surface comprises metal or glass), which is coated, at least in part, with a polyurea according to the invention. invention.
• the invention relates in particular to any metal reinforcement coated with a polyurea according to the invention. It relates in particular to any wire, cable, film or metal plate at least a portion of the surface is made of brass steel, characterized in that said brass steel is itself coated with a polyurea according to the invention.
• sulfur-containing polyaromatic polyamine structural units whose unit of particular formula (II) corresponds to the more particular formula (II-A) or (II-B) in which "m” is equal to 1 for each group ( CH2) m , and where appropriate Z2 are 1,4-dimethylene cyclohexane, and "n” is 0 ( ⁇ - ⁇ ) or 1 (II-B), respectively (Fig. 2A and 2B);
• Polyurea 2 an example of a sequence (recurring structural unit) of a polymer according to the invention (Polyurea 2), resulting from the reaction of a diisocyanate MDI (or MDI precursor) and a polyamine (Prepolymer 2) (FIG. 7);
• a polyurea is a polymer comprising a plurality of urea bonds (-NH-CO-NH-) resulting in a known manner from the addition reaction of a polyamine having at least two primary amine functions on a polyisocyanate (compound carrying at least two isocyanate functions -NCO), especially on a diisocyanate in the case of a polyurea of the linear type.
• the polyurea polymer of the invention therefore comprising, by definition, urea base units (-NH-CO-NH-), has the essential characteristic of further comprising additional units comprising on the one hand at least one (this is ie one or more secondary alcohol function, on the other hand at least one (ie one or more) ether, thioether or secondary amine function in the ⁇ (alpha) position of the secondary alcohol function (that is to say as a reminder and by known convention, carried by a carbon adjacent to the carbon carrying the secondary alcohol function).
• an essential characteristic of the polyurea of the invention is that its additional units comprise at least one ⁇ -hydroxy-ether, ⁇ -hydroxy-thioether or ⁇ -hydroxy-amine unit (secondary amine).
• Polyurea is understood to mean any homopolymer or copolymer, especially a block copolymer, having the additional units above and urea units.
• the additional units comprise at least one unit denoted "M" of formula (A) chosen from the formulas:
• R 1 is an aliphatic group, still more preferably an alkyl group. More particularly, R 1 is alkyl having 1 to 5 carbon atoms, which alkyl may be substituted or unsubstituted; even more particularly, R 1 represents a methyl or an ethyl, especially a methyl.
• R 2 is an aliphatic group, more preferably an alkylidene group. More particularly, R 2 is an alkylidene having 1 to 5 carbon atoms, this alkylidene may be substituted or unsubstituted; still more particularly, R 2 represents a methylidene.
• F n represents NH, that is to say that the additional units in this case comprise at least one secondary alcohol function and a secondary alpha amino function one of the other.
• the corresponding formulas (A1), (A-2) and (A-3) have been shown below in expanded form:
• M units may be described respectively as ⁇ - ⁇ '-dihydroxy-ether, - ⁇ '-dihydroxy-thioether or ⁇ - ⁇ '-dihydroxy-amine (secondary amine) units, depending on the nature of the F n (respectively O, S or NH).
• F represents NH and the additional units comprise at least one unit of formula (A-1); in other words, in such a case, the general motif "M” is the particular motif denoted "M1" of formula:
• the additional units comprise, in addition to the "M1" unit above, one minus one (that is to say one or more) sulfur atom; in the case where several sulfur atoms are present, the latter can be isolated or in the form of polysulfides.
• each sulfur atom is present in the form of a group of formula -S x -R in which "x" is preferably an integer of 1 to 8 and R represents hydrogen or a group hydrocarbon containing a heteroatom, preferably having 1 to 10 carbon atoms.
• This sulfur atom or this sulfur group may be incorporated in an aliphatic group, for example comprising 1 to 30, more particularly 1 to 20 carbon atoms, or a cycloaliphatic group, for example comprising 3 to 30, more particularly 3 to 20 carbon atoms. More preferably, this sulfur atom, in particular in the form of the group of formula -S x -R above, is present on an aromatic group, the latter preferably having 6 to 30, more preferably 6 to 20 carbon atoms.
