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    • 专利摘要:
    The present invention relates to a method of modifying a natural rubber comprising at least the following steps: i. providing at least one natural rubber and epoxidizing said natural rubber to obtain an epoxidized natural rubber, or having a previously epoxidized natural rubber, ii. graft on said epoxidized natural rubber or on said previously epoxidized natural rubber at least one 1,3-dipolar compound having at least one nitrogen atom. The invention also relates to a modified natural rubber obtainable by the process as well as to rubber compositions based on said modified natural rubber.
    公开号:FR3046603A1
    申请号:FR1650182
    申请日:2016-01-11
    公开日:2017-07-14
    发明作者:Etienne Fleury；Baptiste Dit Dominique Francois Jean
    申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；Michelin Recherche et Technique SA France；
    IPC主号:
    专利说明:

    The invention relates to a novel method for modifying a natural rubber, a new modified natural rubber and its use in a new rubber composition, in particular for the manufacture of semi-finished products for tires or for the manufacture of tires.
    Since fuel savings and the need to preserve the environment have become a priority, it is desirable to produce rubber mixtures with good mechanical properties and as low a hysteresis as possible. This reduction in hysteresis is a permanent objective which must, however, be achieved by maintaining the processability, in particular raw, of these mixtures so that they can be used as rubber compositions for the manufacture of various finished or semi-finished products used in the composition of tires, such as, for example, underlays, sidewalls, treads, etc., and in order to obtain tires having a reduced rolling resistance.
    To achieve this objective, many solutions have already been experimented, including the modification of the structure of diene polymers and copolymers. The modification of the chemical structure of a polymer generally impacts its chemical and physical properties as well as the properties of the compositions containing it. This structural modification can in particular be achieved by the introduction of chemical functions using a grafting agent. The introduced functions can, for example, improve the dispersion of the reinforcing filler in the elastomeric matrix and thus make it possible to obtain a more homogeneous material. In the case of certain reinforcing fillers, such as carbon black or silica, a better dispersion of the filler will generally result in a hysteresis decrease in the composition and therefore ultimately in the rolling resistance. By way of illustration of this prior art, mention may be made of the 1,3-dipolar compounds used as grafting and functionalizing agents for polymers, especially diene copolymers. The document WO-A2-2006 / 045088 describes, for example, 1,3-dipolar compounds which allow the grafting of oxazoline, thiazoline, alkoxysilane or allyltin functions. The document WO-A1-2012 / 007441 describes 1,3-dipolar compounds which allow the grafting of nitrogenous associative functions.
    The grafting yields of these compounds on the polymers, in particular synthetic diene copolymers such as polybutadiene (BR), synthetic polyisoprene (IR) and styrene-butadiene copolymer (SBR), are generally high, for example 75% to 100%.
    However, this degree of grafting is not achieved when 1,3-dipolar compounds are used to modify the structure of the natural rubber (the grafting yield is lower than that obtained for synthetic rubbers). For example, it is mentioned in S. Cheawchan et al., Polymer, Vol. 54, Issue 17, 2013, pp. 4501-4510 and in US-A1-2011 / 0054134 and US-A1-2012 / 0046418. that the rate of modification of a compound bearing nitrile oxide dipoles on a natural rubber in solution at 70 ° C or 100 ° C or in mass at room temperature or at 70 ° C reaches a maximum of 60% and after 72 hours of reaction.
    However, there is interest in using natural rubber, especially in compositions for finished or semi-finished products for tires. Indeed, the environmental concerns of the last years militate in favor of the development of products based on raw materials of renewable origin so that they answer as much as possible the concerns of sustainable development by limiting the supplies of raw materials coming from the oil industry for their manufacture.
    There is therefore a need to provide a method for modifying a natural rubber with a 1,3-dipolar compound comprising at least one nitrogen atom, in particular at least one nitrile oxide dipole, this method making it possible to graft with a yield improved chemical groups that can change the properties of natural rubber, including chemical groups that allow a good dispersion of the reinforcing filler.
    An object of the present invention is to provide a method of modifying a natural rubber and a modified natural rubber at least partially overcoming the aforementioned drawbacks.
    This objective is achieved by reacting a 1,3-dipolar compound comprising at least one nitrogen atom, in particular at least one nitrile oxide dipole, on a previously epoxidized natural rubber; which, surprisingly, makes it possible to improve and in particular to increase the grafting yield of said 1,3-dipolar compound.
    A first object of the invention relates to a method of modifying a natural rubber comprising at least the following steps: i. providing at least one natural rubber and epoxidizing said natural rubber to obtain an epoxidized natural rubber, or having a previously epoxidized natural rubber, ii. graft on said epoxidized natural rubber or on said previously epoxidized natural rubber at least one 1,3-dipolar compound having at least one nitrogen atom.
    According to one embodiment of the invention, step (ii) can be carried out in bulk or in solution, preferably in bulk.
    According to one embodiment, step (ii) can be carried out by heating at a temperature greater than or equal to 70 ° C, preferably for at most 4 hours, preferably for at most 2 hours and even more preferably for at most 30 minutes.
    DETAILED DESCRIPTION OF THE INVENTION
    In the present description, any range of values designated by the expression "between a and b" represents the range of values from more than "a" to less than "b" (i.e., terminals a and b). excluded) while any range of values referred to as "a to b" means the range of values from "a" to "b" (ie including strict bounds a and b ). The abbreviation "pce" (usually "phr" in English for "per hundred part of rubber") means parts by weight per hundred parts of elastomers (of the total elastomers if several elastomers are present) or rubber present in the composition of rubber.
    By "majority" or "majority" is meant in the sense of the present invention, the compound is the majority of the compounds of the same type in the composition, that is to say that it is the one that represents the greater amount by mass among the compounds of the same type. In other words, the mass of this compound represents at least 51% of the total mass of the compounds of the same type in the composition. For example, in a system comprising a single elastomer, it is the majority within the meaning of the present invention; and in a system comprising two elastomers, the majority elastomer represents more than half of the total mass of the elastomers, ie the mass of this elastomer represents at least 51% of the total mass of the elastomers. In the same way, a so-called majority charge is that representing the largest mass among the charges of the composition. In other words, the mass of this charge represents at least 51% of the total mass of the charges in the composition.
    The term "heteroatom" refers to any atom other than a hydrogen atom and a carbon atom, preferably nitrogen, oxygen, silicon, sulfur or phosphorus. The term "C1-C4 alkyl" denotes a linear, branched or cyclic hydrocarbon group comprising from 1 to 1 carbon atoms; i and j being integers.
    The term "halogen" means an atom selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I), preferably chlorine (Cl). The term "C1-C4 alkoxyl" refers to a group -OW, wherein W is C1-C4 alkyl as defined above; i and j being integers. The term "C1-C4 heteroalkyl" refers to an alkyl chain comprising from 1 to 1 carbon atoms interrupted by at least one heteroatom, such as N, O or S; i and j being integers. The term "C 1 -C 5 aryl" refers to an aromatic group having from 1 to 1 carbon atoms; i and j being integers. The term "C1-C4 alkylaryl" denotes an alkyl group attached to the remainder of the molecule by an aryl group, all of the carbon atoms of the alkyl group and the aryl group being between 1 and j; i and j being integers. The term "C1-C4 arylalkyl" denotes an aryl group attached to the remainder of the molecule by an alkyl group, all of the carbon atoms of the alkyl and aryl group being between 1 and j; i and j being integers. The term "C 1 -C 5 cycloalkyl" denotes a cyclic saturated hydrocarbon group having from 1 to 1 carbon atoms; i and j being integers.
    For the purposes of the present invention, the term "C1-C4 alkanediyl" means a divalent group of general formula CnH2n derived from an alkane having between 1 and 1 carbon atoms. The divalent group may be linear or branched and optionally substituted.
    The modification process of the invention has the essential characteristic of using as starting material a natural rubber or a previously epoxidized natural rubber.
