Classifications

• • 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
• • 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
  • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
  • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
  • B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/10—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an adhesive surface
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
• • 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
  • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
  • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
  • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
  • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
• • 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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl 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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
• • 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
  • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
  • C09D181/02—Polythioethers; Polythioether-ethers
• • 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
  • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
  • C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
• • 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
  • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
  • C09J179/02—Polyamines
• • 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
  • C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
  • C09J181/02—Polythioethers; Polythioether-ethers
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B1/00—Constructional features of ropes or cables
  • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
  • D07B1/0606—Reinforcing cords for rubber or plastic articles
  • D07B1/0666—Reinforcing cords for rubber or plastic articles the wires being characterised by an anti-corrosive or adhesion promoting coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2202/00—Metallic substrate
  • B05D2202/10—Metallic substrate based on Fe
  • B05D2202/15—Stainless steel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
  • B32B5/022—Non-woven fabric
• • 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
• • 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
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B1/00—Constructional features of ropes or cables
  • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
  • D07B1/0606—Reinforcing cords for rubber or plastic articles

Definitions

• the present invention relates to thermosetting resins, useful in particular in adhesive systems intended in particular for bonding metal to rubber.
• It relates more particularly to metal or metallized reinforcements coated with polymers that can be used as adhesive layers in metal / rubber composites intended for the manufacture of rubber articles such as tires, pneumatic or non-pneumatic, for motor vehicles.
• Metal / rubber composites particularly for motor vehicle tires, are well known. They are most often made of a generally diene rubber matrix, crosslinkable with sulfur, comprising reinforcing elements (or “reinforcements”) metal such as son, films, ribbons or cables made of carbon steel.
• 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.
• the manufacturers of metal / rubber composites are in search of new adhesive solutions for bonding the metal reinforcements to the rubber compositions, while mitigating, at least in part, the aforementioned disadvantages.
• thermosetting type which at room temperature has the same adhesive performance, vis-à-vis the metal and rubber, than the aforementioned polymers but which has once thermoset (crosslinked) further improved thermal and chemical stability
• its specific microstructure very advantageously makes it possible to adjust the flexibility of the molecule according to the particular applications targeted.
• the present invention relates to a metallic or metallized reinforcement, at least the surface of which is at least partly metallic, at least said metal part being coated with a polybenzoxazine comprising at least one repeating units comprising at least one unit corresponding to the formulas ( I) or (II):
• Z 1 represents an at least divalent, aliphatic, cycloaliphatic or aromatic linking group comprising at least one carbon atom and optionally at least one heteroatom selected from O, S, N and P;
• - Xi and X 2 identical or different, represent O or S;
• Ar 2 identical or different, represent a phenylene group, substituted or unsubstituted
• Z 2 represents O or (S) n , the symbol "n" representing an integer equal to 1 or greater than 1.
• the invention relates in particular to such a reinforcement in the form of a wire, film, ribbon or cable, at least part of the surface of which is made of steel, in particular of carbon steel, said steel being able to be a clear steel, that is to say uncoated, or to be coated with at least a second metal called surface metal, the latter being preferably chosen from the group consisting of aluminum, copper, zinc and the alloys of at least one of these metals with at least one other metal.
• the reinforcement of the invention is able to stick to matrices of ethylenically unsaturated polymers such as rubber, this in particular without the need for the use of cobalt salts in these polymer matrices.
• the invention also relates to the use of such a reinforcement for the reinforcement of a rubber article, in particular a pneumatic or non-pneumatic tire for a motor vehicle.
• the invention also relates to any article of rubber, in the uncured state (uncured) or cooked (in the crosslinked state), in particular any tire, pneumatic or non-pneumatic, for a motor vehicle, which is reinforced by at least such a reinforcement.
• the invention as well as its advantages will be readily understood in the light of the detailed description and the following exemplary embodiments, as well as figures relating to these examples which represent or schematize: the general principle of synthesis of a benzoxazine compound with from three compounds, phenol, formaldehyde and amine (R residue of the amine) (Fig. la);
• polybenzoxazine (Polymer noted here P ') suitable for reinforcing the invention of FIG. 9 once its oxazine rings open after heat treatment of Polymer P ( Figure 13); the particular polybenzoxazine (Polymer noted ⁇ -) suitable for the reinforcement of the invention of FIG. 10, after opening its oxazine rings after heat treatment of Polymer P-1 (Fig. 14);
• FIG 18 in radial section, an example of a bandage according to the invention, incorporating a reinforcement according to the invention (FIG 18).
