1,3-dipole compounds containing epoxy groups and their synthetic intermediates
Patent Information
- Application Number
- JP2024538159
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2021-12-23
- Filing Date
- 2022-12-19
- Publication Date
- 2026-01-07
Smart Images
Figure 2023117844000001 
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Abstract
Description
[Technical field]
[0001] The field of the invention is that of modifying agents for the functionalization of unsaturated polymers, i.e. polymers having unsaturated carbon-carbon bonds in their molecular chain. More precisely, these modifying agents are 1,3-dipole compounds carrying epoxy groups. The invention also relates to methods for the synthesis of these compounds and to their synthetic intermediates, and to the use of these modifying agents. [Background technology]
[0002] Modifying the structure of a polymer is particularly desirable when it is desired to combine the polymer and a reinforcing filler together to form a composition, as this modification makes it possible, for example, to improve the dispersion of the reinforcing filler in the polymer matrix, thus obtaining a more homogeneous material and ultimately improving the properties of the composition. The modification of the polymer structure can be carried out in particular by means of functionalizing (or modifying) agents, coupling agents or star-branching agents or postpolymerization agents, in particular with the aim of obtaining a good interaction between the thus modified polymer and the reinforcing filler, whether the reinforcing filler is carbon black or a reinforcing inorganic filler. Many functionalizing agents have been proposed to improve this interaction. For example, document WO 2019 / 102128 A1 discloses as functionalizing agents aromatic nitrile oxide compounds containing an epoxy ring, which are linked to an aromatic ring carrying a nitrile oxide functional group by a divalent -OCH2- group in the meta position relative to the nitrile oxide functional group; the aromatic ring carrying the nitrile oxide functional group is also further substituted with methyl in the ortho, meta and para positions. This functionalizing agent, 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzonitrile oxide, when grafted onto a styrene / butadiene copolymer, makes it possible to improve the hysteresis of an elastomer composition containing such a modified copolymer, compared to an elastomer composition containing an unmodified styrene / butadiene copolymer.
[0003] As fuel economy and the need to protect the environment have become priorities, the need to produce tires having the lowest possible rolling resistance, i.e. tires comprising elastomeric compositions having the lowest possible hysteresis, has been demonstrated. Obtaining an elastomeric composition with the lowest possible hysteresis while at the same time maintaining good performance levels of other properties, such as reinforcement and stiffness, is an ongoing challenge for tire manufacturers. Indeed, it is known that a reduction in the hysteresis of an elastomeric composition is accompanied by a reduction in the curing stiffness. However, the tread must be hard enough to ensure a good level of road behavior of the tire. There is therefore a constant need to have new functionalizing agents available that make it possible to modify the structure of polymers, and in particular the structure of diene elastomers, with the aim of obtaining elastomeric compositions with further improved hysteresis properties compared to the elastomeric compositions of the prior art, without this improvement being obtained at the expense of the stiffness properties. Summary of the Invention
[0004] An object of the present invention is therefore to propose novel polymeric modifiers which, when grafted onto these polymers, make it possible to obtain elastomeric compositions which exhibit an improved rolling resistance / stiffness performance compromise. Pursuing that research, the applicant has surprisingly found that when aromatic nitrile oxides having an epoxy ring in the para or meta position relative to the nitrile oxide functional group and no substituent in the ortho position relative to the nitrile oxide functional group are grafted onto polymers, especially elastomers, containing unsaturated carbon-carbon bonds, it is possible to obtain elastomeric compositions that exhibit an improved rolling resistance / stiffness trade-off. Advantageously, this novel modifier also makes it possible to improve the reinforcing properties of these compositions.
[0005] A first subject of the invention therefore relates to compounds of formula (I) below: [ka] (In the formula: - T is -CHO, -CH=NOH, and -CN + -O - represents a chemical group selected from the group consisting of: - R1 represents a chemical group selected from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group selected from the group consisting of -OCH3 and -OR3; - with the proviso that R1 or R2 is -OR3; R3 represents a chemical group of formula (II)
[0006] [ka] (wherein E represents a divalent C1-C12 hydrocarbon group which may contain one or more heteroatoms; X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; The symbol * represents the point of attachment of the group of formula (II) to the oxygen atom.
