Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
• • 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
  • C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
  • C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
  • C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
  • C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers

Definitions

• the invention relates to the use of an aromatic polyphenol derivative for the manufacture of a phenol-aldehyde resin for reinforcing a rubber composition.
• High rigidity can be obtained using a so-called concentrated vulcanization system, that is to say comprising, in particular, relatively high levels of sulfur and vulcanization accelerator.
• the storage of the raw composition containing a concentrated vulcanization system is likely to cause a decrease in the delay phase of the composition during its vulcanization, that is to say the time before the start of vulcanization.
• the composition may begin to cook prematurely in some shaping tools and the vulcanization kinetics may be varied and the vulcanization yield may be degraded.
• Such a concentrated vulcanization system also penalizes cooked aging. Indeed, there is a degradation of the mechanical properties of the cooked composition, in particular at the limits, for example of elongation at break.
• the methylene acceptor is associated with a curing agent, capable of crosslinking or hardening, also commonly called methylene donor. Examples of such acceptor and methylene donor are described in WO 02/10269.
• methylene donors conventionally used in tire rubber compositions are hexamethylenetetramine (abbreviated to HMT), or hexamethoxymethylmelamine (abbreviated to HMMM or H3M), or hexaethoxymethylmelamine.
• HMT hexamethylenetetramine
• HMMM hexamethoxymethylmelamine
• H3M hexaethoxymethylmelamine
• Methylene acceptors conventionally used in tire rubber compositions are precondensed phenolic resins.
• the object of the invention is to make it possible to reinforce rubber compositions by means of compounds with a low environmental impact.
• the subject of the invention is the use of an aromatic polyphenol derivative comprising at least one aromatic ring bearing at least two -OZ groups in the meta position with respect to each other. the two ortho positions of at least one of the --OZ groups being unsubstituted, and wherein each -OZ group represents a group -O- Si (R-
• the reinforcing phenol-aldehyde resin is based on the aromatic polyphenol derivative and an aldehyde and is manufactured in-situ, by crosslinking, in the rubber composition, in particular during crosslinking. this rubber composition, for example by vulcanization or baking.
• aromatic polyphenol derivatives according to the invention advantageously prevent early crosslinking of a phenol-aldehyde resin based on this aromatic polyphenol derivative and an aldehyde.
• a problem related to the use of certain reinforcing resins, especially those based on aromatic polyphenol and aldehyde is their ability to crosslink early.
• the composition is shaped, for example by calendering, for example in the form of a sheet, a plate, or extruded, for example to form a rubber profile.
• these reinforcing resins based on the aromatic polyphenol and the corresponding aldehyde crosslink and stiffen the composition, which can hinder the shaping of the rubber composition.
• the aromatic polyphenol derivative and the aldehyde react less rapidly than the corresponding aromatic polyphenol and aldehyde.
• This reaction rate can be determined by measuring the evolution of the rheometric torque as a function of time.
• This development describes the stiffening of the composition, particularly as a result of the crosslinking of the phenol-aldehyde resin.
• the aromatic polyphenol derivative according to the invention is a precursor of the corresponding aromatic polyphenol and that the latter makes it possible to avoid early crosslinking of the phenolic resin.
• aldehyde because of the radical Z of each -OZ group which is different from hydrogen.
• the radical Z of each -OZ group would act as a temporary protective group allowing, according to the hypothesis of the inventors, the formation of a hydroxyl function under predetermined reaction conditions and thus the formation of the corresponding aromatic polyphenol.
• the predetermined reaction conditions in which this formation is possible depend on several parameters such as the pressure, the temperature or the chemical species present in the reaction medium.
• reaction conditions are a function of the -OZ group and are easily determinable, or even known to those skilled in the art.
• reaction conditions are the heating of the rubber composition at a temperature greater than or equal to 80 ° C, preferably at 100 ° C and more preferably at 120 ° C
• the aromatic polyphenol derivative according to the invention and the aldehyde can react less rapidly than the corresponding aromatic polyphenol and aldehyde.