• polyurea which is particularly preferred, in which the additional units comprise at least one (that is to say one or more) "Ml" unit as described above and at least one (this is one or more) sulfur atom present on at least one (that is to say one or more) aromatic group, is a polyurea comprising at least recurring structural units of the polyaromatic sulfur-containing polyamine type which each comprise at least one one less than one of formula (I):
• N represents an integer equal to zero or nonzero
• Z 1 and Z 2 which are identical or different, represent a divalent linking group comprising from 1 to 30 carbon atoms;
• Ar 1 , Ar 2 and Ar 3 which are identical or different, represent a phenylene group, at least one of these phenylene groups carrying one, two, three or four groups of formula -S x -R in which "x" is a integer from 1 to 8 and R represents hydrogen or a hydrocarbon group, which may comprise a heteroatom, having from 1 to 10 carbon atoms.
• Polyurea according to the invention which is particularly preferred, must therefore be understood to mean any homopolymer or copolymer, in particular a block copolymer, comprising the structural units with a unit of formula (I) above and urea units (-NH-CO-NH- ).
• x is an integer of 1 to 8, preferably 1 to 4, more preferably 1 or 2, more particularly 1.
• R represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, substituted or unsubstituted, which may comprise a heteroatom such as S, O or N.
• R is an aliphatic group, more preferably an alkyl group. More more preferably, R is an alkyl having 1 to 5 carbon atoms, which alkyl may be substituted or unsubstituted; more particularly, R represents a methyl or an ethyl, even more particularly a methyl.
• R represents hydrogen
• the skilled person will understand that, during the synthesis of the corresponding prepolymer, by reaction of a starting diamine (for example monomer A below) on a diepoxy compound (for example Monomer B hereinafter), the thiol -SH group may be protected against any parasitic reaction with this diepoxy, in a known manner, by a blocking group suitable and known to those skilled in the art, for example as shown in the formulas below:
• each of the groups Ari, Ar 2 and Ar 3 which are identical or different, carries one, two, three or four groups of formula -S x -R, in particular of two groups -SR (x equal to 1) in which R is an alkyl having from 1 to 5 carbon atoms, R being more particularly a methyl or an ethyl, more particularly a methyl.
• Ar l5 Ar 2 and Ar 3 which are identical or different, are each carrying two -S x -R groups, in particular two -SR groups (x equal to 1) in which R is a alkyl having 1 to 5 carbon atoms, R being more particularly a methyl or an ethyl, more particularly a methyl. More preferably still, in such a case, the two groups (-SR), in particular (-SCH 3 ) are in position meta (or position -1,3) with respect to each other on each phenylene group Ar .
• the numbers “m” may be identical or different from one group (CH 2 ) m to another; preferably, each number “m” is equal to 1 or 2, more preferably equal to 1.
• Z 1 and Z 2 which may be identical or different, represent a divalent linking group, preferably a hydrocarbon group, but which may also contain a heteroatom such as S, O or N; they can be substituted or not, saturated or unsaturated; they contain from 1 to 30, preferably from 2 to 20 carbon atoms, more preferably from 2 to 10 carbon atoms. More preferentially, Z 1 and Z 2 represent an aliphatic group comprising from 2 to 20 carbon atoms or cycloaliphatic atoms containing from 3 to 20 carbon atoms, even more preferentially an aliphatic or cycloaliphatic group containing from 3 to 10 carbon atoms. Among these more preferential groups, there will be mentioned in particular 1,4-dimethylene cyclohexane, of formula:
• n is equal to 1 or greater than 1; when “n” is greater than 1, it is in particular comprised in a range from 2 to 20, more preferably from 2 to 10, in particular from 2 to 5.
• the divalent phenylenediamino groups (-HN-Ari-NH-, -HN-Ar 2 -NH- and -HN-AT 3 -H-) may be the same or different.
• the two amino groups (NH) may be in the meta, ortho or para position relative to one another.
• the two amino groups (NH) are in meta position (or -1,3 position) relative to each other.
• the unit of general formula (I) therefore has for structural formula (II) that which has been represented in the appended FIG.
• the divalent phenylenediamino groups (-HN-Ari-NH-, -HN-Ar 2 -NH- and -HN-Ar 3 -NH-), which are identical or different, are chosen among the compounds 3,5-dimethylthio-2,4-toluenediamine, 3,5-dimethylthio-2,6-toluenediamine and mixtures thereof, respectively corresponding to formulas (III-a) and (III-b) below:
• each phenylenediamine group has, for example, the formula (III-a) above for the particular formula
• the formulas (II-A) and (II-B) above then have the following formula: respective particular formulas formulas (II-C) and (II-D) respectively illustrated in Figures 3A and 3B appended.