[0007] Preferentially, in the compounds of formula (I), the T group is --CHO. Preferentially, in the compounds of formula (I), the T group is -CH=NOH. Preferentially, in the compounds of formula (I), the T group is -CN + -O - It is. Preferentially, in the compounds of formula (I), the E group represents a C1-C12 alkanediyl, preferably a C1-C10 alkanediyl, more preferentially a C1-C9 alkanediyl; even more preferentially, E is selected from the group consisting of methanediyl, ethanediyl and propanediyl. Preferentially, in the compounds of formula (I), X1, X2, X3, which may be identical or different, are selected from the group consisting of a hydrogen atom, a C1-C6 alkyl, and a phenyl. Preferentially, in the compounds of formula (I), X1, X2, X3 are identical and are hydrogen atoms.
[0008] Advantageously, the preferred compounds of formula (I) are those of formula (Ia). [ka] (In the formula: - R1 represents a chemical group selected from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group selected from the group consisting of -OCH3 and -OR3; - with the proviso that R1 or R2 is -OR3; R3 represents a chemical group of formula (II)
[0009] [ka] (wherein E represents a divalent C1-C12 hydrocarbon group which may contain one or more heteroatoms; X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; The symbol * represents the point of attachment of the group of formula (II) to the oxygen atom.
[0010] Another subject of the invention relates to a process for preparing a compound of formula (Ia), comprising at least one reaction of a compound of formula (Ib) with an oxidizing agent in the presence of at least one organic solvent SL1, according to the reaction scheme: [ka] (In the formula: - R1 represents a chemical group selected from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group selected from the group consisting of -OCH3 and -OR3; - with the proviso that R1 or R2 is -OR3; R3 represents a chemical group of formula (II)
[0011] [ka] (wherein E represents a divalent C1-C12 hydrocarbon group which may contain one or more heteroatoms; X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; The symbol * represents the point of attachment of the group of formula (II) to the oxygen atom.
[0012] Preferentially, said oxidizing agent is chosen from sodium hypochlorite, N-bromosuccinimide in the presence of a base, N-chlorosuccinimide in the presence of a base, and an aqueous solution of hydrogen peroxide in the presence of a catalyst. Preferentially, the organic solvent SL1 is chosen from chlorinated solvents and solvents of the ester, ether and alcohol types. Preferentially, the process further comprises a step of reaction of the compound of formula (Ic) with hydroxylamine according to the following reaction scheme: [ka] (wherein R1 and R2 are as defined above).
[0013] Preferentially, hydroxylamine is contacted with the compound of formula (Ic) in the form of a hydroxylamine salt in the presence of a base. Preferentially, the process further comprises a step of reaction of a compound of formula (IV) with a compound of formula (III) in the presence of at least one phase transfer agent at a temperature ranging from 10° C. to 120° C., preferentially from 30° C. to 100° C., according to the following reaction scheme: [ka] (- for compounds of formula (IV): R4 represents a chemical group selected from the group consisting of -OCH3, -OCH2CH3, and -OH; R5 represents a chemical group selected from the group consisting of -OCH3 and -OH; provided that R4 or R5 is -OH; for compounds of formula (III): E represents a divalent C1-C12 hydrocarbon group, which may contain one or more heteroatoms; X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; Z represents a nucleofugic group; for compounds of formula (Ic): R1 and R2 are as defined above
[0014] Preferentially, the phase transfer agent is from among phosphonium salts, ammonium salts, and mixtures thereof. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0015] As stated above, a first subject of the invention relates to compounds of formula (I) below: [ka] (In the formula, - T is -CHO, -CH=NOH, and -CN + -O - represents a chemical group selected from the group consisting of: - R1 represents a chemical group selected from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group selected from the group consisting of -OCH3 and -OR3; - with the proviso that R1 or R2 is -OR3; R3 represents a chemical group of formula (II)
[0016] [ka] (wherein E represents a divalent C1-C12 hydrocarbon group which may contain one or more heteroatoms; X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; The symbol * represents the point of attachment of the group of formula (II) to the oxygen atom)
[0017] The present invention and its advantages will be readily understood in light of the following description and exemplary embodiments. In this text, all percentages given are percentages by weight unless expressly indicated otherwise. Furthermore, any interval of values indicated by the expression "between a and b" denotes a range of values extending from greater than a to less than b (i.e., the limits a and b are excluded), whereas any interval of values indicated by the expression "a to b" means a range of values extending from a to b (i.e., including the exact limits a and b). The compounds mentioned in the specification may be of fossil origin or bio-based. In the latter case, they may be derived partially or completely from biomass or may be obtained from renewable raw materials derived from biomass. Of course, the compounds mentioned may also come from the reuse of already used materials, i.e. they may come partially or completely from a recycling process or may be obtained from raw materials that themselves come from a recycling process. This concerns, inter alia, polymers, plasticizers, fillers, etc.