    According to a first implementation of the process according to the invention, the starting material is a natural rubber which is epoxidized. Natural rubber can be in the form of a solid, it is then a dry natural rubber. Natural rubber may also be in liquid form and more precisely in the form of latex, that is to say in the form of particles dispersed in a liquid, in particular water. This is called natural rubber latex. Natural rubber latex can exist in various forms as described in Chapter 3 "Latex concentrates: properties and composition" by K.F.Gaseley, A.D.T. Gordon and TD Pendle in "Natural Rubber Science and Technology", Roberts AD, Oxford Univeristy Press-20, 1988. In particular, several forms of natural rubber latex are marketed: natural rubber latexes called "field" ("filed"). latex ")," natural "latex rubber (" concentrated natural rubber latex "), deproteinized latex or prevulcanized latex. Field natural rubber latex is a latex in which ammonia has been added to prevent premature coagulation. The concentrated natural rubber latex corresponds to a field latex which has undergone a treatment corresponding to a washing followed by a new concentration. The different categories of concentrated natural rubber latex are listed in particular according to ASTM D 1076-06. Among these concentrated natural rubber latexes, there are in particular concentrated natural rubber latexes of quality called "HA" ("High Ammonia") and quality called "LA" ("Low Ammonia"); Advantageously used for the invention concentrated natural rubber latex HA grade. The latex can be used directly or previously diluted in water to facilitate its implementation. Natural rubber latexes can be made from rubber, Dandelion or Guayule; preferably hevea. Epoxidation can be carried out on a natural rubber latex or on a dry natural rubber. Preferably, the epoxidation is carried out on a natural rubber latex to form an epoxidized latex, which can in particular be dried. The epoxidation of such natural rubbers is known per se. Those skilled in the art will be able to adapt the epoxidation technique according to the type of natural rubber to be epoxidized. By way of example of an epoxidation technique, mention may be made, in a non-limiting manner, of processes based on chlorohydrin or bromohydrin, direct oxidation processes or processes based on hydrogen peroxides, alkyl hydroperoxides or peracids (such as peracetic acid or performic acid).
    According to a second implementation of the process according to the invention, the starting material is a previously epoxidized natural rubber. Natural Epoxidized Natural Rubbers (ENR) are commercially available. As for the preceding variant, these rubbers can be obtained by epoxidation of the natural rubbers, for example by chlorohydrin or bromohydrin-based processes.
    Whatever the variant used, the epoxidized natural rubber or the previously epoxidized natural rubber may have an epoxidation level of less than or equal to 50 mol% and preferably greater than or equal to 0.5 mol%, preferably ranging from from 1 to 45 mol%, more preferably from 2 to 30 mol%.
    By "epoxidation rate" expressed as molar percentage (mol%) is meant the number of moles of cis-1,4-polyisoprene-epoxidized units present in the rubber polymer per 100 moles of total monomer units in the same polymer. The epoxidation rate can be measured in particular by means of 1H NMR analysis. For example, the cis-1,4-polyisoprene units, i.e. the CH2-C (CH3) = CH-CH2 unit, and the cis-1,4-polyisoprene-epoxidized units of the epoxidized natural rubber or previously epoxidized natural rubber are quantified by integration of the massifs of the characteristic signals of the protons of the CH group of the cis-1,4 polyisoprene at 5.1 ppm and the protons of the CHO group of the epoxy ring at 2.6 ppm.
    Both implementations of the modification process according to the invention are equivalent, that is to say that the previously epoxidized natural rubber is equivalent to the natural rubber which has undergone an epoxidation reaction, except that they may have different advantages. In particular, the first implementation can allow access to epoxidized natural rubbers having an epoxidation rate other than those available on the market, thus to obtain customary epoxidation rates. The second implementation of the method according to the invention is advantageous when the natural rubber at the desired epoxidation rate is commercially available because it can thus reduce the number of process steps.
    For the sake of simplification, we will speak in the following description of epoxidized natural rubber independently for a natural rubber previously epoxidized or for a natural rubber having undergone an epoxidation reaction. The other essential compound of the modification process of the invention is a 1,3-dipolar compound having at least one nitrogen atom.
    For the purposes of the present invention, the term "1,3-dipolar compound" means any electrically neutral chemical compound carrying at least one dipole, that is to say a positive charge and a negative charge in one of their main canonical formulas, and capable of forming a dipolar cycloaddition [1,3] on an unsaturated carbon-carbon bond. For further details, those skilled in the art can refer to the definition given by IUP AC (International Union of Pure and Applied Chemistry) in the glossary of class names of organic compounds and structure-based reactivity intermediates. (IUPAC Recommendations 1995, PAC, 1995, 67, 1307).
    By "1,3-dipolar compound having at least one nitrogen atom" is meant in the sense of the present invention a 1,3-dipolar compound whose dipole comprises at least one nitrogen atom.
    More particularly, the 1,3-dipolar compound having at least one nitrogen atom can comprise at least one nitrile oxide dipole, an imine nitrile dipole or a nitrone dipole.
    For the purposes of the present invention, nitrile oxide is understood to mean a dipole corresponding to the formula -C = N-> O, including its mesomeric forms.
    By imine nitrile is meant in the sense of the present invention a dipole corresponding to the formula -C = N ^ N, including its mesomeric forms.
    For the purposes of the present invention, the term "nitrone" means a dipole corresponding to the formula -C = N (-> O) -, including its mesomeric forms.
    Preferably, the 1,3-dipolar compound having at least one nitrogen atom may comprise at least one nitrile oxide dipole.
    According to one embodiment of the invention, the nitrile oxide dipole of the 1,3-dipolar compound may belong to a unit corresponding to formula (I) as described below. In other words, the nitrile oxide dipole of the 1,3-dipolar compound can be attached to the remainder of said compound by an optionally substituted phenyl group and can thus belong to a group D corresponding to the general formula (I): in which :
    - RI, R2, R3, R4, R5, identical or different, represent a hydrogen atom, a halogen atom, a C1-C5 alkyl, a C1-C5 alkoxyl or a covalent bond for attachment to the rest of the 1,3-dipolar compound; with the proviso that at least one of R1, R2, R3, R4, R5 represents said covalent bond. Those skilled in the art understand that the 1,3-dipolar compound according to this embodiment and its variants is composed of the unit of formula (I) and a residue, also called residue of the 1,3-dipolar compound, linked between them by said covalent bond.
    More preferentially, the group D can correspond to the general formula (I) in which: R 1, R 3, R 5, which are identical or different, represent a hydrogen atom, a C 1 -C 5 alkyl or a C 1 -C 5 alkoxyl; R2, R4 represent a hydrogen atom or a covalent bond allowing the attachment to the remainder of the 1,3-dipolar compound; with the proviso that at least one of R2, R4 represents said covalent bond and that at least one of R1, R5 is not a hydrogen atom.
    More preferably still, the group D can correspond to the general formula (I) in which: R 1, R 3, R 5, which are identical or different, represent a hydrogen atom, a methyl, an ethyl, a propyl, a methyloxy, a ethyloxy, propyloxy; R2, R4 represent a hydrogen atom or a covalent bond allowing the attachment to the remainder of the 1,3-dipolar compound, provided that at least one of R2, R4 represents said covalent bond and that at least one RI, R5 is not a hydrogen atom.
    Preferably, the remainder of the 1,3-dipolar compound is a chemical group intended to be grafted onto the epoxidized natural rubber by reaction of the [3 + 2] cycloaddition of the 1,3-dipolar compound bearing said chemical group on the double bonds of the polymer chain.
    Thus, the 1,3-dipolar compound used in the context of the invention may carry both a dipole formed by three atoms on which the charges are delocalised, at least one of which is an atom of nitrogen, and both of at least one chemical group to be grafted onto the epoxidized natural rubber. In other words, the 1,3-dipolar compound further comprises at least one chemical group.
    The chemical group may in particular be any group of atoms which, once grafted onto the polymer makes it possible to modify the chemical and physical properties thereof with respect to the ungrafted polymer, in particular for example makes it possible to ensure good interaction between the polymer and the reinforcing fillers when the polymer is mixed with reinforcing fillers.
    Preferably, the chemical group may be a hydrocarbon chain which may optionally contain at least one heteroatom. For example, the hydrocarbon chain may be linear, cyclic and / or branched; optionally interrupted by at least one heteroatom and / or wherein at least one hydrogen atom carried by a carbon atom has been substituted with a heteroatom.
    More preferably, the chemical group may be chosen from hydrocarbon groups, optionally substituted nitrogen or sulfur heterocycles, esters, phosphates, dialkylamino and associative groups comprising at least one nitrogen atom.
    Advantageously, the 1,3-dipolar compound may also be represented by the following formula (II): G-E-D (II) in which: the symbol G represents the chemical group as defined above, including its preferred modes; the symbol D represents the group of formula (I) defined above, including its preferred modes; and the symbol E represents a spacer connecting G to D.