• benzoxazines are compounds of general formula:
• the appended figure recalls the general principle of synthesis of a benzoxazine, here from (condensation reaction) of a molecule of phenol, two molecules of formaldehyde and an amine (R denoting the residue of the amine) , with elimination of two molecules of water.
• Figure lb recalls the opening mechanism ("ring-opening") of the oxazine ring of such a compound during a thermal contribution (represented by the symbol ⁇ ).
• ring-opening the opening mechanism of the oxazine ring of such a compound during a thermal contribution
• Many benzoxazine compounds or monomers can thus be synthesized using various phenols and amines depending on their types of substituents. These substituent groups can then provide polymerizable sites and allow the synthesis of various benzoxazine (or polybenzoxazines) polymers.
• Benzoxazines and polybenzoxazines derived therefrom are products now well known to those skilled in the art; to mention just a few examples of publication, mention may be made of the articles "Polybenzoxazines - New high performance thermosetting resins: synthesis and properties"; N. N. Ghosh et al, Prog. Polym. Sci. 32 (2007), 1344-1391, or "Recent Advancement on Poly 'Benzoxazine - A Newly Developed High Performance Thermoset", Y. Yaggi et al., J. Polym. Sci. Part A: Polym. Chem. : Flight. 47 (2009), 5565-5576, as well as for example patents or patent applications US 5,543,516, WO 2013/148408.
• the polybenzoxazines have the remarkable capacity, at high temperature (for example, typically above 150 ° C or even 200 ° C depending on their particular micro structure), to open their oxazine and thus to lead to structures of polyphenolic thermosetting resins.
• the specific polybenzoxazine suitable for reinforcing the invention is derived from a benzoxazine (hereinafter referred to as "Monomer M") of the halogenated type which has the following generic formula (A), "Hal” representing a (at least one , that is to say one or more) halogen:
• FIG. 2 gives the general synthesis scheme, under thermal contribution and with removal of water, from a halogenated phenol, p-formaldehyde and a diamine.
• Z 1 represents a linking group (spacer or spacer) that is at least divalent, that is to say that it could comprise more than two covalent bonds, for example three or four bonds. covalent. Preferably, is divalent, that is, contains only two covalent bonds.
• Zi can be aliphatic, cycloaliphatic or aromatic. This group, which may be ethylenically saturated or unsaturated, comprises by definition at least one (that is to say one or more) carbon atom, and optionally at least one (that is to say one or more) heteroatom selected from O (oxygen), S (sulfur), N (nitrogen) and P (phosphorus).
• an aliphatic group comprising 1 to 20, more preferably 1 to 16, in particular 1 to 12 carbon atoms, or a cycloaliphatic group comprising 3 to 20, more preferably 3 to 16, in particular 3 to 12 carbon atoms. More preferably still, represents a C1-C20, preferably C1-C16, in particular C1-C12, alkylene group.
• Each benzene ring of the M monomer carries at least one (i.e. one or more) halogen.
• one or more hydrogen atoms of at least one or of each benzene ring may be substituted (or not) by different substituents, for example by functional groups which may promote adhesion of the polymer to the metal and / or rubber.
• each benzene ring of the monomer M carries a single halogen (Hal) or at most two, more preferably one and only one halogen, the latter being more preferably located in the para position of oxygen. of the oxazine cycle.
• Hal halogen
• Hal represents bromine
• FIG. 3 illustrates a possible synthetic scheme, starting from a specific diamine of the aliphatic type (polyethylene diamine), of a particular halogenated benzoxazine of formula (A-1), this benzoxazine being usable as a monomer (Monomer noted as Ml) for the subsequent synthesis of a polybenzoxazine suitable for the reinforcement according to the invention.
• Ml halogenated benzoxazine of formula
• FIG. 4 illustrates another possible synthesis scheme, this time from a specific diamine of the aromatic type (p-xylylenediamine), of another example of a particular halogenated benzoxazine of formula (A-2), usable as a monomer (Monomer noted M-2) for the subsequent synthesis of another polybenzoxazine suitable for reinforcing the invention.