• the sulfur-containing polyaromatic polyamine-containing structural amine units of formula (I) which have been previously described and the basic unit units with urea units (-NH-CO-H -) are connected to each other in a pattern corresponding to formula (IV) below:
• ATI, Ar 2, X, 'n', 'm' and Z ⁇ have the meanings given above;
• Y represents the sequence:
• Z 3 represents a divalent aliphatic, cycloaliphatic or aromatic linking group, the aliphatic group preferably having 1 to 30 (more preferably 1 to 20) carbon atoms, the cycloaliphatic group preferably from 3 to 30 (more preferably 3 to 20) carbon atoms, the aromatic group from 6 to 30 (more preferably 6 to 20) carbon atoms.
• the polyurea polymer of the invention is preferably a polymer of the linear type, thus resulting essentially from the addition of a polyamine having only two primary amine functions and a diisocyanate.
• the diisocyanate used may be aromatic or aliphatic; it may be a monomer, a prepolymer or quasi-prepolymer, or even a polymer.
• the diisocyanate from which the polymer of the invention is derived is selected from the group consisting of the following aromatic compounds: diphenylmethane diisocyanate (abbreviated "MDI”), toluene diisocyanate (“TDI”), naphthalene diisocyanate (“NDI”), 3,3'-bitoluene diisocyanate (“TODI”), para-phenylene diisocyanate (“PPDI”), their different isomers, and mixtures of these compounds and / or isomers.
• MDI diphenylmethane diisocyanate
• TDI toluene diisocyanate
• NDI naphthalene diisocyanate
• TODI 3,3'-bitoluene diisocyanate
• PPDI para-phenylene diisocyanate
• an MDI or a TDI is used, more preferably still an MDI.
• MDI All isomers of MDI (in particular 2,2'-MDI, 2,4'-MDI, 4,4'-MDI) and their mixtures are usable, as well as so-called polymeric MDIs (or "PMDI") comprising oligo-mothers. of the following formula (with p equal to or greater than 1):
• aliphatic diisocyanate compounds such as, for example, 1,4-tetramethylene diisocyanate, 1,6-hexane diisocyanate (“HDI”), 1,4-bis (isocyanatomethyl) -cyclohexane, 1,3-bis (isocyanatomethyl) -cyclohexane, 1,3-bis (isocyanatomethyl) benzene, 1,4-bis (isocyanatomethyl) benzene, isophorone diisocyanate (“IPDI”), bis (4-iso-cyanatocyclohexyl) methane diisocyanate (“H12MDI”), 4,4'-dicyclohexylmethane diisocyanate (“H13MDI”).
• HDI 1,4-tetramethylene diisocyanate
• HDI 1,4-bis (isocyanatomethyl) -cyclohexane
• the diisocyanate used is 4,4'-MDI (4,4'-diphenylmethane diisocyanate) having the formula: or, if several diisocyanates are used, is the majority diisocyanate by weight, preferably representing in the latter case more than 50% of the total weight of the diisocyanate compounds.
• the invention is not limited to a polyurea of the linear type (as a reminder, in the case of a diisocyanate), it may also be used, in particular in order to increase the Tg of the polymer of the invention by forming a three-dimensional network, a triisocyanate compound such as for example a trimer of MDI triazine ring of formula below:
• FIGS. 4 to 9 represent preferred examples of polyureas according to the invention as well as various possible synthetic schemes of these polymers.
• FIG. 4 represents an example of a sequence of a polymer (hereinafter “Polyurea”) according to the invention, resulting from the reaction of an MDI monomer and a starting diamine. (hereinafter "Prepolymer 1”) of general formula:
• FIG. 7 represents another example of linking of a polymer ("Polyurea 2") according to the invention, resulting from the reaction of an MDI monomer and another starting diamine (hereinafter "prepolymer”). 2 ”) of the general formula:
• Ar 1; Ar 2 , Ar 3 , and Z 2 have the general definitions previously given for the units of formula (I), and more particularly the characteristics corresponding to the final unit of formula ( ⁇ - ⁇ ), namely that the two amino groups are in the meta position, one per ratio to each other on each phenylene group (Ari, Ar 2 and Ar 3 ), "m” is equal to 1 for each group (CH 2 ) m , "n” is equal to 1 and Z 1 and Z 2 represent the 1,4-dimethylene cyclohexane.
• FIGS 8 and 9 illustrate examples of methods that can be used for the synthesis of Prepolymer 2 and Polyurea 2, respectively, which processes will be described in detail later.
• the polymer of the invention may comprise from ten to several hundred, preferably from 20 to 200 structural units with a unit of formula (I), in particular structural units as represented by way of examples in FIGS. 7 and 9.
