Classifications

• • 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
• • 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
• • 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
  • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
  • C08G65/4031—(I) or (II) containing 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
  • C08G65/4056—(I) or (II) containing 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
  • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
• • 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
  • C09D179/00—Coating compositions 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 C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • 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
  • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • 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
• • 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
  • 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
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
• • 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
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2938—Coating on discrete and individual rods, strands or filaments

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 an unsaturated, generally diene, sulfur-crosslinkable unsaturated rubber matrix comprising reinforcing elements (or "reinforcements") of metal such as carbon steel wires, films, ribbons or cables.
• 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): - -
• 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.
• FIGS. 1 to 12 represent or schematize: the general principle of synthesis of a benzoxazine compound from of three compounds, phenol, formaldehyde and amine (R residue of the amine) (Fig. la);
• FIG 12 in radial section, an example of a bandage according to the invention, incorporating a reinforcement according to the invention (FIG 12).
• 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 ⁇ ).
• 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 Polybenzoxazine - 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.
• each benzene ring of the two oxazine rings bears at least one (i.e. one or more) radical G; benzoxazine itself thus bears at least two G radicals.
• the (at least) two radicals G are chosen from the group consisting of:
• R 1, R 2 and R 3 which may be identical or different, represent an alkyl having 1 to 4 carbon atoms; and aliphatic hydrocarbon groups having 1 to 8 carbon atoms, or cycloaliphatic groups containing 3 to 8 carbon atoms, or aromatics comprising 6 to 12 carbon atoms, these hydrocarbon groups, ethylenically saturated or unsaturated, optionally further comprising at least one heteroatom selected from O, S, N and P. - -
• the two oxazine rings are connected to each other by a central aromatic group whose benzene ring or ring (also called a ring or a central benzene ring) carries one, two, three or four groups of formula - S x -R in which "x" is an integer from 1 to 8 and R represents hydrogen or a hydrocarbon group containing 1 to 10 carbon atoms and optionally a heteroatom selected from O (oxygen), S (sulfur), N (nitrogen) and P (phosphorus).
• the two nitrogen atoms of the oxazine rings are, with respect to each other, in any position (ie ortho, meta or para) on the central benzene nucleus.
• these two nitrogen atoms are in the meta position with respect to each other; in other words, the benzoxazine (Monomer in this case noted M-0) from which derives the polybenzoxazine suitable for reinforcing the invention then responds preferentially to the generic formula (A-0) which follows: -0)
• FIG. 2 gives the general synthesis scheme of this benzoxazine of formula (A-0), under thermal contribution and with removal of water, from a specific phenol bearing at least one (ie one or more) radical G, paraformaldehyde and finally a specific sulfurized aromatic diamine of formula:
• the central benzene nucleus is and preferably carrying two groups of formula -S x -R, these two groups being more preferably in the meta position with respect to each other on the benzene ring.
• "x" is in a range from 1 to 4, more preferably equal to 1 or 2.
• R is preferably an alkyl having more preferably 1 to 5 carbon atoms, even more preferably a methyl or an ethyl, in particular a methyl.
• polymer By polymer is meant herein any homopolymer or copolymer, especially block copolymer, with recurring structural units having at least one unit of formula (I) or (II) above; the polymer can of course comprise both units of formula (I) and units of formula (II).
• one or more hydrogen atoms of at least one or each benzene ring of the two oxazine rings, as well as than those of the central benzene cycle could optionally be - - also substituted by various substituents (for example a methyl or ethyl group), in particular by functional groups (for example a vinyl group) likely to promote the adhesion of the polymer to the metal and / or to the rubber .
• substituents for example a methyl or ethyl group
• functional groups for example a vinyl group
• the polybenzoxazine that is suitable for the reinforcement of the invention then comprises at least recurring structural units comprising (at least) a unit corresponding to formula (I-bis) (before opening the oxazine rings) or formula (II- (bis) (after opening of the cycles) below:
• each benzene ring of the two oxazine rings carries a single radical G or a maximum of two, more preferably one and only one radical G .
• the polybenzoxazine that is suitable for the reinforcement of the invention therefore has the essential characteristic of comprising at least recurring structural units comprising (at least) a unit corresponding to formula (Ia) (before opening of the oxazine rings) or formula (II-a) (after opening of the cycles) below: - -
• x is 1 and R is methyl.
• the polybenzoxazine suitable for reinforcing the invention comprises recurring units comprising at least one unit corresponding to formulas (Ia-1) or (Ib-1) (before opening the oxazine rings), (II-a-1) or (II-b-1) (after opening cycles) below: - -
• the (at least two) radicals G represent a halogen such as bromine, chlorine, fluorine or iodine.
• FIG. 3 gives a general synthesis scheme, under thermal contribution and with removal of water, from a halogenated phenol bearing at least one (that is to say one or more) halogen (represented by the symbol "Hal"), p-formaldehyde and the sulphurous aromatic diamine specific of the preceding FIG. 2, of a particular halogenated benzoxazine of formula (Al) (Monomer noted as Ml) usable for the synthesis of a - - Polybenzoxazine suitable for the reinforcement of the invention.