• This reaction rate can be determined by measuring the evolution of the rheometric torque as a function of time.
• This development describes the stiffening of the composition, particularly as a result of the crosslinking of the phenol-aldehyde resin.
• the -O-Z group is such that the reaction between the aromatic polyphenol derivative according to the invention and the aldehyde allows the crosslinking of a phenol-aldehyde resin.
• the -OZ group is such that the reaction between the aromatic polyphenol derivative according to the invention and the aldehyde allows the crosslinking of a phenol-aldehyde resin under the same reaction conditions, preferably the same reaction temperature conditions. that a phenol-aldehyde resin based on the corresponding aromatic polyphenol (having hydroxyl groups instead of -OZ groups) and the same aldehyde.
• the temperature is greater than or equal to 120 ° C., preferably greater than or equal to 140 ° C.
• the specific combination of the aldehyde and the aromatic polyphenol derivative according to the invention makes it possible to obtain excellent stiffness maintenance of the rubber composition with the increase in temperature, this maintenance being greater in most embodiments, to that of the rubber compositions lacking a reinforcing resin.
• the specific combination of the aldehyde and this aromatic polyphenol derivative also makes it possible to obtain excellent rigidity maintenance of the rubber composition with the increase in temperature, this maintenance being equivalent, or even greater, in certain embodiments. to that of conventional rubber compositions which include HMT or H3M methylene donors.
• the inventors at the origin of the invention hypothesize that the aromatic polyphenol derivative according to the invention (containing hydroxyl groups in place of the -OZ groups) is a precursor of the corresponding aromatic polyphenol. .
• this makes it possible to avoid an immediate crosslinking of the phenol-aldehyde resin because of a reaction which would generate, off-line, the hydroxyl functions function from the aromatic polyphenol derivative (containing hydroxyl groups instead of -OZ groups).
• the -OZ groups act as temporary protective groups allowing, according to the hypothesis of the inventors, the formation of hydroxyl functions under predetermined reaction conditions (in other words the regeneration of the aromatic polyphenol corresponding to the derivative).
• aromatic polyphenol derivative is used because of the existing structural similarity between this compound called “aromatic polyphenol derivative” and the corresponding aromatic polyphenol. Indeed, the aromatic polyphenol derivative is a compound having a structure similar to that of the corresponding aromatic polyphenol but in which the hydrogen of at least two hydroxyl functions is replaced by the radical Z.
• aromatic polyphenol derivative according to the invention it should not be understood that it may be a pre-condensed resin which comprises hydroxyl functions allowing the reaction with the aldehyde.
• all -O-Z groups are the same. However, in other embodiments, at least two -O-Z groups are different.
• each -OZ group is preferably free of reactive function with respect to the aldehyde.
• each radical R 1, R 2 and R 3 is preferably free of reactive function vis-à-vis the aldehyde.
• each -OZ group is preferably devoid of reactive function with respect to the other constituents of the rubber composition.
• each radical R 1, R 2 and R 3 is preferably free of reactive function vis-à-vis the other constituents of the rubber composition.
• reactive function here is meant a function that would react under reaction conditions necessary for the regeneration of the aromatic polyphenol and under the reaction conditions necessary for the crosslinking of the phenol-aldehyde resin.
• the molar mass of each -OZ group is less than or equal to 1000 g. mol "1.
• the molar mass of each -OZ group is between 15 g. mol" 1 and 1000 g. mol "1 , preferably between 15 g mol -1 and 500 g. mol "1 .
• the carbon products mentioned in the description may be of fossil origin or biobased. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass.
• the term "resin-based” it is of course understood to include a resin comprising the mixture and / or the reaction product of the various basic constituents used for this resin, some of which may be intended for react or likely to react with one another or with their surrounding chemical environment, at least in part, during the various phases of the process for manufacturing the composition, the composites or the tire, in particular during a cooking step.
• the aldehyde is derived from a precursor of this aldehyde.
• a precursor of formaldehyde would be hexamethylenetetramine (HMT).
