Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
  • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
  • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
  • C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
  • C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
• • 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
  • 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

Definitions

• the present invention relates to the monomers used for the synthesis of thermosetting resins, intended in particular for adhesive systems in particular for bonding metal to rubber.
• benzoxazine compounds capable of synthesizing polybenzoxazines used in particular as adhesive layers in metal / rubber composites intended for the manufacture of rubber articles such as tires, pneumatic or non-pneumatic, for vehicles.
• Metal / rubber composites especially 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.
• reinforcing elements or "reinforcements”
• 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, that the aforementioned polymers but which has once thermoset (crosslinked) thermal and chemical stability further improved and whose specific microstructure, moreover, very advantageously allows to adjust the flexibility of the molecule according to the particular applications.
• the present invention relates to a sulfated benzoxazine of formula (A):
• each benzene ring of the two oxazine rings carries at least one radical denoted "G";
• the two oxazine rings are connected to each other by a central aromatic group whose benzene ring carries one, two, three or four groups of formula -S x -R in which "x" is an integer of 1 to 8 and R represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms and optionally a heteroatom selected from O, S, N and P;
• 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 invention also relates to the use of a compound according to the invention for the synthesis of a polybenzoxazine, as well as any polybenzoxazine derived from at least one benzoxazine compound according to the invention.
• the invention also relates to any method for synthesizing a polybenzoxazine by polycondensation of a compound according to the invention, especially with, as second monomer, an aromatic diol or thiol compound.
• 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 FIGS. 1 to 11 which represent or schematize: the general principle of synthesis of a benzoxazine compound from three compounds, phenol, formaldehyde and amine (R residue of the amine) (Fig. la);
• 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 name just a few examples of publication one can
• polybenzoxazines have the remarkable capacity, at high temperature (for example, typically above 150 ° C or even 200 ° C depending on their particular microstructure), to open their oxazine and thus lead to structures of polyphenolic thermosetting resins.
• each benzene ring of the two oxazine rings bears at least one (i.e. one or more) G radical; 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 aliphatic cycloalkyl having 3 to 8 carbon atoms, or aromatic containing 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 ring or central benzene ring) carries one, two, three or four groups of formula -S x -R in which "x" is an integer of 1 to 8 and R is hydrogen or a hydrocarbon group
• 201 7PAT00231WO - - having 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 denoted M-0) of 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 ring bears two groups of formula -S x -R, these two groups being more preferably in the meta position with respect to the other on this central benzene nucleus.
• "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.
• Polybenzoxazine (Polymer "P"), derived from the benzoxazine of the invention of formula (A) described above, therefore has the essential feature of comprising recurring structural units comprising at least one unit corresponding to formula (I). (before opening of the oxazine rings) or formula (II) (after opening of the cycles) below:
• 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).
• the two symbols "*" (identical or different) represent any attachment of the unit to a carbon atom or a heteroatom (preferably selected from O , S, N and P), attachment or bond resulting from the opening of the oxazine rings at a sufficient thermal input ( ⁇ ).
• one or more hydrogen atoms of at least one or each benzene ring of the two oxazine rings, as well as that those of the central benzene ring, could optionally also be 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 metal and / or rubber.
• substituents for example a methyl or ethyl group
• functional groups for example a vinyl group
• the polybenzoxazine derived from the benzoxazine compound 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 of a single G. radical
• the polybenzoxazine derived from the compound of the invention has the essential feature of comprising at least recurring structural units comprising (at least) a unit corresponding to formula (Ia) (before opening of the oxazine cycles) or formula (II-a) (after opening of the cycles) below:
• x is 1 and R is methyl.
• the polybenzoxazine derived from the compound of 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) identical or different 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 (A-1) (Monomer noted M-1), according to the invention, usable for
• halogen 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.
• A hydrocarbon group
• 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 sulfurized aromatic diamine specific to FIGS. 2 and 3 above, of a particular benzoxazine according to the invention, of formula (A-2) (Monomer noted M-2), usable for the synthesis of a polybenzoxazine.
• FIG. 5 gives another possible scheme of synthesis, from a halogenated phenol, of paraformaldehyde and of a specific example of disulfurized aromatic diamine, namely 3,5-bis (methylthio) -2,6-toluenediamine.
• formula (b) above another example of particular halogenated benzoxazine according to the invention, of formula (A-3) (Monomer noted M-3), used for the synthesis of a polybenzoxazine.
• Figure 6 gives another possible scheme of synthesis, from another phenol (the symbol “A” has been previously described), paraformaldehyde and 3,5-bis (methylthio) -2,6-toluenediamine.
• formula (b) above another example of benzoxazine of formula (A-4) (Monomer noted M-4) used for the synthesis of a polybenzoxazine.
• 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 disulfurized benzoxazine of the invention responds at least in part to 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, this time 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 preceding disulfide aromatic diamine (Compound 3), another example of benzoxazine according to the invention, of formula (A) -5) (Monomer noted M-5), used in particular for the synthesis of a sulfurized polybenzoxazine.