• Its glass transition temperature Tg measured by DSC (Differential Scanning Calorimetry), for example according to ASTM D3418, is preferably greater than 50 ° C., more preferably greater than 100 ° C., in particular between 130 ° C. and 250 ° C. .
• this polymer of the invention is advantageously usable as a hydrophobic coating on any type of substrate, especially metal or glass, or as adhesion primer on any type of metal reinforcement, such as for example a wire, a film, a plate or a cable of carbon steel, brass or non-brass, particularly intended to reinforce an unsaturated rubber matrix such as natural rubber. 5.
• metal reinforcement such as for example a wire, a film, a plate or a cable of carbon steel, brass or non-brass, particularly intended to reinforce an unsaturated rubber matrix such as natural rubber.
• Prepolymers 1 and 2 also respectively denoted Monomers C1 and C2, from Monomer A and Monomer B, then those of Polyureas 1 and 2 from the respective Prepolymers 1 and 2 ( C1 and C2 monomers) and a D monomer (blocked MDI caprolactam). Then are described syntheses of two other polymers according to the invention (Polyureas 3 and 4).
• Prepolymers 1 and 2 (also called Monomers C1 and C2), whose respective formulas are given in FIGS. 5 and 8, were prepared from two monomers A and B, according to the procedures schematized in FIGS. 5 and 8, as explained in detail below.
• the monomer A is the product "Ethacure 300" (supplier Albemarle, Belgium), available in the form of a relatively viscous liquid, of brownish color; About 96% is composed of a mixture of 3,5-bis (methylthio) -2,4-toluenediamine isomers and 3,5-bis (methylthio) 2,6-toluenediamine (weight ratio of about 4 / 1 according to chromatographic analysis).
• Monomer B is 1,4-cyclohexane dimethanol diglycidyl ether (abbreviated "CHXDE”) (Aldrich supplier, Switzerland), available as a technical grade (about 61% of a mixture of cis / trans diepoxides). According to the available technical data (see for example US 201/00039982), CHXDE is a complex chemical mixture containing diepoxides (about 61%), residual cyclohexane dimethanol (about 2%), monoepoxides (about 8%) and finally polymeric epoxide species (about 29%). According to the NMR analysis, the epoxide equivalent weight "EEW” (epoxide equivalent weight) of the compound used here is equal to about 159 (theoretical EEW equal to 128 in the case of a pure compound).
• EW epoxide equivalent weight
• both Monomers A and B above were first purified as follows.
• the product "Ethacure 300" (about 40 g) is deposited in a chromatography column (700 g of silica); a hexane / dichloromethane / ethyl acetate solvent mixture (10: 8: 2 ratio) is used as the mobile phase.
• the 2,4-toluenediamine isomer is eluted first followed by the second 2,6-toluenediamine isomer. Under these conditions, the impurities (green-blue color) are not eluted and can be easily separated from the targeted constituents.
• Prepolymer 2 (C2 Monomer) was similarly prepared from the same two compounds (150 mg of Monomer A and 180 mg of Monomer B), the mixture being heated at 170 ° C for one and a half hours (without solvent THF) in a 25 ml flask equipped with a condenser, the reaction being carried out in air.
• the reaction product thus obtained (Prepolymer 2 or C2 Monomer) had a Tg of about + 31 ° C (second DSC pass).
• the thin layer of polyurea 1 thus obtained revealed an excellent adhesion to the glass (impossibility of separating the glass polymer by pulling).
• This Polyurea PI analyzed by DSC, had a Tg of about 190 ° C. (second pass).
• Prepolymer 2 (Monomer C2, 0.702 mmol) was partially dissolved in 12 ml of DTP heated initially for 2 min at about 110 ° C; then, by heating the medium at 170 ° C for 30 min, a well soluble product is obtained. 336 mg of Monomer D (0.702 mmol) were then added and mixed into an agitator (vortex device) until the Monomer D was completely dissolved.
• the final Polyurea 2 thus obtained in the form of a thin film, revealed excellent adhesion to the steel plate (impossibility of pulling the polymer away from the metal).
• This Polyurea 2 analyzed by DSC between -80 ° C. and + 200 ° C. (at a ramp of 10 ° C./min) had a Tg of approximately 160 ° C. (second pass).