• the invention makes it possible to manufacture a rubber composition
• a rubber composition comprising at least one phenol-aldehyde resin based on at least one aromatic polyphenol derivative according to the invention and at least one aldehyde.
• the invention also makes it possible to manufacture a rubber composition comprising at least one aromatic polyphenol derivative according to the invention and at least one aldehyde.
• the invention may also make it possible to implement a method of manufacturing a rubber composition, comprising a step of mixing at least one aromatic polyphenol derivative according to the invention and at least one aldehyde.
• At least one elastomer is also mixed with the composition.
• the invention may also make it possible to implement a method of manufacturing a rubber composition in the cooked state, comprising:
• a step of manufacturing a raw rubber composition comprising a step of mixing at least one aromatic polyphenol derivative according to the invention and at least one aldehyde,
• crosslinking step by vulcanization or baking can be replaced by a crosslinking step using another crosslinking system that sulfur.
• the aromatic polyphenol derivative according to the invention comprises at least one aromatic ring bearing at least two -OZ groups in the meta position with respect to each other, the two ortho positions of at least one of these -OZ groups being unsubstituted.
• the aromatic polyphenol derivative is used to generate a delay phase during the crosslinking of a phenol-aldehyde resin based on the aromatic polyphenol derivative and an aldehyde, by example as described below.
• the aromatic polyphenol derivative may be, in another embodiment, a pre-condensed resin based on:
• the aromatic polyphenol derivative comprises a pre-condensed resin based on at least one aromatic polyphenol as described in any of the embodiments described in the present application, the hydroxyl functions of the pre-condensed resin free at the end of the condensation of the precondensed resin being substituted with -OZ groups.
• At least one compound comprising at least one aldehyde function.
• the carbon blacks could for example already be incorporated into the isoprene elastomer in the form of a masterbatch (see for example applications WO 97/36724 or WO 99/16600).
• organic fillers other than carbon blacks
• reinforcing inorganic fillers are particularly suitable inorganic fillers of the siliceous type, in particular of silica (SiO 2 ), or of the aluminous type, in particular alumina (Al 2 O 3 ).
• the silica used may be any reinforcing silica known to those skilled in the art, especially any precipitated or pyrogenated silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / boy Wut.
• the rubber composition comprises various additives.
• the rubber compositions may also comprise all or part of the usual additives usually used in elastomer compositions for the manufacture of tires, for example plasticizers or extension oils, which are of aromatic nature. or non-aromatic, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents or even adhesion promoters.
• the vulcanization system comprises a vulcanization accelerator and / or a vulcanization retarder.
• the generated residue remains only temporarily in the composition either because it comes out spontaneously under the conditions of manufacture of the composition, for example in the form of gas, especially in the case where the residue is volatile, or because it implements an optional step of extracting this residue in the method of manufacturing the composition.
• the or at least one aldehyde is an aromatic aldehyde.
• Such an aldehyde is very advantageous. Indeed, the Applicants have discovered during their research that the aromatic aldehyde makes it possible to avoid the production of formaldehyde in contrast to conventional methylene donors. Indeed, the combination of phenolic resin conventionally used as a methylene acceptor with HMT or ⁇ 3 ⁇ as a methylene donor in the state of the art, produces formaldehyde during the vulcanization of the rubber composition. However, it is desirable to reduce or even eventually eliminate formaldehyde rubber compositions because of the environmental impact of these compounds and recent regulatory developments, including European regulations, on this type of compound.
• X includes N, S or O
• R represents -H or -CHO
• the aldehyde is of general formula
• R represents -CHO.
• X represents O.
• aldehyde of general formula (A) represents O and R represents -CHO.
• the aldehyde used is then 2,5-furanedicarboxaldehyde and is of formula (B'b):
• X comprises N.
• X represents the aldehyde used is of formula (Ca):
• X represents NR1 'with R1' representing a radical selected from the group consisting of alkyl, aryl arylalkyl, alkylaryl, cycloalkyl radicals.