• Figures 5, 6 and 7 illustrate three other possible synthetic schemes, always from halogenated phenol and paraformaldehyde on the one hand, and on the other hand different specific diamines, all of the aliphatic type, other examples of benzoxazines particular of the respective formulas (A-3), (A-4) and (A-5), usable as monomers (Monomers respectively denoted M-3, M-4 and M-5) for the synthesis of polybenzoxazines suitable for the reinforcement of the invention.
• FIG. 8 illustrates another possible synthetic scheme, starting from a halogenated phenol, paraformaldehyde and a specific aliphatic polyamine, this time consisting of a triamine, tris (3-aminopropyl) amine, of another example of a compound (Halogenated) benzoxazine particular of formula (A-6) usable as a monomer (Monomer noted M-6) for the synthesis of another polybenzoxazine suitable for the reinforcement of the invention.
• a halogenated phenol, paraformaldehyde and a specific aliphatic polyamine this time consisting of a triamine, tris (3-aminopropyl) amine, of another example of a compound (Halogenated) benzoxazine particular of formula (A-6) usable as a monomer (Monomer noted M-6) for the synthesis of another polybenzoxazine suitable for the reinforcement of the invention.
• the polybenzoxazine (“P" polymer) that is suitable for the reinforcement of the invention therefore has the essential characteristic of comprising recurring structural units comprising at least one unit corresponding to formula (I) (before opening the oxazine rings) or formula (II) ( after opening cycles) below: I) H)
• Zi has the main definition and the preferential definitions already given previously for the compound (monomer) benzoxazine;
• Xi and X 2 identical or different, represent O (oxygen) or S (sulfur);
• Z 2 represents O or (S) n , the symbol "n” representing an integer equal to 1 (case of a single sulfur atom) or greater than 1 (case of several sulfur atoms).
• polymer is intended to be understood herein any homopolymer or copolymer, especially a block copolymer, with recurring structural units comprising at least one unit of formula (I) or (II) above; the polymer of the invention can of course comprise both units of formula (I) and units of formula (II).
• FIG. 9 represents a general scheme for the synthesis, by polycondensation, of such a polybenzoxazine (Polymer P) that is suitable for the invention, from the halogenated benzoxazine of formula (A) of FIG. 2 (M monomer) and another monomer, of generic formula denoted (B), which has the characteristic of being of the aromatic diol or thiol type (generic monomer denoted "N").
• Ar 2 each represent an unsubstituted benzene ring
• X 1 and X 2 each represent either a sulfur atom or an oxygen atom
• Z 2 represents O or S (ie "n" equal to 1), more preferably S;
• Zi represents (CH 2 ) X in which "x" preferably varies from 1 to 20, more preferably from 1 to 16, in particular from 1 to 12. More preferentially, it is the set of preferential characteristics above which is checked simultaneously.
• one or more hydrogen atoms of at least one or each benzene ring Ari and Ar 2 could be substituted (or not) by a single or more substituents, identical or different, for example by functional groups capable of promoting the adhesion of the polymer to the metal and / or rubber.
• FIG. 10 represents a particular synthetic scheme of a specific polybenzoxazine (Polymer denoted by P1) of formula (1-1) that is suitable for the reinforcement according to the invention, from a particular halogenated benzoxazine (Monomer M-7) of formula (A-7) and another specific monomer (Nl Monomer) of formula (B1) of the sulfur aromatic diol type (4,4'-thiodiphenol).
• P1 polybenzoxazine
• A-7 halogenated benzoxazine
• Nl Monomer another specific monomer of formula (B1) of the sulfur aromatic diol type (4,4'-thiodiphenol).
• each benzene ring of monomer M-7 carries one and only one halogen (Hal), more preferably bromine, this halogen being more particularly located in the para position of the oxygen of the oxazine ring.