    Preferably, the 1,3-dipolar compound may correspond to formula (II) in which: the chemical group G can be chosen from hydrocarbon groups, optionally substituted nitrogenous heterocycles, optionally substituted sulfur heterocycles, esters, phosphates, dialkylamino and associative groups comprising at least one nitrogen atom; - D and E being defined above.
    Nitrogenous or sulfurous heterocycles may be suitable in particular those containing 5 to 6 members. They can be saturated or unsaturated and optionally substituted by a C1-C20 hydrocarbon group. Preferably, the nitrogen-containing or sulfur-containing heterocyls may be chosen from optionally substituted 2H-1,3-oxazoline rings, optionally substituted 2H-1,3thiazoline rings, 5,6-dihydro-4H-1,3-cyclones or optionally substituted oxazines, optionally substituted 5,6-dihydro-4H-1,3-thiazine rings, optionally substituted imidazole rings, the substituents being as defined above.
    Among the optionally substituted imidazoles may be suitable in particular those corresponding to the general formula (ΙΠ)
    (ΠΙ) wherein: - R6, R7, R8, R9, identical or different, represent a covalent bond which connects the imidazole ring to the spacer E, a hydrogen atom, a hydrocarbon group C1-C20 or R8 and R9 together with the carbon atoms to which they are attached form an aryl ring, and with the proviso that at least one of R6, R7, R8, R9 represents said covalent bond.
    Preferably, the optionally substituted imidazoles may correspond to formula (III) in which: R6, R7, R8, R9, which may be identical or different, represent a covalent bond which connects the imidazole ring with the spacer E, an atom of hydrogen, C1-C12 alkyl (preferably C1-C6 alkyl) or R8 and R9 form with the carbon atoms to which they are attached a benzene ring, and - provided that at least one of the R6 , R7, R8, R9 represents said covalent bond.
    Among the esters which may be suitable in particular those having the formula C (O) -O-R 10 with R 10 representing a C 1 -C 20 hydrocarbon group, preferably a C 1 -C 12 hydrocarbon group, more preferably representing a C 2 -C 4 hydrocarbon group. This. Preferably, R 10 is C 1 -C 6 alkyl, more preferably R 10 is methyl or ethyl.
    Among the phosphates may be in particular those corresponding to the formula -O-P (O) (OR 11) (OR 12) with R 11 and R 12, identical or different, representing a hydrogen atom, an alkyl, an aryl or an alkylaryl. Preferably, R 11 and R 12 are the same and are C 1 -C 12 alkyl, preferably C 1 -C 6 alkyl, preferably methyl or ethyl.
    Among the dialkylamino groups may especially be suitable those corresponding to the formula -NR13R14 in which RI 3 and RI4, identical or different, represent a C 1 -C 6 alkyl. For example, a Ν, Ν-dimethylamino group, a Ν, Ν-diethylamino group or an N-ethyl, N-propylamino group may be mentioned. Preferably, R13 and R14 are the same and are methyl.
    By "associative group" is meant groups capable of associating with each other by hydrogen, ionic or hydrophobic bonds. According to a preferred embodiment of the invention, these are groups capable of associating with hydrogen bonds.
    When the associative groups are capable of associating with hydrogen bonds, each associative group comprises at least one donor site and one acceptor site with respect to the hydrogen bonding so that two identical associative groups are self-complementary and can to associate with each other by forming at least two hydrogen bonds. The associative groups are particularly likely to associate with hydrogen bonds to functions present on any other compound, for example on reinforcing fillers such as silica or carbon black.
    Preferentially, the associative group comprising at least one nitrogen atom may be chosen from the following formulas (IV), (V) (VI), (VII) and (VIII):
    in which: R 5 represents a hydrocarbon group which may optionally contain heteroatoms, Q represents an oxygen or sulfur atom or NH, preferably an oxygen atom, the symbol * represents an indirect attachment to the dipole of compound 1, 3 dipolar, especially to E.
    Preferably, the associative group comprising at least one nitrogen atom is a heterocycle of formula (IV), di or tri-nitrogenated, with 5 or 6 atoms, preferably diazotized, and comprising at least one carbonyl function. The spacer E can be a covalent bond, an atom or a group of atoms and can connect at least one chemical group G to at least one group D. When E is a group of atoms, it can be thus any type grouping atoms known per se. The spacer E must not, or very little, interfere with the dipole (s) and the chemical group (s) of the compound 1, -3 dipolar intended to be grafted. The spacer can therefore be considered as an inert group, that is to say that it does not have alkenyl or alkynyl functions capable of reacting with the dipole or associative groups as defined above. The spacer E may preferably be a linear, branched, cyclic, optionally substituted hydrocarbon-based chain, provided that the substituents are inert with respect to the dipole (s) and the function (s) to be grafted. The hydrocarbon chain may comprise one or more heteroatoms. Preferably, the spacer E is a C1-C20 alkanediyl, -OR16-, -C (O) -N (H) R16-, -N (H) R16- with R16 a C1-C20 alkanediyl. Preferably, the spacer E may be a C 1 -C 6 alkanediyl, -OR 16 -, -C (O) -N (H) R 16 -, -N (H) R 16 - with R 16 a C 1 -C 6 alkanediyl. This. By way of examples of C 1 -C 6 alkanediyl, there may be mentioned in particular a methylene -CH 2 - group, an ethylene -CH 2 -CH 2 - group, a propylene -CH 2 -CH 2 -CH 2 - group, a butylene -CH 2 group -CH2-CH2-CH2-, etc.
    According to a preferred embodiment of the invention, the 1,3-dipolar compound may correspond to the formula (II) GED (Π) in which: D corresponds to the formula (I) in which: R 1, R 3, R5, which may be identical or different, represent a hydrogen atom, a C1-C5 alkyl or a C1-C5 alkoxyl; R2, R4 represent a covalent bond allowing attachment to E or a hydrogen atom; with the proviso that at least one of R 2, R 4 represents said covalent bond and that at least one of R 1, R 5 is not a hydrogen atom; G represents a hydrocarbon-based group, an optionally substituted 5- to 6-membered nitrogen or sulfur heterocycle, an ester, a phosphate, a dialkylamino or an associative group comprising at least one nitrogen atom; E represents a covalent bond or a chain; hydrocarbon optionally substituted and optionally interrupted by one or more heteroatoms.
    According to another preferred embodiment of the invention, the 1,3-dipolar compound may correspond to formula (II) GED (II) in which: - D corresponds to formula (I) in which: - RI, R3 R5, which may be identical or different, represents a hydrogen atom, a methyl, an ethyl, a propyl, a methyloxy, an ethyloxy or a propyloxy; R2, R4 represent a covalent bond allowing attachment to E or a hydrogen atom; and - provided that at least one of R2, R4 is said covalent bond and at least one of R1, R5 is not hydrogen; G is selected from the group consisting of - hydrocarbon groups, - esters corresponding to the formula C (O) -O-RIO with RIO representing a C1-C20 hydrocarbon group, preferably a C1-C12 hydrocarbon group, more preferably, a C 1 -C 6 hydrocarbon group, still more preferably R 10 is C 1 -C 6 alkyl, more preferably R 10 is methyl or ethyl; the phosphates -O-P (O) (OR) (OR 12) with R 11 and R 12, which may be identical or different, representing a hydrogen atom, an alkyl, an aryl or an alkylaryl, preferably identical R 11 and R 12 being a C1-C12 alkyl, more preferably C1-C6 alkyl, even more preferably methyl or ethyl; the NR13R14 dialkylaminos in which R13 and R14, which are identical or different, represent a C1-C6 alkyl, preferably R13 and R14 are identical and are methyl; the imidazoles of formula (III) in which R6, R7, R8, R9, which may be identical or different, represent a covalent bond which connects the imidazole ring with the spacer E, a hydrogen atom or a C 1 -C 12 alkyl ( preferably C 1 -C 6 alkyl) or R 8 and R 9 together with the carbon atoms to which they are attached form a benzene ring, and with the proviso that at least one of R 6, R 7, R 8, R 9 represents said covalent bond; and the associative groups comprising at least one nitrogen atom and being chosen from formulas (IV), (V) (VI), (VII) and (VIII), preferably being a heterocycle of formula (IV)) di or triazoté, at 5 or 6 atoms, preferably di nitrogenous, and comprising at least one carbonyl function; E represents a covalent bond or a group of atoms chosen from C1-C20 alkanediyls, -OR16- groups, -C (O) -N (H) R16- groups, -N (H) R16 groups; with R16 a C1-C20 alkanediyl, preferably with R16 a C1-C10 alkanediyl.