• R1' representing a radical selected from the group consisting of alkyl, aryl arylalkyl, alkylaryl, cycloalkyl radicals.
• the aldehyde used is of formula (Cb):
• X represents S.
• the aldehyde used is of formula (Da):
• X represents S.
• the aldehyde used is of formula (D'to):
• R represents -CHO in the variant of the aldehyde of formula (IVa) and is then 2,5-thiophene dicarboxaldehyde.
• X represents SR2 'with R2' representing a radical chosen from the group consisting of alkyl, aryl arylalkyl, alkylaryl and cycloalkyl radicals.
• R2' representing a radical chosen from the group consisting of alkyl, aryl arylalkyl, alkylaryl and cycloalkyl radicals.
• the aldehyde used is of formula (Db):
• X represents R3'-S-R2 'with R2', R3 'each representing, independently of one another, a radical chosen from the group consisting of alkyl, aryl arylalkyl, alkylaryl, cycloalkyl radicals.
• the aldehyde used is of formula (De):
• the aromatic aldehyde is selected from the group consisting of 1,4-benzenedicarboxaldehyde, furfuraldehyde, 2,5-furanedicarboxaldehyde and mixtures of these compounds.
• the composition is free of formaldehyde.
• each aldehyde other than each aromatic aldehyde as described above is preferably different from formaldehyde.
• the composition is then also preferably free of formaldehyde.
• the or each aldehyde of the phenol-aldehyde resin is different from formaldehyde.
• formaldehyde free means that the formaldehyde mass content by weight of the aldehyde or aldehydes is strictly less than 1%.
• the composition may comprise formaldehyde.
• the composition then comprises a mass content of formaldehyde by total weight of the aldehyde or at least 10%, preferably 5% and more preferably 2%.
• the rubber composite is reinforced with at least one reinforcement element embedded in the rubber composition comprising a phenol-aldehyde resin based on an aromatic polyphenol derivative according to the invention.
• This rubber composite can be prepared according to a process comprising at least the following steps:
• a first step combining at least one reinforcing element with a rubber composition (or elastomer, both terms being synonymous) to form a reinforced rubber composite of the reinforcing element;
• the textile reinforcing elements mention may be made of the textile reinforcing elements, metallic or hybrid textile-metal.
• This textile material may consist of a yarn or fiber or also of a fabric made from yarns or fibers, for example a woven fabric with warp yarns and weft yarns, or else a crossed fabric with crossed threads.
• this textile material of the invention is selected from the group consisting of monofilaments (or single son), multifilament fibers, assemblies of such son or fibers, and mixtures of such materials. It is more particularly a monofilament, a multifilament fiber or a twist.
• wire or fiber is generally meant any elongate element of great length relative to its cross section, whatever the shape of the latter, for example circular, oblong, rectangular or square, or even flat, this wire can be rectilinear as non-rectilinear, for example twisted or corrugated.
• the largest dimension of its cross section is preferably less than 5 mm, more preferably less than 3 mm.
• This wire or this fiber may take any known form, it may be for example an elementary monofilament of large diameter (for example and preferably equal to or greater than 50 ⁇ ), a multifilament fiber (constituted of a plurality of elementary filaments of small diameter, typically less than 30 ⁇ ), of a twisted or cabled textile formed of several textile fibers or monofilaments twisted or cabled together, or of an assembly, a group, a row of yarns or fibers such as, for example, a strip or strip comprising several of these monofilaments, fibers, twisted or cabled grouped together, for example aligned in a main direction, rectilinear or not.
• the textile materials may be organic or polymeric material, such as inorganic material.
• inorganic materials mention will be made of glass and carbon.
• the invention is preferably implemented with materials of polymeric material, thermoplastic type as non-thermoplastic.
• polymeric materials of the non-thermoplastic type include for example aramid (aromatic polyamide) and cellulose, natural as artificial, such as cotton, rayon, linen, hemp.
• polymeric materials of the thermoplastic type mention may be made of preferentially aliphatic polyamides and polyesters.