• This halogen (Hal) is more preferably bromine or chlorine, more preferably bromine; the latter being more preferably still in the para position of the oxygen of each oxazine ring.
• the (at least two) identical or different radicals G represent a group chosen from -ORi, -SRi, -NR 2 R 3 ; R 1, R 2 and R 3 , which may be identical or different, represent an alkyl having 1 to 4 carbon atoms.
• the (at least two) identical or different radicals G represent a hydrocarbon group (represented by the symbol "A") aliphatic having 1 to 8 carbon atoms, or cycloaliphatic having 3 to 8 atoms carbon, or aromatic having 6 to 12 carbon atoms, this hydrocarbon group "A", ethylenically saturated or unsaturated, optionally having a (at least one) heteroatom selected from O, S, N and P.
• FIG. 4 gives a general synthesis scheme, under thermal contribution and with elimination of water, from a halogenated phenol carrying at least one (ie one or more) such group "A Of paraformaldehyde and the sulphurous aromatic diamine specific to FIGS. 2 and 3 above, of a particular benzoxazine of formula (A-2) (Monomer noted M-2) usable for the synthesis of a polybenzoxazine suitable for reinforcement of the 'invention.
• FIG. 5 gives another possible scheme of synthesis, from a halogenated phenol, of paraformaldehyde and of a specific example of disulfide aromatic diamine, namely the
• the (at least two) groups "A", which are identical or different, represent an aliphatic hydrocarbon group, ethylenically saturated or unsaturated, comprising 1 to 6, in particular 1 to 4 carbon atoms, which may optionally comprise at least one (i.e., one or more) heteroatom selected from O, S, N and P. - -
• the polymer which is suitable for the reinforcement of the invention is derived from a disulfurized benzoxazine which at least partly meets one of the two formulas (A-5) and (A-5bis). ) (Monomers respectively denoted M-5 and M-5bis) below:
• FIG. 7 is a particular case of FIG. 6, which describes another synthesis scheme, starting from a particular example of a phenol (Compound 1) corresponding to such a preferential definition (here, phenol carrying an ethylenic unsaturation and a methoxyl group), paraformaldehyde (Compound 2) and the particular example of the above disulfide aromatic diamine (Compound 3), another example of benzoxazine of formula (A-5) (Monomer noted M-5) usable for the synthesis of a sulfurized polybenzoxazine suitable for the reinforcement of the invention.
• phenol Compound 1
• Compound 2 paraformaldehyde
• Compound 3 the particular example of the above disulfide aromatic diamine
• preferential sulphurous aromatic diamines By way of examples of preferential sulphurous aromatic diamines, mention has already been made in particular of the compounds 3,5-bis (methylthio) -2,4-toluenediamine, 3,5-bis (methylthio) -2,6-toluenediamine and their mixtures .
• phenol compounds here, for example methoxyphenols
• A the aliphatic hydrocarbon type, ethylenically saturated or unsaturated, containing 1 to 6, in particular 1 to 4 carbon atoms, which may comprise -
• at least one (that is to say one or more) heteroatom selected from O, S, N and P may be cited for example the following compounds:
• the polybenzoxazine polymer which is suitable for the reinforcement of the invention can be obtained by polycondensation of a benzoxazine of formula (A) or (A-0) as described in detail previously as a first monomer and as a second monomer an aromatic diol or thiol compound.
• This aromatic diol or thiol compound more preferably corresponds to formula (B):
• - Xi and X 2 identical or different, represent O or S;
• Ar 2 identical or different, represent an aromatic group, preferably phenylene;
• Z represents O or (S) n , the symbol "n" representing an integer equal to or greater than 1.
• the polybenzoxazine suitable for 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 oxazine rings) or (II- 1) (after opening cycles):
• the two nitrogen atoms of the oxazine rings are, with respect to each other, in any position (that is ortho , meta or para) on the central benzene nucleus that separates them.
• the polybenzoxazine that is suitable for the reinforcement of the invention then comprises recurring structural units comprising (at least) a unit corresponding to formula (I-1a) (before opening the oxazine rings) or formula (II-1a) (after opening cycles) below:
• one or more hydrogen atoms of at least one or each aromatic nucleus Ari and Ar 2 may be substituted by various substituents, identical or different, for example by functional groups that may promote the adhesion of the polymer to the metal and / or rubber.
• FIG. 8 depicts a general synthesis scheme of a sulphurized polybenzoxazine (Polymer denoted P-1) suitable for the reinforcement of the invention, of formula (I-1a) above, from the halogenated benzoxazine of formula (A) -6) (M-6 monomer) above and another monomer of generic formula (B) (monomer denoted "N") of the aromatic diol or thiol type; as well as this example of sulphurised polybenzoxazine (Polymer denoted here ⁇ - of formula II-IIa) once its oxazine rings have been opened after heat treatment of Polymer P-1.
• P-1 sulphurized polybenzoxazine
• X 1 and X 2 each represent either a sulfur atom or an oxygen atom
• Z represents O or S (ie "n" equal to 1), more preferably S.