• Test 3 Adhesion tests in a metal / rubber composite
• Polyurea 1 was prepared as described above and illustrated in FIG. 4, this time by simultaneous reaction of Monomers A (150.5 mg), B (180 mg) and D (336 mg), in dissolving the 3 compounds in 8 ml of DPT, without using THF solvent and without going through the Prepolymer 1 step. After the compounds dissolved in the DPT, 0.1 ml of the solution was uniformly deposited on a brass-coated steel strip (steel with carbon content equal to about 1%) of dimensions 10 cm ⁇ 0.5 cm ⁇ 0.2 mm; then the whole was placed in an oven at 175 ° C (air ventilation) for 15 min, then an additional 15 min at 175 ° C under vacuum.
• Monomers A 150.5 mg
• B 180 mg
• D 336 mg
• 0.1 ml of the solution was uniformly deposited on a brass-coated steel strip (steel with carbon content equal to about 1%) of dimensions 10 cm ⁇ 0.5 cm ⁇ 0.2 mm; then the whole was placed in an oven at 175 ° C (
• the brass steel strip thus coated with the Polyurea film 1 itself covered with the thin layer of ENR was then placed in a conventional rubber composition for tourism tire belt reinforcement, based on natural rubber, carbon black and silica as a filler, and a vulcanization system (sulfur and sulfenamide accelerator); this composition being free of cobalt salt. Then the metal / rubber composite specimen thus prepared was placed in a press and baked (vulcanized) at 165 ° C for 30 min at a pressure of 20 bar.
• a new polymer according to the invention (Polyurea 3) was synthesized by reaction in solution (solvent DTP) of Monomer C (Prepolymer 1, addition product of monomers A and B both used in this assay in purified form) with solid MDI (here in unblocked form, Sigma Aldrich), according to the following procedure.
• solvent DTP solvent to which Monomer C (Prepolymer 1, addition product of monomers A and B both used in this assay in purified form) with solid MDI (here in unblocked form, Sigma Aldrich), according to the following procedure.
• solvent DTP solvent
• Prepolymer 1 Prepolymer 1, addition product of monomers A and B both used in this assay in purified form
• solid MDI here in unblocked form, Sigma Aldrich
• a first solution of 1.5 g of 3,5-bis (methylthio) -2,4-toluenediamine was prepared in 30 ml of DTP which was placed in an addition funnel and a second solution of 1.75 g of diphenylmethane diisocyanate (MDI) dissolved in 30 ml of DTP and placed in a second addition funnel, all under nitrogen.
• MDI diphenylmethane diisocyanate
• the yellow transparent solution (1.5 ml) thus obtained was deposited on a glass plate (10 cm ⁇ 10 cm) in a uniform manner and then placed in an oven at 170 ° C. (air ventilation) for 15 min. followed by treatment for 15 min at 190 ° C under vacuum to remove any trace of solvent.
• the final Polyurea 3 thus obtained in the form of a thin film, revealed excellent adhesion on the one hand to the glass (impossibility of separating the glass from the glass by pulling), on the other hand in a metal composite specimen ( brass steel plate) / rubber (systematic failure in the rubber matrix) as previously described.
• polymer (Polyurea 3) was precipitated by pouring, with stirring, 20 ml of the preceding yellow polymer solution into a mixture of solvent (800 ml) hexane / 2-propanol (ratio 1/1), then cooling everything between 0 and + 5 ° C for 1 hour.
• the white precipitate in powder form was then isolated by filtration and then dried in an oven at 60 ° C under vacuum for 2 hours.
• To the white solid was added 5 ml of acetone and the soluble residues were thus extracted from the polymer at 40 ° C for 1 min. This operation was repeated twice.
• Polyurea 3 thus purified showed no residue of 3,5-bis (methylthio) -2,4-toluene diamine.
• Polyurea as amended (Polyurea 4), containing additional units polyoxazolidine, was then analyzed by DSC between 80 ° C and 330 ° C: it exhibited a Tg of about 233 ° C on the 2nd passage and about 244 ° C DSC 3rd pass. It was stable up to 280 ° C with partial decomposition above 300 ° C (endothermic).
• the preceding tests demonstrate that the polyurea polymer of the invention, characterized in particular by a high glass transition temperature, a high thermal and chemical stability, has excellent adhesion to glass or metal.
• this polymer used in particular as a metal adhesion primer in metal / rubber composites, this polymer very advantageously makes it possible to bond the metal to the rubber matrices by using simple textile glues such as "RFL" (resorcinolformaldehyde latex) glues. or other equivalent adhesive compositions, or directly (i.e., without use of such glues) to these rubber matrices when the latter contain, for example, suitable functionalized unsaturated elastomers such as epoxidized elastomers.
• RTL resorcinolformaldehyde latex
• cobalt salts or other metal salts in the rubber compositions intended to be connected to brass-plated metal reinforcements.

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