• aliphatic polyamides that may be mentioned in particular are polyamides 4-6, 6, 6-6, 11 or 12.
• polyesters that may be mentioned for example PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene) terephthalate), PBN (polybutylene naphthalate), PPT (polypropylene terephthalate), PPN (polypropylene naphthalate).
• metallic is meant by definition one or more wire elements constituted predominantly (that is to say for more than 50% of its mass) or integrally (for 100% of its mass) of a metallic material.
• the metallic material is steel, more preferably carbonaceous perlitic (or ferrito-pearlitic) steel advantageously comprising between 0.4% and 1.2% by weight of carbon.
• the metal reinforcing element may be a monofilament, a cable comprising several metal monofilaments or a multi-strand cable comprising several cables then called strands.
• the metal monofilaments or strands are assembled by twisting or wiring. It is recalled that there are two possible techniques of assembly:
• the metal monofilaments or the strands undergo both a collective twist and an individual twist around their own axis, which generates a couple of untwist on each of the monofilaments or strands;
• the metal monofilaments or the strands undergo only a collective torsion and do not undergo individual torsion around their own axis.
• the reinforcing element comprises several monofilaments and is of the gummed type in situ, that is to say that the reinforcing element is gummed from the inside, during its manufacture even by an eraser filling.
• Such metallic wire elements are known to those skilled in the art.
• the composition of the filling rubber may or may not be identical to the rubber composition in which the reinforcing element is embedded.
• Such tires are for example those intended to equip tourism-type motor vehicles, SUV ("Sport Utility Vehicles”), two wheels (including bicycles, motorcycles), aircraft, such as industrial vehicles chosen from vans, " Heavy goods vehicles "- that is to say metro, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering vehicles -, other transport vehicles or Handling.
• SUV Sport Utility Vehicles
• two wheels including bicycles, motorcycles
• aircraft such as industrial vehicles chosen from vans, " Heavy goods vehicles "- that is to say metro, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering vehicles -, other transport vehicles or Handling.
• FIG. 1 represents in a very schematic manner (without compliance with a specific scale), a radial section of a tire according to the invention for a truck-type vehicle.
• This tire 1 comprises an apex 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 top 2 is surmounted by a strip of bearing 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 of at least one sheet reinforced by so-called "radial” cables, for example metallic, that is to say that these cables are arranged substantially parallel to each other and extend from a 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 beads 4 and passes through the middle of the crown frame 6).
• radial cables for example metallic
• This tire 1 of the invention has for example the characteristic that at least one crown reinforcement 6 and / or its carcass reinforcement 7 comprises a rubber composition comprising a phenol-aldehyde resin based on a derivative of aromatic polyphenol according to the invention. ⁇ 0177 ⁇ Process for producing the aromatic polyphenol derivative
• aromatic polyphenol derivative as defined above is manufactured by means of a process in which:
• an aromatic polyphenol comprising at least one aromatic ring bearing at least two OH hydroxyl functional groups in the meta position with respect to each other, the two ortho positions of at least one of the OH hydroxyl functions being unsubstituted , and
• LG-Si (R-R 2 R 3 ) with R 1, R 2 and R 3 representing, independently of one another, a hydrocarbon radical or a substituted hydrocarbon radical and LG representing a nucleofugal group.
• the conditions of the reaction between the aromatic polyphenol and the compound of formula LG-Si are well known to those skilled in the art.
• the process according to the invention is carried out by first reacting, in an organic solvent, the aromatic polyphenol with a base, more preferably an organic base, and then introducing the compound of formula LG-Si. (RiR 2 R 3 ) in the reaction mixture.
• the reaction is conducted between 20 ° C and 50 ° C for a few hours, for example between 1 hour and 10 hours.
• the LG nucleofuge group represents a halogen. It is recalled that the halogens correspond to the elements F, Cl, Br and I.
• LG represents chlorine.
• the manufacturing method described above and hereinafter makes it possible to manufacture the rubber composition comprising a phenol-aldehyde resin based on an aromatic polyphenol derivative according to the invention.