• the compound of formula (B) above corresponds to at least one of the particular formulas (B1 (B-2) or (B-3) below:
• the polybenzoxazine polymer that is suitable for the reinforcement of the invention may be obtained by homopolymerization of a benzoxazine of formula (A) or (A-0) as described above.
• FIG. 9 illustrates a synthesis scheme of another polybenzoxazine (Polymer P-2 'of formula II-2) that is suitable for the reinforcement of the invention, with its open oxazine rings, this time obtained by simple homopolymerization of benzoxazine halogenated compound of formula (A-5) (Monomer M-5) above.
• the polymer which is suitable for the reinforcement of the invention is derived from a polysulfurized brominated benzoxazine which at least partly satisfies one of the two formulas (A-7) and (A-7bis) (Monomers respectively denoted M-7 and M-7bis) below:
• FIG. 10 gives an example of a synthesis, from brominated phenol (compound 4), p-formaldehyde (compound 2) and 3,5-bis (methylthio) -2,6-toluenediamine (compound 3), from this polysulfurized brominated benzoxazine of formula (A-7) (Monomer noted M-7) usable for the synthesis of polybenzoxazines (Polymer P-3 and P-3 'of Figure 11) suitable for the reinforcement according to the invention.
• A-7 Polysulfurized brominated benzoxazine of formula (A-7) (Monomer noted M-7) usable for the synthesis of polybenzoxazines (Polymer P-3 and P-3 'of Figure 11) suitable for the reinforcement according to the invention.
• each benzene ring of the two oxazine benzoxazine rings of formula (A) is carrier one and only one halogen (Hal), more preferably bromine, located in the para position of the oxygen of the oxazine ring.
• Hal halogen
• FIG. 11 describes the synthesis of a sulphurized polybenzoxazine (Polymer P-3) that is suitable for reinforcing the invention, from the particular halogenated benzoxazine of - - formula (A-7) (Monomer M-7) above and another particular monomer of formula (B-1) (Nl Monomer) of the sulfur aromatic diol type (carrying a thioether function), and that the structure of this polymer once its open oxazine cycles (Polymer noted P-3 ').
• the syntheses of Figures 10 and 11 will be described in more detail in the following embodiments.
• the polybenzoxazme 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 8, 9 and 11.
• the polybenzoxazme described above 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 RFL-type textile glue comprising at least one diene elastomer such as natural rubber, or any equivalent adhesive known to impart adhesion.
• a conventional RFL-type textile glue comprising at least one diene elastomer such as natural rubber, or any equivalent adhesive known to impart adhesion.
• suitable 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.
• the polybenzoxazme previously described is intended for 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 (conventionally narrower film width at more equal - - 5 cm) or a steel cable, especially 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 (conventionally narrower film width at more equal - - 5 cm) or a steel cable, especially 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. 12 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 another - - so as to form an angle 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 beads 4 and passes 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.
• Compound 3 was isolated, by chromatography on silica gel, from 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 approximately 4 / 1 according to chromatographic analysis).
• Compound 3 was isolated, by chromatography on silica gel, from 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 approximately 4 / 1 according to chromatographic analysis).
• 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-7 monomer (1 eq, 1.5 g, 2.79 mmol) of formula (A-7) 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 for 17 h and then allowed to cool to room temperature (20 ° C).
• reaction mixture is then distilled at 90 ° C (vacuum 3 mbar) for removal of solvents and volatile residues, and the solid precipitate thus obtained is washed with 250 ml of distilled water; during this washing, to extract the carbonate, acid (1% aqueous HCl) is added dropwise to neutral pH.
• acid 1% aqueous HCl
• the precipitate is again washed with 100 ml of distilled water, dried under vacuum at 80 ° C overnight (about 12 hours).
• This Polymer P-3 in the form of a light yellow powder, was also analyzed by DSC (Differential Scanning Calorimetry) between -80 ° C and + 350 ° C in 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 + 350 ° C) an apparent glass transition (Tg) at 163 ° C followed by an exotherm (corresponding to the opening of the oxazine rings, and the crosslinking of the polymer) to above 200 ° C, with two maxima at about 270 ° C and 299 ° C.
• Tg apparent glass transition
• the ribbon 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), all of 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 gluing step followed by drying (2 min at 100 ° C) and then heat treatment (5 min at 200 ° C).
• the ribbon 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 latex. rubber (about 16%> of NR, SBR and VP-SBR rubbers); it was finally oven dried for 2 min at 130 ° C and then heat treated for 5 min at 200 ° C.
• the brass ribbon thus coated with the polybenzoxazine film and then glued was then placed between two layers of conventional rubber composition for a passenger car tire belt, a composition based on natural rubber, carbon black, and silica. charge, 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 150 ° C for 30 min at a pressure of 20 bar. - -
• 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.
• suitable functionalized unsaturated elastomers such as epoxidized elastomers.
• metal substrates 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 of the invention have the remarkable ability, at high temperature, to open their oxazine rings and thus lead to a resin structure polyphenolic thermosetting. This gives them better thermal stability.
• 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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• 2017
  • 2017-06-14 FR FR1755353A patent/FR3067646A1/fr not_active Withdrawn
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