• Hal halogen
• the polybenzoxazine of the reinforcement of the invention is characterized by recurring units comprising at least one unit corresponding to the particular formulas (1-1) (before opening the benzoxazine rings) or (II-1 ) (after opening cycles): 1-1)
• FIG. 11 represents another particular synthetic scheme of another specific polybenzoxazine (Polymer denoted P-2) suitable for the invention, of formula (1-2), from the specific halogenated benzoxazine (Monomer M-7) preceding and another specific monomer (Monomer N-2) of formula (B-2), aromatic thiol type (also carrying an ether function).
• FIG. 12 represents another particular synthetic scheme of another specific polybenzoxazine (Polymer denoted P-3) suitable for the reinforcement according to the invention, of formula (1-3), from the specific halogenated benzoxazine (Monomer M- 7) and another specific monomer (Monomer B2) of the aromatic thiol type (additionally carrying a thioether function).
• Polymer denoted P-3 suitable for the reinforcement according to the invention, of formula (1-3), from the specific halogenated benzoxazine (Monomer M- 7) and another specific monomer (Monomer B2) of the aromatic thiol type (additionally carrying a thioether function).
• each benzene ring of M-7 Monomer carries one and one only halogen (Hal), more preferably bromine, located more particularly in the para position of the oxygen of the oxazine ring.
• Hal halogen
• FIGS. 13 and 14 also represent the polybenzoxazines that are suitable for the reinforcement according to the invention (here respectively denoted P 'and ⁇ - ⁇ ) of FIGS. 9 and FIG. 10, once their oxazine cycles open.
• the polybenzoxazine of the reinforcement of the invention may comprise from ten to several hundred, preferably from 50 to 300 structural units with units of formula (I) and / or (II), in particular structural units as represented by examples in Figures 10 to 14 and 17.
• the polybenzoxazine of the invention is advantageously usable, as an adhesion primer or as a single adhesive layer, for coating the reinforcement of the invention and adhering the latter to rubber.
• any known adhesive system for example a conventional textile glue of the RFL type comprising at least one diene elastomer such as natural rubber, or any equivalent adhesive known to impart adhesion satisfactory between rubber and conventional polymers such as polyester or polyamide, such as for example the adhesive compositions described in patent applications WO 2013/017421, WO 2013/017422, WO 2013/017423, WO 2015/007641, WO 2015 / 007,642.
• a physical treatment may consist, for example, of a treatment by radiation such as an electron beam or by plasma; a chemical treatment may for example consist of a prior passage in an epoxy resin bath and / or isocyanate compound.
• connection between the metal reinforcement provided with its polybenzoxazine layer and the rubber layer with which it is in contact will be definitively ensured during the final curing (crosslinking) of the rubber article concerned. .
• the polybenzoxazine described above can be used especially on any type of metal reinforcement, typically of the filiform type such as for example a wire, a film (by convention, having a width greater than 5 cm), a ribbon (by convention narrower film of width at most equal to 5 cm) or a steel cable, in particular carbon steel, intended in particular to reinforce an unsaturated rubber matrix such as natural rubber.
• metal reinforcement typically of the filiform type such as for example a wire, a film (by convention, having a width greater than 5 cm), a ribbon (by convention narrower film of width at most equal to 5 cm) or a steel cable, in particular carbon steel, intended in particular to reinforce an unsaturated rubber matrix such as natural rubber.
• the steel especially carbon steel, may be a clear steel, that is to say uncoated, or coated at least in part with at least one layer (thus intermediate layer, arranged between steel and polybenzoxazine layer) a second metal known as a surface metal, said surface metal being preferably selected from the group consisting of aluminum, copper, zinc and the alloys of at least one of these metals with at least one other metal (belonging to this group or not).
• a second metal known as a surface metal
• the surface metal is brass.
• Carbon steel is preferentially as commonly used in steel cords for motor vehicle tires; but it is of course possible to use other steels, for example stainless steels.
• carbon steel When carbon steel is used, its carbon content is preferably between 0.4% and 1.2%, especially between 0.5% and 1.1%.
• the invention applies in particular to any steel of the type Steel cord with standard resistance (called “NT” for “Normal Tensile”), with high resistance (called “HT” for “High Tensile”), with very high resistance ( said “SHT” for “Super High Tensile”) as ultra high resistance (called “UHT” for “Ultra High Tensile”).
• the invention also relates to any rubber article, in the green (that is to say uncrosslinked) or baked (in the crosslinked state), in particular any pneumatic or non-pneumatic tire for a motor vehicle, comprising a reinforcement according to the invention.