• the rubber composition may be manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art:
• a first phase of work or thermomechanical mixing at high temperature, up to a maximum temperature of between 110 ° C. and 190 ° C., preferably between 130 ° C. and 180 ° C.,
• the method comprises the following steps:
• the non-productive phase is conducted in a single thermomechanical step during which is introduced, in a suitable mixer such as a conventional internal mixer, in a first step all the basic constituents necessary (diene elastomer, reinforcing filler, etc.), then in a second step, for example after one to two minutes of mixing, the other additives, any optional charge recovery or implementation agents, with the exception of of the crosslinking system, the aromatic polyphenol derivative according to the invention and the aldehyde.
• the total mixing time in this non-productive phase is preferably between 1 and 15 minutes.
• the mixture thus obtained After cooling the mixture thus obtained, it is then incorporated in an external mixer such as a roll mill, maintained at low temperature (for example between 40 ° C. and 100 ° C.), the crosslinking system, the aldehyde and the derivative of aromatic polyphenol according to the invention. The whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
• an external mixer such as a roll mill, maintained at low temperature (for example between 40 ° C. and 100 ° C.)
• the whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
• composition thus obtained in the green state can then be shaped, for example calendered, for example in the form of a sheet, a plate especially for a characterization in the laboratory, or extruded, for example to form a rubber profile used for the manufacture of a tire.
• a vulcanization step of the composition the composite or the blank during which the phenol-aldehyde resin based on the aromatic polyphenol derivative according to the invention and the aldehyde is crosslinked.
• the vulcanization step is carried out at a temperature greater than or equal to 120 ° C., preferably greater than or equal to 140 ° C.
• the composition is obtained in the cooked state.
• the process comprises the following steps: incorporating in an elastomer, during a first step, a reinforcing filler, the derivative of the aromatic polyphenol and the aldehyde, by thermomechanically kneading the whole. up to a maximum temperature of between 110 ° C and 190 ° C;
• the rigidity of the rubber composition comprising a phenol-aldehyde resin based on an aromatic polyphenol derivative according to the invention is greatly increased with respect to a rubber composition devoid of reinforcing resin;
• the rigidity of the rubber composition comprising a phenol-aldehyde resin based on an aromatic polyphenol derivative according to the invention can be improved with respect to a rubber composition using a conventional reinforcing resin based on a methylene acceptor with ⁇ or ⁇ 3 ⁇ as a methylene donor;
• the maintenance of the rigidity of the rubber composition according to the invention at elevated temperatures is greater than that of rubber compositions lacking a reinforcing resin and equivalent, or even greater in certain embodiments, to that of the compositions of conventional rubbers which include HMT or H3M methylene donors;
• a retardation phase exists during the crosslinking of the phenol-aldehyde resin based on an aromatic polyphenol derivative according to the invention making it possible to avoid the early crosslinking of the resin with respect to a phenol-aldehyde resin crosslinked directly to from aromatic polyphenol and aldehyde;
• the phenol-aldehyde resin based on an aromatic polyphenol derivative according to the invention and a preferably aromatic aldehyde is free of formaldehyde and does not generate during its formation.
• T0, T1 and T2 and 11 to 13 were prepared as indicated above and are summarized in Table 1 attached below.
• compositions T0 to T2 and 11 to 13 have a common part in their formulations (expressed in phr, parts by weight per hundred parts of elastomer): 100 phr of natural rubber, 75 phr of carbon black N326, 1, 5 phr of N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine, 1.5 phr of stearic acid, 5 phr of ZnO, 1 phr of N-tertiarybutyl-2-benzothiazole sulfonamide and 2.5 20H insoluble sulfur.
• composition T0 does not include any reinforcing resin added to this common part.
• the T1 composition comprises a reinforcing resin based hexa-methylenetetramine (1, 6 phr) and a pre-condensed phenolic resin (4 phr).
• the composition T1 represents a conventional composition of the state of the art having a rigidity greater than that of the composition T0.