    According to a particular embodiment of the invention, the preferred 1,3-dipolar compound may in particular be chosen from the compounds corresponding to the formulas below (IX), (X), (XI), (XII), (ΧΙΠ), (XIV), (XV), (XVI), (XVII), (XVIII), (XIX) and their mesomeric forms:
    The 1,3-dipolar compound that is more particularly preferred may be chosen in particular from the compounds corresponding to the formulas above (IX), (X), (XI), (ΧΠ), (XIII), (XIV), (XV) , (XVI), and (XIX), including their mesomeric forms.
    The 1,3-dipolar compound which is more particularly preferred may be the compound of formula (XIV) or the compound of formula (XIX).
    In the remainder of the present description for the sake of simplification, the expression "1,3-dipolar compound" will be used to designate the 1,3-dipolar compound having at least one nitrogen atom used in the process according to the invention. as well as its favorite shapes.
    The 1,3-dipolar compound can be synthesized by any chemical reactions well known to those skilled in the art. By way of example, reference may be made to the synthetic methods described in applications PCT / EP2015 / 060926, PCT / EP2015 / 060926, FR 15/56565, WO-A2-2006 / 045088, FR15 / 51635, WO-A1. -2015/059269, WO-A1-2015 / 059271, WO-A1-2012 / 007684, WO-A1-2012 / 007441, WO-A1-2012 / 007442 and WO-A1-2014 / 090756.
    In particular, the 1,3-dipolar compound carrying both a nitrile oxide dipole and a dialkylamino group can be obtained, for example, according to the procedure described in the article J. Org. Chem., 1967, 32 (7), pp 2308-2312.
    The grafting of the 1,3-dipolar compound on the epoxidized natural rubber is carried out by reacting said epoxidized natural rubber with the 1,3-dipolar compound as defined above. During the reaction, the dipole of the 1,3-dipolar compound forms covalent bonds with the chain of the epoxidized natural rubber. The grafting yield is particularly high, preferably greater than 60%. By "graft yield" or "yield" is meant the molar percentage content of 1,3-dipolar compound grafted on the epoxidized natural rubber chain with respect to the molar percentage content of 1,3-dipolar compound introduced as starting reagent.
    By "molar level of the 1,3-dipolar compound" is meant the number of moles of 1,3-dipolar compound used per 100 units of epoxidized natural rubber, that is to say for 100 monomer units of the epoxidized natural rubber. (isoprene monomer unit and epoxidized isoprene monomer unit). For example, if the level of 1,3-dipolar compound is 1 mol% for a natural rubber epoxidized with 50% epoxide, this means that there is 1 mole of 1,3-dipolar compound per 100 isoprene units. epoxidized or non-epoxidized.
    The grafting of the 1,3-dipolar compound is carried out by [3 + 2] cycloaddtion of the 1,3-dipolar compound dipole on unsaturation, in particular a carbon-carbon double bond, of the epoxidized natural rubber chain. The mechanism of the cycloaddition can be illustrated by the following generic reaction schemes: • Cycloaddition of a nitrile oxide on an unsaturation or double bond of the polymer (here an isoprene unit)
    • Cycloaddition of a nitrone on an unsaturation or double bond of the polymer (here an isoprene unit)
    • Cycloaddition of a nitrile imine on an unsaturation or double bond of the polymer (here an isoprene unit)
    The grafting of the 1,3-dipolar compound can be carried out in bulk, for example in an internal mixer or an external mixer such as a roller mixer. It can also be carried out in solution, continuously or discontinuously. The modified natural rubber can be separated from its solution by any type of means known to those skilled in the art and in particular by a stripping operation with water vapor.
    According to one embodiment, the grafting reaction can be carried out by heating the reaction mixture to a temperature greater than or equal to 70 ° C, and preferably for not more than 4 hours; preferably for not more than 2 hours and even more preferably for not more than 30 minutes.
    According to one embodiment of the invention, the level (in molar percentage (% mol)) of the 1,3-dipolar compound may range from 0.1 to 10 mol%, preferably from 0.1 to 5 mol%.
    Another object of the present invention relates to a modified natural rubber obtainable, in particular being obtained, according to any of the embodiments of the modification method, including its preferred modes.
    This modified natural rubber may comprise, statistically distributed within the chain, cis-1,4 isoprene units, epoxidized cis-1,4 isoprene units and units resulting from the [3 + 2] cycloaddition of at least one 1,3-dipolar compound as defined above.
    The modified natural rubber of the invention is particularly suitable for use in reinforced rubber composition for the manufacture of semi-finished and finished products such as tires. Indeed, the presence on the epoxy cycle elastomer and chemical groups, in particular chemical groups capable of interacting with a reinforcing filler, improves the performance of the tire, in particular the adhesion performance and rolling resistance.
    Thus, another subject of the present invention relates to a rubber composition based on: at least one modified natural rubber that can be obtained or obtained by the process described above, irrespective of the variant of the process used , at least one reinforcing filler, and at least one crosslinking system.
    "Rubber composition based on" means a rubber composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being capable of or intended to react with each other, less in part, during the various phases of manufacture of the composition, in particular during its crosslinking or vulcanization.
    The modified natural rubber may consist, according to the invention, of a mixture of several modified natural rubbers according to the invention.
    According to one embodiment of the invention, the rubber composition may also, in addition to the modified natural rubber, comprise at least one other diene elastomer. This or these other diene elastomers may then be present in the composition in proportions of between 0 and 60 phr (the limits of this range being excluded), preferably at most 49 phr, even more preferably at most 30 phr.
    According to one embodiment of the invention, the mass fraction of the natural rubber modified in the composition may be the majority. In other words, the modified natural rubber may represent at least 51% of the total mass of all the elastomers present in the composition. Preferably, the level of modified natural rubber may be at least 51 phr, in particular at least 70 phr.
    According to another embodiment of the invention, the amount of modified natural rubber may range from 51 phr to 100 phr, preferably this level may be equal to 100 phr.
    By "diene elastomer" is intended to be understood according to the invention any elastomer of synthetic origin constituted at least in part (that is to say a homopolymer or a copolymer) of monomer (s) diene (s) (ie, carrier (s) of two carbon-carbon double bonds, conjugated or not).
    These diene elastomers can be classified into two categories: "essentially unsaturated" or "essentially saturated". The term "essentially unsaturated" is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%); Thus, diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated" diene elastomers ( low or very low diene origin, always less than 15%). In the category of "essentially unsaturated" diene elastomers, the term "highly unsaturated" diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
    These definitions being given, the term "diene elastomer" may be understood more particularly to be used in the compositions according to the invention: (a) - any homopolymer of a conjugated diene monomer, especially any homopolymer obtained by polymerization of a diene monomer conjugate having from 4 to 12 carbon atoms; (b) - any copolymer obtained by copolymerization of one or more conjugated dienes with each other or with one or more vinyl aromatic compounds having from 8 to 20 carbon atoms; (c) - a ternary copolymer obtained by copolymerization of ethylene, an α-olefin having 3 to 6 carbon atoms with a non-conjugated diene monomer having from 6 to 12 carbon atoms, for example elastomers obtained from ethylene, propylene with a non-conjugated diene monomer of the aforementioned type such as in particular 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene; (d) - a copolymer of isobutene and isoprene (butyl rubber), as well as the halogenated versions, in particular chlorinated or brominated, of this type of copolymer.
    Although it applies to any type of diene elastomer, the person skilled in the tire art will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b). ) above.
    In the case of copolymers of type (b), these contain from 20% to 99% by weight of diene units, and from 1 to 80% by weight of vinylaromatic units. As conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5) alkyl-1,3-butadienes, such as for example 2 3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1, 3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene. Suitable vinyl aromatic compounds are, for example, styrene, ortho-, meta-, para-methyl styrene, the "vinyl-toluene" commercial mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene and divinylbenzene. vinylnaphthalene.