• phenol Compound 1
• Compound 2 paraformaldehyde
• Compound 3 the particular example of the preceding disulfide aromatic diamine
• benzoxazine according to the invention of formula (A) -5) (Monomer noted M-5), used in particular for the synthesis of a sulfurized polybenzo
• phenol compounds here, for example methoxyphenols
• A aliphatic, ethylenically saturated or unsaturated hydrocarbon type, comprising 1 to 6, in particular 1 to 4 carbon atoms, which may optionally comprise at least one (or more) heteroatom selected from O, S, N and P
• phenol compounds here, for example methoxyphenols
• A aliphatic, ethylenically saturated or unsaturated hydrocarbon type, comprising 1 to 6, in particular 1 to 4 carbon atoms, which may optionally comprise at least one (or more) heteroatom selected from O, S, N and P
• the benzoxazine according to the invention of formula (A) described above is particularly intended (as monomer M) for the synthesis of a polybenzoxazme by polycondensation, in particular by polycondensation with at least one aromatic diol or thiol compound as a second monomer ("Monomer N").
• 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 derived from the sulfurized benzoxazine 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 of the 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 resulting from the benzoxazine 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-1bis) ) (after opening of the 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 describes a general synthesis scheme of a sulphurized polybenzoxazine (Polymer denoted by P1) of formula (I-1bis) above, according to the process of the invention, by polycondensation of the halogenated benzoxazine according to the invention of formula (A-6) (Monomer M-6) above with 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 herein as P-1 'of formula II-1a) once its oxazine rings have been opened after heat treatment of Polymer P-1.
• P1 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 (B-1, (B-2) or (B-3) below:
• the polybenzoxazine polymer 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 ⁇ -2), with its open oxazine rings, obtained this time by simple homopolymerization of the particular halogenated benzoxazine according to the invention of Formula (A-5) (Monomer M-5) above.
• the benzoxazine of the invention is a boron and disulfurized benzoxazine at least partly satisfying 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 brominated disulfurized benzoxazine of formula (A-7) (Monomer noted M-7) usable for the synthesis of polybenzoxazines (Polymer P-3 and P-3 'of Figure 11) according to the method of the invention.
• each benzene ring of the two oxazine benzoxazine rings of formula ( A) is carrying one and only one halogen (Hal), more preferably bromine, located in the para position of the oxygen of the oxazine ring.
• Hal halogen
• Figure 11 depicts the synthesis of a sulfated polybenzoxazine (Polymer P-3) from the particular halogenated benzoxazine of formula (A-7) (Monomer M-7) above and another particular monomer of formula (B1) (Nl Monomer) of the aromatic diol type
• the polybenzoxazine derived from the benzoxazine compound 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. as examples in FIGS. 8, 9 and 11.
• This polybenzoxazine derived from the benzoxazine of the invention is advantageously usable, as an adhesion primer or as a single adhesive layer, for coating a metal substrate, at least one substrate whose at least one surface is at least partly metallic and adhere the latter to rubber. It is particularly useful on any type of metal reinforcement, such as for example a wire, a film or a steel cable, in particular carbon steel, intended in particular to reinforce an unsaturated rubber matrix such as natural rubber. To adhere the rubber to the polybenzoxazme layer, any known adhesive system, for example a conventional textile glue of the "RFL" type (resorcinol-formaldehyde-latex) may also be used.
• RNL resorcinol-formaldehyde-latex
• 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 1 (2 eq; 4.93 g, 30 mmol) is then poured into the flask and then ethanol (51 ml). The presence of ethanol is important here, preventing the formation of unstable triazine intermediate product.
• This synthesis is carried out according to the procedure schematized in FIG. 11, as described in detail below, from two monomers: the benzoxazine of the invention obtained in the preceding step (Monomer M-7) and the aromatic diol sulfur of formula (B1) (4,4'-thiodiphenol; Monomer N1); this in the presence of sodium carbonate (Na 2 CO 3 , product Sigma Aldrich 13418), solvents (anhydrous) DMA ( ⁇ , ⁇ -dimethylacetamide, product Sigma Aldrich 38839) and toluene (product Acros Organics No. 364411000).
• the two monomers (M-7 and Nl) are pre-dried under vacuum (10 mbar) at 60 ° 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-7 Monomer (1 eq; 1.5 g, 2.79 mmol) of formula (A-7) is then first introduced into the flask, followed by the Nl Monomer of formula (B1) (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).
• the 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); the polymer P-3 of FIG. 11 was thus obtained, as attested by the RM NMR analysis (500 MHz).
• 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 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) above 200 ° C, with two maxima at about 270 ° C and 299 ° C. During the second and third DSC runs conducted between -80 ° C and + 350 ° C, no apparent glass transition was visible.
• DSC Densonic Scanning Calorimetry
• 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 sizing 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 rubber latex ( 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.
• RFL glue about 81% by weight of water
• formalin about 2%
• a rubber latex about 16% of NR, SBR and VP-SBR rubbers
• 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 benzoxazine according to the invention allows the synthesis of polymers offering metal reinforcements the major advantage of being able to then be glued to rubber matrices using simple textile glues such as RFL glues, or directly (c) that is, without use of such adhesives) 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 derived from the benzoxazines 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.
• 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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