• the composition T2 comprises a phenol-aldehyde resin based on phloroglucinol and 1,4-benzene-dicarboxaldehyde.
• the composition T2 comprises 7 phr of phloroglucinol and 14 phr of 1,4-benzenedicarboxaldehyde.
• each composition 11 to 13 comprises a phenol-aldehyde resin based on an aromatic polyphenol derivative according to the invention and an aldehyde, preferably an aromatic aldehyde, indicated in the table. 1 in molar proportions 1 (aromatic polyphenol derivative according to the invention) / 2 (aldehyde), and with in each composition 11 to 13 14 phr of aldehyde.
• Each aromatic polyphenol derivative according to the invention in each composition 11 to 13 comprises at least one aromatic ring bearing at least two -OZ groups in the meta position with respect to each other, the two ortho positions. at least one of -OZ being unsubstituted and wherein each -OZ is -O-Si (R-
• Aromatic polyphenol derivatives of compositions 11 to 13 are Aromatic polyphenol derivatives of compositions 11 to 13
• Each aromatic polyphenol derivative according to the invention of the resin of each composition 11 to 13 is chosen from the group consisting of aromatic polyphenol derivatives of formula (I), (II), (IV) and (V) described above and mixtures of these aromatic polyphenol derivatives.
• Each aromatic polyphenol derivative according to the invention of each composition 11 to 13 comprises a single aromatic ring, here benzene, bearing three, and only three, -OZ groups in the meta position relative to each other. .
• aromatic polyphenol derivatives according to the invention of each composition 11 to 13 the remainder of the aromatic ring is unsubstituted.
• the two ortho positions of each -O-Z group are unsubstituted.
• aromatic polyphenol derivatives of general formula (II) obtained from phloroglucinol.
• Each aromatic polyphenol derivative according to the invention of each composition 11-13 shows -OZ groups each representing a group -0-Si (RIR 2 R 3) with R, R 2, R 3 representing, independently a on the other, a radical selected from the group consisting of alkyl, aryl, arylalkyl, alkylaryl, cycloalkyl, alkenyl.
• R 1, R 2 and R 3 represents, independently of one another, a radical chosen from the group consisting of methyl, ethyl, propyl, phenyl, allyl and vinyl radicals and even more preferentially a chosen radical. in the group consisting of methyl, ethyl, propyl, butyl, allyl, vinyl.
• LG Cl
• an organic base for example, 40 g of phloroglucinol are dissolved in 800 ml of chloroform. Then, 109 g of triethylamine. Then 107 g of trimethylsilyl chloride CISi (CH 3 ) 3 are added dropwise to the reaction medium at room temperature. The whole is left at room temperature with stirring for 3 hours.
• the aromatic polyphenol derivative of the composition 12 is such that
• the 1 H NMR spectrum of the aromatic polyphenol derivative (6) is shown in FIG. 3A ( 1 H NMR (CDCl 3 , 300 MHz): 6.15-5.60 (9H, m), 5.89 (3H, s), 0.15 (18H). , s)).
• the 1 H NMR spectrum of the aromatic polyphenol derivative (7) is shown in FIG. 4A ( 1 H NMR (CDCl 3 , 300 MHz): 7.70-7.30 (30H, m), 6.03 (3H, s), 0.59 (9H). , s)).
• Each aldehyde of each composition 11 to 13 is a preferably aromatic aldehyde and is selected from the group consisting of 1,3-benzenedicarboxaldehyde, 1,4-benzenedicarboxaldehyde, an aldehyde of formula (A):
• X includes N, S or O
• R represents -H or -CHO
• the aldehyde is selected from the group consisting of 1,4-benzenedicarboxaldehyde, furfuraldehyde, 2,5-furanedicarboxaldehyde and mixtures of these compounds.
• the aldehyde of each composition 11 to 13 is 1,4-benzenedicarboxaldehyde.