    Preferably, the diene elastomer may be chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (BR), butadiene copolymers, polyisoprenes (PI), isoprene copolymers and mixtures of these elastomers. Such copolymers may be more preferably chosen from the group consisting of copolymers of butadiene and a vinylaromatic monomer, more particularly butadiene-styrene copolymer (SBR), isoprene-butadiene copolymers (BIR), copolymers of isoprene and a vinylaromatic monomer, more particularly the isoprene-styrene copolymer (SIR) and the isoprene-butadiene-styrene copolymers (SBIR). Of these copolymers, copolymers of butadiene and a vinylaromatic monomer, more particularly the butadiene-styrene copolymer (SBR), are particularly preferred.
    These diene elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used. The diene elastomers can be, for example, block, random, sequenced or microsequential, and can be prepared in dispersion or in solution. The diene elastomer may be star-shaped, coupled, functionalized or otherwise, in a manner known per se, by means of functionalising, coupling or starring agents known to those skilled in the art.
    The rubber composition according to the invention comprises at least one reinforcing filler, for example carbon black or a reinforcing inorganic filler such as silica with which a coupling agent is associated in a known manner, or a mixture of these two. types of charge.
    Suitable carbon blacks are all carbon blacks, used individually or in the form of mixtures, in particular blacks of the HAF, ISAF, SAF type conventionally used in tires (so-called pneumatic grade blacks). It is also possible to use, according to the targeted applications, blacks of higher series FF, FEF, GPF, SRF. The carbon blacks could for example already be incorporated into the diene elastomer in the form of a masterbatch, before or after grafting and preferably after grafting (see, for example, applications WO-A2-97 / 36724 or WO-Al-99 / 16600).
    "Reinforcing inorganic filler" means any inorganic or mineral filler, irrespective of its color and origin (natural or synthetic), also called "white" filler, "clear" filler or even "non-black" filler. ("Non-black filler") as opposed to carbon black; this inorganic filler being able to reinforce on its own, without any other means than an intermediate coupling agent, a rubber composition intended for the manufacture of pneumatic tires, in other words able to replace, in its reinforcing function, a conventional carbon black of pneumatic grade. Such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface, requiring to be used as a reinforcing filler the use of an agent or coupling system intended to ensure a binding stable chemical charge and elastomeric matrix.
    Inorganic reinforcing fillers are particularly suitable mineral fillers of the siliceous type such as silica. The silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g, especially between 60 and 300 m2 / g. Highly dispersible precipitated silicas ("HDS") include, for example, "Ultrasil 7000" and "Ultrasil 7005" silicas from Evonik, "Zeosil 1165MP, 1135MP and 1115MP" silicas and "Zeosil" silica. Solvay Premium 200 ", the" Hi-Sil EZ150G "silica from the PPG company, the" Zeopol 8715, 8745 and 8755 "silicas from the Huber Company, the high surface area silicas as described in the WO-application A1-03 / 016387.
    In the present disclosure, the BET surface area is determined in a known manner by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society" Vol. 60, page 309, February 1938, more precisely according to the French standard NF ISO 9277 of December 1996 (volumetric method (5 gas point: nitrogen - degassing: 1 hour at 160 ° C. - relative pressure range p / po: 0.05 at 0.17) The CTAB specific surface is the external surface determined according to the French standard NF T45-007 of November 1987 (method B).
    Of course, inorganic reinforcing filler is also understood to mean mixtures of different reinforcing inorganic fillers, in particular highly dispersible silicas as described above or a mixture of siliceous type inorganic fillers and inorganic non-siliceous fillers. Non-siliceous inorganic fillers that may be mentioned include mineral fillers of the aluminous type, in particular alumina (Al 2 O 3) or (oxides) aluminum hydroxides, or reinforcing titanium oxides, for example described in US Pat. B 1-6,610,261 and US-B2-6,747,087. Non-siliceous inorganic fillers, when present, are minor in the reinforcing filler. The physical state under which the reinforcing filler is present is indifferent, whether in the form of powder, microbeads, granules, beads or any other suitable densified form. Of course, reinforcing filler is also understood to mean mixtures of different reinforcing fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below. Those skilled in the art will understand that as an equivalent load of the reinforcing inorganic filler described in this paragraph, it would be possible to use a reinforcing filler of another nature, in particular an organic filler such as carbon black, since this filler reinforcing would be covered with an inorganic layer such as silica, or would comprise on its surface functional sites, including hydroxyl, requiring the use of a coupling agent to establish the connection between the filler and the elastomer. By way of example, mention may be made, for example, of carbon blacks for tires as described, for example, in documents WO-A2-96 / 37547, WO-A1-99 / 28380.
    According to one embodiment of the invention, the reinforcing filler may be mainly composed of carbon black, preferably it may comprise at least 51% by weight of carbon black relative to the total weight of the reinforcing filler. Preferably, the reinforcing filler may consist of 100% by weight of carbon black relative to the total weight of the reinforcing filler.
    If the reinforcing filler comprises less than 100% by weight of carbon black relative to the total weight of the reinforcing filler, the additional filler is provided by at least one other reinforcing filler, especially an inorganic reinforcing filler such as silica.
    According to another embodiment of the invention, the reinforcing filler may be predominantly a reinforcing inorganic filler, that is to say a reinforcing filler other than carbon black. It may preferably comprise more than 51% by weight, relative to the total weight of the reinforcing filler, of one or more reinforcing inorganic filler (s), in particular a reinforcing inorganic filler such as silica. Preferably, the reinforcing filler may exclusively consist of an inorganic reinforcing filler, especially exclusively made of silica. In other words, the reinforcing filler may consist of 100% by weight relative to the total weight of the reinforcing filler of a reinforcing inorganic filler such as silica.
    If the reinforcing filler comprises less than 100% by weight of inorganic reinforcing filler with respect to the total weight of the reinforcing filler, the additional filler is provided by at least one other reinforcing filler, such as, for example, carbon black. According to this variant, when the carbon black is present, it may be used in the composition at a content of less than 20 phr, more preferably less than 10 phr (for example may range from 0.5 to 20 phr, in particular may range from 2 to 10 phr).
    Preferably, the total reinforcing filler content (that is to say, according to the variants, the carbon black content, the level of inorganic reinforcing filler such as silica or the carbon black content and inorganic reinforcing filler. such as silica) can range from 30 to 200 phr, more preferably from 40 to 150 phr. The person skilled in the art knows how to adapt this total reinforcing filler content in the composition as a function of the different specific applications aimed at.
    The rubber compositions in accordance with the invention may also contain reinforcing organic fillers which may replace all or part of the carbon blacks or other reinforcing inorganic fillers described above. Examples of reinforcing organic fillers that may be mentioned include functionalized polyvinyl organic fillers as described in WO-Al-2006/069792, WO-A1-2006 / 069793, WO-Al-2008/003434 and WO-A1- 2008/00343 5.
    When the reinforcing filler comprises a filler requiring the use of a coupling agent to establish the bond between the filler and the modified natural rubber and between the filler and the other diene elastomer when present, the rubber composition according to the invention may furthermore comprise, in a conventional manner, an agent capable of efficiently providing this link. When the silica is present in the composition as a reinforcing filler, an at least bifunctional coupling agent (or bonding agent) is used in known manner in order to ensure a sufficient chemical and / or physical connection between the filler inorganic (surface of its particles) and the modified natural rubber and between the filler and the other diene elastomer when present, in particular organosilanes or bifunctional polyorganosiloxanes. As coupling agent, mention may be made of polysulfurized silanes, said to be "symmetrical" or "asymmetrical" according to their particular structure, as described, for example, in the applications WO-Al-03/002648 (or US Pat. 2005/016651) and WO-Al-03/002649 (or US-A1-2005 / 016650).
    In particular, polysulphide silanes having the following general formula (XX): Z - A - Sx - A - Z (XX) in which: - x is an integer of 2 to 8 (preferably from 2 to 5); the symbols A, which may be identical or different, represent a divalent hydrocarbon radical (preferably a C 1 -C 18 alkylene group or a C 6 -C 12 arylene group, more particularly a C 1 -C 10, especially C 1 -C 4, alkylene, in particular propylene); the symbols Z, which are identical or different, correspond to one of the following three formulas:
    in which: the radicals R1, substituted or unsubstituted, identical or different from each other, represent a C 1 -C 18 alkyl, C 5 -C 18 cycloalkyl or C 6 -C 18 aryl (preferably C 1 -C 6 alkyl, cyclohexyl) groups; or phenyl, especially C1-C4 alkyl groups, more particularly methyl and / or ethyl). the radicals R2, substituted or unsubstituted, which are identical to or different from one another, represent a C1-C15 alkoxyl or C5-C18 cycloalkoxyl group (preferably a group chosen from C1-C10 alkoxyls and C5-C15 cycloalkoxyls, more preferably still another group chosen from C1-C4 alkoxyls, in particular methoxyl and ethoxyl).