• This bandage of the invention can be intended for all types of motor vehicles, in particular passenger vehicles or industrial vehicles such as heavy vehicles, civil engineering, other commercial vehicles transport or handling.
• FIG. 18 very schematically shows (without respecting a specific scale) a radial section of a tire according to the invention, for example for a motor vehicle of the tourism type or for a vehicle heavy.
• This tire 1 has a crown 2 reinforced by a crown reinforcement or belt 6, two sides 3 and two beads 4, each of these beads 4 being reinforced with a rod 5.
• the crown 2 is surmounted by a tread not shown in this schematic figure.
• a carcass reinforcement 7 is wound around the two rods 5 in each bead 4, the upturn 8 of this armature 7 being for example disposed towards the outside of the tire 1 which is shown here mounted on its rim 9.
• the carcass reinforcement 7 is in known manner constituted for example by at least one rubber ply reinforced by so-called "radial" reinforcements, that is to say that these reinforcements are arranged substantially parallel to each other and extend from one bead to the other so as to form an angle of between 80 ° and 90 ° with the median circumferential plane (plane perpendicular to the axis of rotation of the tire which is located midway between the two bead 4 and goes through the middle of the crown frame 6).
• the belt 6 is for example constituted, also in a manner known per se, by at least two rubber sheets called “working plies” or “triangulation plies”, superimposed and crossed, reinforced with metal reinforcements arranged substantially parallel to each other.
• the belt 6 may comprise, for example, a rubber sheet called a "hooping sheet" reinforced by so-called “circumferential" reinforcing threads, that is to say that these reinforcing threads are arranged substantially parallel to each other and extend substantially circumferentially about the tire so as to form an angle preferably within a range of 0 to 10 ° with the medial circumferential plane.
• circumferential reinforcing son have the primary function, it is recalled, to resist the centrifugation of the top at high speed.
• the bandage 1 of the invention has for example the essential feature that at least its belt (6) and / or its carcass reinforcement (7) comprises a reinforcement according to the invention. According to another possible embodiment of the invention, it is the bead zone which can be reinforced with such a reinforcement; it is for example the rods (5) which could consist, in whole or in part, of such a reinforcement according to the invention. 5. EXAMPLES OF CARRYING OUT THE INVENTION
• This oil then undergoes a first purification on an SiO 2 column, using a diethyl ether / cyclohexane eluent, in a volume ratio of the two solvents varying from 10:35 (initial) to 10:20 (final).
• the purified fractions containing the monomer (M-8) are combined and the solvents evaporated.
• a light yellow solid is thus obtained.
• the latter is placed in methanol (1 g for 80 ml) and heated at reflux (65 ° C) for 30 min. The solution is then allowed to cool to room temperature (about 20 ° C.) to crystallize the monomer.
• the solid product obtained is isolated by filtration (Buchner filter).
• FIG. 16 reproduces the 1H NMR spectrum (500 MHz) of the M-8 monomer thus synthesized, dissolved in CD 2 Cl 2 . This NMR analysis gives the following results:
• This synthesis is carried out according to the procedure schematized in FIG. 17, as described in detail below, from two monomers: the benzoxazine obtained in the preceding step (Monomer M-8) and the sulfur aromatic diol of formula ( B1) (4,4'-thiodiphenol; N-1 Monomer) already described in Figure 10; this in the presence of sodium carbonate (Na 2 CO 3 , product Sigma Aldrich 13418), solvents (anhydrous) DMA (N, N-dimethylacetamide, product Sigma Aldrich 38839) and toluene (product Acros Organics No. 364411000).
• the two monomers (M-8 and N-1) are pre-dried under vacuum at 50 ° C overnight, as are the sodium carbonate but at a temperature of 150 ° C.
• the synthesis is carried out in a 100 ml round-necked four-neck flask equipped with a nitrogen inlet, thermometer, magnetic stirrer and a Dean Stark separator topped with a condenser and condenser. a distillation bridge (provided with a heating cap).
• the apparatus is dried under vacuum using a hot air gun until the thermometer reaches a temperature of at least 100 ° C in the reaction flask. The whole is allowed to cool to room temperature (20 ° C.), then the apparatus is put under a stream of nitrogen throughout the synthesis.