• the reinforcing filler was incorporated into an elastomer by thermomechanically kneading the whole until a maximum temperature of between 110 ° C. and 190 ° C. was reached. Then the whole was cooled to a temperature below 110 ° C. Then, during a second step, the crosslinking system, the phenol, the aromatic polyphenol or the aromatic polyphenol derivative according to the invention and the aldehyde were incorporated. At the end of this second step, the mixture was heated to 150 ° C until the maximum rheometric torque was obtained in order to vulcanize the composition and crosslink the phenol-aldehyde resin. Then, a characterization of the rigidity at 23 ° C. of the composition was carried out during a tensile test.
• the measurements are carried out at 150 ° C. with an oscillating chamber rheometer according to DIN 53529 - Part 3 (June 1983).
• the evolution of the rheometric torque as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization and crosslinking of the phenol-aldehyde resin.
• the presence of a delay phase is determined when the increase in the rheometric torque over 10 minutes of the tested composition is less than the increase in the rheometric torque over 10 minutes of a control composition comprising the corresponding aromatic polyphenol and the same aldehyde, here the composition T2.
• the presence of such a delay phase is indicated in Table 1.
• FIGS. 2B to 4B show each curve representing the evolution of the rheometric torque respectively of the compositions 11 to 13 as well as those representing the evolution of the rheometric torque of the compositions T0, T1 and T2.
• each composition according to the invention 11 to 13 has a rigidity at 23 ° C equivalent to or even greater than that of the composition T1. In addition, unlike T1, each composition 11 to 13 does not produce formaldehyde during its vulcanization.
• Each composition 11 to 13 has a retardation phase and a rigidity which, although lower than that of the composition T2 in certain examples described, is sufficient to allow a strengthening of the rubber composition.
• this rigidity can be increased by modifying other parameters such as the levels of aromatic polyphenol derivative according to the invention and of aldehyde used.
• composition 11 to 13 exhibits a stiffness performance at elevated temperatures (Cmax) improved with respect to the strength of the composition T0.
• the compositions 11 to 13 have a strength of rigidity at high temperatures (Cmax) at least equal (12) or even significantly higher (11 and 13) than that of the composition T1.
• retardation phase and the rigidity at 23 ° C. can be chosen as functions of the application by varying the -OZ group and in particular the Ri, R 2 and R 3 groups .
• aromatic polyphenol derivatives comprising several aromatic rings, for example benzene, may be envisaged, at least two of them each carrying at least two groups. -OZ in meta position relative to each other. The two ortho positions of at least one of the -O-Z groups of each aromatic ring are unsubstituted.
• an aromatic polyphenol derivative comprising at least one aromatic ring bearing at least two -OZ groups in the meta position with respect to each other, the two ortho positions of at least one of the groups -OZ being unsubstituted and wherein each -OZ group represents a group -O-Si (RiR 2 R 3) with R 1, R 2 , R 3 representing, independently of one another, a hydrocarbon radical or a substituted hydrocarbon radical by using it to generate a retardation phase when crosslinking a phenol-aldehyde resin based on the aromatic polyphenol derivative and an aldehyde independently of its use for the manufacture of a phenol-aldehyde-reinforcing resin a rubber composition.
• an aromatic polyphenol derivative comprising at least one aromatic ring bearing at least two OZ groups in the meta position with respect to each other, the two ortho positions. at least one of -OZ being unsubstituted and wherein each -OZ is -O-Si (RiR 2 R 3 ) with R 1, R 2 , R 3 being independently of one another , a hydrocarbon radical or a substituted hydrocarbon radical by using it in a phenol-aldehyde resin to maintain the stiffness of a rubber composition with increasing temperature regardless of its use for manufacture a phenol-aldehyde resin for reinforcing a rubber composition.
• the characteristics of the aromatic polyphenol derivative and the aldehyde described above also apply to this use in a phenol-aldehyde resin to maintain the stiffness of the rubber composition with increasing temperature.
• Hexa-methylenetetramine from Sigma-Aldrich, purity> 99%
• Precondensed resin SRF 1524 from Schenectady, 75% diluted
• Phloroglucinol from Alfa Aesar, 99% pure

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