    In the case of a mixture of polysulfurized alkoxysilanes corresponding to the formula (XX) above, in particular common commercially available mixtures, the average value of the "x" is a fractional number preferably between 2 and 5, more preferably close to 4. But the invention can also be advantageously implemented for example with disulfide alkoxysilanes (x = 2). By way of examples of polysulphurized silanes, mention may be made more particularly of bis (C 1 -C 4 alkoxy-C 1 -C 4 alkylsilyl-C 1 -C 4 alkyl) polysulfides (especially disulfides, trisulphides or tetrasulfides), as for example polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl). Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT, of formula [(C2H50) 3Si (CH2) 3S2] 2 or bis (triethoxysilylpropyl) disulfide, abbreviated as TESPD, is especially used. formula [(C2H50) 3Si (CH2) 3S] 2. Mention may also be made, by way of preferred examples, of polysulfides (in particular disulphides, trisulphides or tetrasulfides) of bis- (C 1 -C 4 monoalkoxyl) -dialkyl (C 1 -C 4) silylpropyl), more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide, as described above. in the aforementioned patent application WO-A1-02 / 083782 (or US-B2-7,217,751). By way of example of coupling agents other than a polysulfurized alkoxysilane, mention may be made in particular of bifunctional POS (polyorganosiloxanes) or hydroxysilane polysulfides (R2 = OH in formula (XX) above) as described. for example in patent applications WO-A1-02 / 30939 (or US-B 1-6,774,255), WO-A1-02 / 31041 (or US-A-2004/051210), and WO-A1-2007 / 061550 or silanes or POS bearing azo-dicarbonyl functional groups, as described for example in patent applications WO-A1-2006 / 125532, WO-A1-2006 / 125533, WO-A1-2006 / 125534. As examples of other sulphurized silanes, mention may be made, for example, of silanes carrying at least one thiol function (-SH) (called mercaptosilanes) and / or of at least one blocked thiol function, as described for example in patents or patent applications US-B2-6,849,754, WO-A1-99 / 09036, WO-A2-2006 / 023815, WO-A2-2007 / 098080, WO-A1-2010 / 072685 and WO-A2-2008 / 055986.
    Of course, mixtures of the coupling agents described above could also be used, as described in particular in the aforementioned application WO-A1-2006 / 125534.
    The content of coupling agent may advantageously be less than 20 phr, it being understood that it is generally desirable to use as little as possible. Typically the level of coupling agent may represent from 0.5% to 15% by weight relative to the amount of inorganic filler. Its level is preferably may range from 0.5 to 12 phr, more preferably may be in a range from 3 to 10 phr. This level can be easily adjusted by those skilled in the art according to the level of inorganic filler used in the composition. These preferred ranges apply to any of the embodiments of the invention.
    The composition according to the invention may also contain, in addition to the coupling agents, activators for coupling the reinforcing filler or, more generally, processing aid agents that may be used in known manner, thanks to an improvement in the dispersion. of the charge in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to implement in the green state.
    The rubber compositions in accordance with the invention may also comprise all or part of the usual additives normally used in elastomer compositions intended for the manufacture of tires, for example pigments, protective agents such as anti-ozone waxes, chemical antiozonants, anti-oxidants, anti-fatigue agents, reinforcing or plasticizing resins, acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M) as described, for example, in the application WO 02/10269, vulcanization activators, adhesion promoters such as cobalt-based compounds, plasticizing agents, preferably non-aromatic or very weakly aromatic selected from the group consisting of naphthenic oils, paraffinic oils, MES oils, TDAE oils, ethers plasticizers, ester plasticizers, hydrocarbon resins having a high Tg, preferably greater than 30 ° C, as described for example in the applications WO-Al-2005/087859, WO-A1-2006 / 061064 and WO-A1-2007 / 017060, and mixtures of such compounds.
    The composition according to the invention comprises a chemical crosslinking system which allows the formation of covalent bonds between the elastomer chains. The chemical crosslinking system may be a vulcanization system or a one or more peroxide compound system.
    According to a first preferred variant, the crosslinking system is a vulcanization system, that is to say a system based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator. To this basic vulcanization system can be added, incorporated during the first non-productive phase and / or during the productive phase as described later, various known secondary accelerators or vulcanization activators such as zinc oxide. , stearic acid or equivalent compounds, guanidine derivatives (in particular diphenylguanidine), or known vulcanization retarders.
    When sulfur is used, it can be used at a preferential rate ranging from 0.5 to 12 phr, in particular from 1 to 10 phr. These preferred ranges apply to any of the embodiments of the invention. The primary vulcanization accelerator may be used at a preferred level ranging from 0.5 to 10 phr, more preferably from 0.5 to 5.0 phr. These preferred ranges apply to any of the embodiments of the invention.
    It is possible to use as accelerator (primary or secondary) any compound capable of acting as accelerator for vulcanization of diene elastomers in the presence of sulfur, in particular thiazole-type accelerators and their derivatives, accelerators of the thiuram type, zinc dithiocarbamates. These accelerators are for example selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS"), tetrabenzylthiuram disulfide ("TBZTD"), N-cyclohexyl-2-benzothiazyl sulfenamide ("CBS"), N, N dicyclohexyl-2-benzothiazyl sulphenamide ("DCBS"), N-tert-butyl-2-benzothiazyl sulphenamide ("TBBS"), N-tert-butyl-2-benzothiazyl sulphenimide ("TBSI"), zinc dibenzyldithiocarbamate (" ZBEC ") and mixtures of these compounds.
    According to a second variant, when the chemical crosslinking is carried out using one or more peroxide compounds, the level of said peroxide compound (s) can range from 0.01 to 10 phr. As peroxidic compounds that can be used as chemical crosslinking systems, mention may be made of acyl peroxides, for example benzoyl peroxide or p-chlorobenzoyl peroxide, peroxide ketones, for example methyl ethyl ketone peroxide or peroxyesters, for example butylperoxyacetate, t-butylperoxybenzoate and t-butylperoxyphthalate, alkyl peroxides, for example dicumyl peroxide, di-t-butyl peroxybenzoate and 1,3-bis (t-butyl peroxyisopropyl) benzene, hydroperoxides, for example t-butyl hydroperoxide). The peroxide compound (s) may be incorporated during the production phase as described later.
    Another object of the invention is a process for preparing the rubber composition described above.
    The rubber composition according to the invention may be manufactured in suitable mixers, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first phase of work or thermomechanical mixing (sometimes referred to as "phase"). non-productive ") at high temperature, up to a maximum temperature ranging from 130 ° C to 200 ° C, preferably from 145 ° C to 185 ° C, followed by a second mechanical working phase (sometimes referred to as "productive" phase) at a lower temperature, typically below 120 ° C, for example from 60 ° C to 100 ° C, finishing phase during which the chemical crosslinking system is incorporated.
    In general, all the basic constituents of the composition of the invention, with the exception of the chemical crosslinking system, namely the reinforcing filler or fillers, the coupling agent if appropriate, can be incorporated in an intimate manner. , by kneading, with the modified natural rubber and with the other diene elastomers optionally present or with the epoxidized or epoxidized natural rubber in the presence of at least one 1,3-dipolar compound, during the first so-called non-productive phase, that is to say that is introduced into the mixer and that is kneaded thermomechanically, in one or more steps, at least these different basic constituents until reaching the maximum temperature ranging from 130 ° C to 200 ° C, preferably from 145 ° C to 185 ° C. This first phase is then followed by a second phase of mechanical work (sometimes called a "productive" phase) at a lower temperature, typically below 120 ° C, for example between 60 ° C and 100 ° C, finishing phase at during which is incorporated the chemical crosslinking system.
    After the incorporation of all the ingredients of the rubber composition, the final composition thus obtained can then be calendered, for example in the form of a sheet or a plate, in particular for a characterization in the laboratory, or else extruded, to form for example a rubber profile used as a finished product or semi-finished.
    According to one embodiment of the invention, the grafting of the 1,3-dipolar compound as defined above on the epoxidized or previously epoxidized natural rubber can be carried out beforehand, according to the process of the invention, in the preparation of the composition of rubber. Thus, it is the modified natural rubber which is introduced during the first so-called non-productive phase.