• the M-8 monomer (1 eq, 1.5 g, 2.79 mmol) of formula (A-8) is then first introduced into the flask, followed by the N-1 monomer of formula (B 1) (1). eq, 0.61 g or 2.79 mmol). 20 ml of DMA (solvent of the two monomers) are then added, and then as Na 2 CO 3 base (3 eq, 0.89 g or 8.36 mol) in suspension in 4 ml of toluene. The whole is purged under N 2 for 5 min, then the reaction medium is heated to 105 ° C.
• the distillation bridge of the Dean Stark apparatus is heated to 110 ° C (with the heating cap) to facilitate azeotropic distillation (water distillation / toluene) for about 90 minutes. Then the temperature of the reaction medium is gradually increased, by reducing by 10 ° C. every 30 min, until reaching 130 ° C. This temperature is left overnight (12 h), then allowed to cool to room temperature (20 ° C).
• the reaction mixture is finally poured into 250 ml of distilled water, with vigorous stirring (magnetic stirring bar); it is stirred for 30 minutes (20 ° C.) and the precipitate thus obtained is isolated by filtration (Buchner filter) and washed with 100 ml of distilled water; during this washing, to extract the carbonate, 10% aq. acid (HCl) is added dropwise to neutral pH.
• the precipitate is again washed with 100 ml of distilled water, dried under vacuum at 80 ° C overnight (about 12 hours).
• This Polymer P-4 in the form of a beige powder, was also analyzed by DSC (Differential Scanning Calorimetry) between -80 ° C and + 260 ° C along a ramp of 10 ° C / min (DSC apparatus). 822-2 "from Mettler Toledo, nitrogen atmosphere). The analysis showed at the first pass (between -80 ° C and + 260 ° C) an exotherm (corresponding to the opening of the oxazine rings, and the crosslinking of the polymer) beyond 200 ° C, with a maximum at 240 ° C. During the second and third passages of DSC conducted between -80 ° C and + 260 ° C, no apparent glass transition (Tg) was visible, which demonstrates the very high thermal stability of the polymer suitable for the invention. .
• DSC Different Scanning Calorimetry
• this last step is accompanied by a pronounced change in color of the polymer, turning bright yellow.
• the reinforcement of the invention provided on the surface of its thin layer (thickness 5 to 10 ⁇ ) of polybenzoxazine thus formed, was then subjected to a conventional sizing operation in two stages (sizing two baths) firstly by immersion in a first aqueous bath (about 94% water) based on epoxy resin (polyglycerol polyglycidyl ether, about 1%) and isocyanate compound (blocked caprolactam, about 5%), first step of sizing followed by drying (2 min at 100 ° C) and then heat treatment (5 min at 200 ° C).
• the reinforcement thus treated was immersed in a second aqueous bath of RFL glue (about 81% by weight of water) based on resorcinol (about 2%), formalin (about 1%) and a rubber latex ( about 16% of rubbers NR, SBR and VP-SBR); it was finally oven dried for 2 min at 130 ° C and then heat treated for 5 min at 200 ° C.
• RFL glue about 81% by weight of water
• formalin about 2%
• a rubber latex about 16% of rubbers NR, SBR and VP-SBR
• conventional rubber composition for passenger 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.
• the specific polybenzoxazine described in detail in the present application offers the metal reinforcements of the invention the major advantage of being able to then be glued to rubber matrices using simple textile glues such as RFL glues, or directly (That is, without the use of such glues) to these rubber matrices, for example when they contain suitable functionalized unsaturated elastomers such as epoxidized elastomers.
• metal reinforcements coated or not with adhesive metal layers such as brass, as well as surrounding rubber matrices devoid of metal salts, in particular cobalt salts, can be used.
• the polybenzoxazines suitable for the reinforcements of the invention have the remarkable ability, at high temperature, to open their oxazine rings and thereby lead to polyphenolic thermosetting resin structure. This gives them better thermal stability without visible phase transition at temperatures above 200 ° C.
• Their specific microstructure finally makes it possible, very advantageously, to adjust the flexibility of the molecule according to the particular applications concerned.

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• 2015
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