    Thus, according to this embodiment of the process, it may comprise at least the following steps: incorporating into the modified natural rubber, at least one reinforcing filler and in particular all the other constituents of the composition when they are present, exception of the crosslinking system, by thermomechanically kneading the whole, in one or more times, until a maximum temperature of 130 ° C to 200 ° C, preferably 145 ° C to 185 ° C, is reached. the whole at a temperature below 100 ° C, - then incorporate at least one chemical crosslinking system, - knead the whole to a maximum temperature below 120 ° C, - extrude or calender the rubber composition thus obtained.
    According to another embodiment of the invention, the grafting of the 1,3-dipolar compound as defined above on the epoxidized or epoxidized natural rubber can be carried out concomitantly with the preparation of the rubber composition. In this case, the epoxidized natural rubber or the previously epoxidized natural rubber and the 1,3-dipolar compound are introduced during the so-called non-productive first phase. Preferably, the reinforcing filler and the other diene elastomer, when it is optionally present, are then added subsequently during this same non-productive phase in order to prevent any parasitic reaction with the 1,3-dipolar compound.
    Thus, in this second embodiment of the method, it may comprise at least the following steps: dispose of at least one natural rubber and epoxidize said natural rubber to obtain an epoxidized natural rubber, or have a natural rubber beforehand epoxidized, incorporate in the epoxidized natural rubber or in the previously epoxidized natural rubber, at least one 1,3-dipolar compound having at least one nitrogen atom, and as described above, subsequently incorporating at least one reinforcing filler, and optionally all the constituents of the composition, with the exception of the chemical crosslinking system, by thermomechanically kneading the whole, in one or more times, until reaching a maximum temperature ranging from 130 ° C. to 200 ° C., preferably ranging from 145 ° C to 185 ° C, cool all at a temperature below 100 ° C, then incorporate at least one chemical crosslinking system, ma lax everything to a maximum temperature below 120 ° C, extrude or calender the rubber composition thus obtained.
    In this embodiment, the incorporation of at least one 1,3-dipolar compound epoxidized natural rubber or natural rubber previously epoxidized can be carried out at a temperature greater than or equal to 70 ° C. Those skilled in the art will understand that when the rubber composition comprises at least one other diene elastomer as described above, the rubber composition may preferably be manufactured according to the first embodiment of the process in order to avoid any parasitic reaction between this other diene elastomer and the 1,3-dipolar compound. The invention also relates to a finished or semi-finished rubber product comprising at least one rubber composition according to the invention or obtainable according to one of the methods of the invention, more particularly a finished product or semi-finished rubber for tire. Preferred variants and modes of the rubber composition of the invention apply to the finished or semi-finished product. A semi-finished product may for example be a tread. The invention also relates to a tire which comprises at least one semi-finished product as described above.
    The aforementioned features of the present invention, as well as others, will be better understood on reading the following description of several embodiments of the invention, given by way of illustration and not limitation.
    EXEMPLARY EMBODIMENTS 1, Origin of the Reagents, Preparation of the NRs and Characterizations 1.1 Origins of the Reagents Hydrogen peroxide (30% by weight in water) and formic acid (95%) come from Aldrich. Polyisoprene NIPOL 2200 comes from Nippon Zeon. 1.2 Preparation of nitrile oxides a) Synthesis of 2,4,6-trimethylphenyl-3- (2- (2-oxoimidazolidin-1-yl) ethoxy) nitriloxide (Compound A)
    The synthesis of this compound is described in patent FR2962737 b) Synthesis of N, N, 3,5-tetramethyl-4 - [(oxido-X 5 -azanylidyne) methyl] aniline (compound B)
    The synthesis of compound B is described in article J. Or g. Chem., 1967, 32 (7), pp 2308-2312 1.3 Preparation of natural rubbers
    A deproteined natural rubber (deproteinized NR) and a plasticized natural rubber (plasticized NR) are used for comparison.
    The deproteinized NR rubber is derived from a natural rubber latex which has undergone five successive centrifugations and then dried at 65 ° C. under partial vacuum and nitrogen sweeping for 48 hours.
    The plasticized NR rubber is prepared according to the conventional methods described in the following patent applications FR1377363, FR2391225, KR2009033559, JP200241407.
    The natural rubber is epoxidized according to the following procedure to obtain 25% ± 2% molar epoxidized natural rubbers (25% molar ENR (ENR 25)):
    The first step is to devolatilize the ammonia of a latex of a natural rubber called HA. To do this, the 60% polyisoprene latex is left under moderate stirring for 24 hours (until the pH is neutralized) in the presence of 3 phr of nonionic surfactant to stabilize it. After this step, pure formic acid ([HCOOH] / [olyisoprene unit] = 0.3) is added dropwise (for a minimum of 15 minutes). The reaction medium is then heated to 53 ° C. before adding hydrogen peroxide (30% H 2 O 2). The amount of H 2 O 2 added is dependent on the desired epoxidation rate (see Table 1). After stirring for 24 hours at 53 ° C., the chemical reaction is stopped by cooling to room temperature and then neutralizing with sodium hydroxide (1.3 equivalents). The latex is then destabilized by addition of steam (stripping) for 30 minutes, then creped, washed with water and dried for 48 hours at 65 ° C under partial vacuum and under nitrogen flushing.
    Table 1.
    The molar percentage of epoxy ring obtained at the end of the treatment is determined by NMR according to the method described below. 1.4 Measurements and tests used
    The elastomers and rubber compositions are characterized, before and after firing, as indicated below. 1.4.1 - Determination of the epoxide level
    The determination of the epoxide level is carried out by NMR analysis. The spectra are acquired on a BRUKER 500 MHz Avance spectrometer equipped with a BBIz-grad 5mm wideband probe for soluble samples and on a BRUKER 500MHz Avance spectrometer equipped with a 4mm * H / 13C HRMAS probe for samples. insoluble. The quantitative H NMR experiment uses a 30 ° single pulse sequence and a 5 second repetition time between each acquisition. 256 accumulations are made. The samples (approximately 25 mg) are solubilized in deuterated chloroform (approximately 1 ml).
    The NMR * H spectra of these samples show the presence of signals at 2.6 and 1.2 ppm attributed to epoxy units. • 2.6 ppm: -CH group No. 4. • 1.2 ppm: -CH3 group No. 3.
    1.4.2 - Determination of the Grafted 1,3-Dipolar Compound Level on the Rubbers Tested
    The determination of the level of 1,3-dipolar compound grafted on the natural rubber chain or on the synthetic polyisoprene chain is carried out by NMR analysis. The spectra are acquired on a BROKER 500 MHz Avance spectrometer equipped with a BBIz-grad 5 mm wide band probe for soluble samples and on a BRUKER 500MHz Avance spectrometer equipped with a HRMAS 4mm * H / 13C probe for samples. insoluble. The quantitative NMR * H experiment uses a 30 ° single pulse sequence and a 5 second repetition time between each acquisition. 256 accumulations are made. The samples (about 25 mg) are solubilized in deuterated chloroform (about 1 ml), washing with it to remove excess unreacted 1,3-dipolar compound.
    o Characterization of the ENRs modified by compound A
    The 1 H NMR spectrum makes it possible to quantify the grafted nitrile oxide units by integrating the characteristic signals of the CH2N and CH20 protons which appear at a chemical shift of between 3.1 and 3.8 ppm. The HSQC 2D NMR spectrum makes it possible to verify the nature of the grafted pattern by virtue of the chemical shifts of the carbon and proton atoms.
    o Characterization of the ENRs modified by compound B
    The 1 H NMR spectrum makes it possible to quantify the grafted nitrile oxide units by integration of the characteristic signals of the CH3N protons which appear at a chemical shift of between 3.1 and 3.3 ppm. The 2D NMR spectrum HSQC 113 · H-C makes it possible to verify the nature of the grafted pattern by virtue of the chemical shifts of the carbon and proton atoms. 2, - Examples of preparation of modified natural rubbers 2.1 Method of modification of natural rubber
    In all cases, the 1.3-dipolar compound to be tested (see Table 2), 30 g of test natural rubber or of synthetic polyisoprene is incorporated on a roll tool (external mixer at 30 ° C.) ( see Table 2). The mixture is homogenized in 15 wall passes. This mixing phase is followed by a heat treatment at 120 ° C. in a press at 10 bar pressure for 30 minutes.
    The percentage of epoxy ring before and after the implementation of the modification process is determined by NMR according to the method indicated above.
    The molar percentage of 1,3-dipolar compound which was grafted at the end of the process on the natural rubbers to be tested and on the synthetic polyisoprene is determined by NMR according to the method described above.
    The grafting yield corresponds to the percentage molar percentage of 1,3-dipolar compound grafted onto the natural rubber or synthetic polyisoprene chain relative to the molar percentage of 1,3-dipolar compound introduced as a starting reagent.
    The results obtained are shown in Table 2 below.
    Table 2
    * outside the invention ** according to the invention
    The graft yield of a 1,3-dipolar compound on a synthetic polyisoprene (NIPOL 2200) is greater than 90%.
    The grafting yield of a 1,3-dipolar compound on a natural rubber, whether deproteinized or plasticized, is low and at most equal to 56%.
    On the other hand, surprisingly, when the natural rubber is epoxidized, a grafting yield of greater than 60% is observed. Furthermore, it is observed that the molar percentage of epoxidized 1,4-cis isoprene unit before and after grafting has not been modified, indicating that the epoxy ring is not modified during the grafting reaction.
    The graft yield is not affected by the nature of the chemical group carried by the 1,3-dipolar compound. Indeed, the grafting yield is identical for compound A and for compound B.
    权利要求:
    Claims (18)
    [1" id="c-fr-0001]
    A method of modifying a natural rubber comprising at least the following steps: i. providing at least one natural rubber and epoxidizing said natural rubber to obtain an epoxidized natural rubber, or having a previously epoxidized natural rubber, ii. graft on said epoxidized natural rubber or on said previously epoxidized natural rubber at least one 1,3-dipolar compound having at least one nitrogen atom.
    [2" id="c-fr-0002]
    2. The method of claim 1, wherein said epoxidized natural rubber or said previously epoxidized natural rubber has an epoxidation rate of less than or equal to 50 mol%, and preferably greater than or equal to 0.5 mol%, preferably ranging from from 1 to 45 mol%, more preferably from 2 to 30 mol%.
    [3" id="c-fr-0003]
    3. Method according to claim 1 or 2, wherein step (ii) is carried out in bulk or in solution, preferably in bulk.
    [4" id="c-fr-0004]
    4. Method according to any one of claims 1 to 3, wherein the 1,3-dipolar compound comprises at least one nitrile oxide dipole, imine nitrile or nitrone.
    [5" id="c-fr-0005]
    5. The method of claim 4, wherein the 1,3-dipolar compound comprises at least one nitrile oxide dipole.
    [6" id="c-fr-0006]
    6. Process according to claim 5, in which the nitrile oxide dipole belongs to a unit corresponding to the general formula (I) in which:

    - RI, R2, R3, R4, R5, identical or different, represent a hydrogen atom, a halogen atom, a C1-C5 alkyl, a C1-C5 alkoxyl or a covalent bond for attachment to the rest of the 1,3-dipolar compound; provided that at least one of R1, R2, R3, R4, R5 represents said covalent bond.
    [7" id="c-fr-0007]
    7. Method according to any one of claims 1 to 6, wherein step (ii) is carried out by heating at a temperature greater than or equal to 70 ° C, preferably for at most 4 hours, preferably during at most 2 hours and even more preferably for not more than 30 minutes.
    [8" id="c-fr-0008]
    The process according to any of claims 1 to 7, wherein the level of said 1,3-dipolar compound is from 0.1 to 10 mol%, preferably from 0.1 to 5 mol%.
    [9" id="c-fr-0009]
    9. Process according to any one of claims 1 to 8, wherein the 1,3-dipolar compound carries at least one chemical group intended to be grafted onto the epoxidized natural rubber, said chemical group being a hydrocarbon chain which can optionally contain a heteroatom.
    [10" id="c-fr-0010]
    10. The method of claim 9, wherein the chemical group is selected from hydrocarbon groups, optionally substituted nitrogen or sulfur heterocycles, esters, phosphates, dialkylamino and associative groups comprising at least one nitrogen atom.
    [11" id="c-fr-0011]
    11. The method of claim 10, wherein the associative group comprising at least one nitrogen atom is chosen from the following formulas (IV), (V) (VI), (VII) and (VIII):



    in which: R 5 represents a hydrocarbon group which may optionally contain heteroatoms, Q represents an oxygen or sulfur atom or NH, preferably an oxygen atom, the symbol * represents an indirect attachment to the dipole of compound 1, 3 dipolar.
    [12" id="c-fr-0012]
    12. The method of claim 10 and 11, wherein the 1,3-dipolar compound is selected from the compounds of formulas (IX), (X), (XI), (XII), (XIII), (XIV) , (XV), (XVI), (XVII), (XVIII), (XIX) and their mesomeric forms:






    [13" id="c-fr-0013]
    13. Modified natural rubber obtainable by the process defined in any one of claims 1 to 12.
    [14" id="c-fr-0014]
    14. Rubber composition based on: - at least one modified natural rubber according to claim 13, - at least one reinforcing filler, and - at least one crosslinking system.
    [15" id="c-fr-0015]
    15. The method of manufacturing a composition according to claim 14, the method comprising at least the following steps: incorporating at least one reinforcing filler into the modified natural rubber, by thermomechanically kneading the whole, in one or more times, until to reach a maximum temperature ranging from 130 ° C. to 200 ° C., preferably from 145 ° C. to 85 ° C., to cool the assembly to a temperature of less than 100 ° C., then to incorporate at least one chemical crosslinking system, to mix the all up to a maximum temperature below 120 ° C, - extrude or calender the rubber composition thus obtained.
    [16" id="c-fr-0016]
    16. A method of manufacturing a composition according to claim 14, the method comprising at least the following steps: - dispose of at least one natural rubber and epoxidize said natural rubber to obtain an epoxidized natural rubber, or have a rubber previously epoxidized natural, - incorporate in the epoxidized natural rubber of the previous step, at least one 1,3-dipolar compound having at least one nitrogen atom, subsequently incorporate at least one reinforcing filler, while thermomechanically kneading the whole, in one or more times until reaching a maximum temperature of 130 ° C to 200 ° C, preferably 145 ° C to 185 ° C, cooling all to a temperature below 100 ° C, then minus a chemical crosslinking system, knead the whole up to a maximum temperature below 120 ° C, extrude or calender the rubber composition thus obtained.
    [17" id="c-fr-0017]
    17. A finished or semi-finished rubber product comprising at least one rubber composition defined according to claim 14 or obtainable by the process according to claim 15 or 16.
    [18" id="c-fr-0018]
    18. A tire comprising at least one semi-finished product defined according to claim 17.
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    同族专利:
    公开号 | 公开日
    EP3402828A1|2018-11-21|
    US20190048102A1|2019-02-14|
    CN108473598A|2018-08-31|
    CN108473598B|2020-06-09|
    EP3402828B1|2020-04-01|
    WO2017121950A1|2017-07-20|
    FR3046603B1|2017-12-29|
    US10711071B2|2020-07-14|
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    法律状态:
    2017-01-20| PLFP| Fee payment|Year of fee payment: 2 |
    2017-07-14| PLSC| Publication of the preliminary search report|Effective date: 20170714 |
    2018-01-19| PLFP| Fee payment|Year of fee payment: 3 |
    2019-09-27| ST| Notification of lapse|Effective date: 20190906 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1650182A|FR3046603B1|2016-01-11|2016-01-11|METHOD FOR MODIFYING NATURAL RUBBER AND MODIFIED NATURAL RUBBER|FR1650182A| FR3046603B1|2016-01-11|2016-01-11|METHOD FOR MODIFYING NATURAL RUBBER AND MODIFIED NATURAL RUBBER|
    EP17702679.6A| EP3402828B1|2016-01-11|2017-01-10|Process for modifying of natural rubber and modified natural rubber|
    US16/068,939| US10711071B2|2016-01-11|2017-01-10|Method for modifying a natural rubber, and modified natural rubber|
    PCT/FR2017/050049| WO2017121950A1|2016-01-11|2017-01-10|Method for modifying a natural rubber, and modified natural rubber|
    CN201780005421.5A| CN108473598B|2016-01-11|2017-01-10|Process for modifying natural rubber and modified natural rubber|
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