[0018] The expression "composition based on" should be understood to mean a composition comprising a mixture of the various components used and / or the product of an in situ reaction of the various components used, some of which can and / or are intended to react with one another, at least in part, during the various stages of the preparation of the composition; thus the composition can be in a fully or partially crosslinked or non-crosslinked state. The expression "parts by weight per 100 parts by weight of elastomer" (or phr) is to be understood in the present invention as meaning parts by weight per 100 parts by weight of elastomer. The term "1,3-dipole compound" is understood according to the definition given by IUPAC. By definition, a 1,3-dipole compound contains a dipole. + -O - If it is, then the dipole is a nitrile oxide. In the present invention, the term "hydrocarbon chain" means a molecular chain comprising one or more carbon atoms and one or more hydrogen atoms.
[0019] The expression "Ci-Cj alkyl" refers to a linear, branched or cyclic hydrocarbon radical containing from i to j carbon atoms; i and j are integers. The expression "Ci-Cj aryl" refers to an aromatic radical containing from i to j carbon atoms; i and j are integers. The term "Ci-Cj alkanediyl" is understood to mean a hydrocarbon radical derived from a Ci-Cj alkane as defined above, by removing two hydrogen atoms. Thus, alkanediyl is a divalent radical. The invention and its advantages will be readily understood in light of the following description and exemplary embodiments.
[0020] In the compounds of formula (I), the chemical group T is -CN + -O - -CH=NOH, and -CHO, and are represented as follows, where the symbol (**) represents the point of attachment to the aromatic ring: [ka]
[0021] Advantageously, among the compounds of formula (I), the compounds of formula (Ia) are particularly preferred since they are polymer modifiers. [ka] (In the formula: - R1 represents a chemical group selected from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group selected from the group consisting of -OCH3 and -OR3; - with the proviso that R1 or R2 is -OR3; R3 represents a chemical group of formula (II)
[0022] [ka] (wherein E represents a divalent C1-C12 hydrocarbon group which may contain one or more heteroatoms; X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; The symbol * represents the point of attachment of the group of formula (II) to the oxygen atom)
[0023] More advantageously, among the compounds of formula (Ia), more particularly preferred compounds are those of formula (Ia1). [ka] (In the formula: - R1 represents a chemical group selected from the group consisting of -OCH3 and -OCH2CH3; more preferentially, R1 represents -OCH3; - E represents a divalent C1-C12 hydrocarbon group, which may contain one or more heteroatoms; - X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl.
[0024] Advantageously, among the compounds of formula (I), the compounds of formula (Ib) are particularly preferred since they are synthetic intermediates for the compounds of formula (Ia). [ka] (In the formula: - R1 represents a chemical group selected from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group selected from the group consisting of -OCH3 and -OR3; - with the proviso that R1 or R2 is -OR3; R3 represents a chemical group of formula (II)
[0025] [ka] (wherein E represents a divalent C1-C12 hydrocarbon group which may contain one or more heteroatoms; X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; The symbol * represents the point of attachment of the group of formula (II) to the oxygen atom)
[0026] More advantageously, among the compounds of formula (Ib), the more particularly preferred compounds are those of formula (Ib1). [ka] (In the formula: - R1 represents a chemical group selected from the group consisting of -OCH3 and -OCH2CH3; more preferentially, R1 represents -OCH3; - E represents a divalent C1-C12 hydrocarbon group, which may contain one or more heteroatoms; - X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl.
[0027] The above compounds of formula (Ib1) are also of particular interest as they are synthetic intermediates for the preferred compounds of formula (Ia1).
[0028] Advantageously, among the compounds of formula (I), the compounds of formula (Ic) are particularly preferred since they are synthetic intermediates for the compounds of formula (Ib). [ka] (In the formula: - R1 represents a chemical group selected from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group selected from the group consisting of -OCH3 and -OR3; - with the proviso that R1 or R2 is -OR3; R3 represents a chemical group of formula (II)
[0029] [ka] (wherein E represents a divalent C1-C12 hydrocarbon group which may contain one or more heteroatoms; X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; The symbol * represents the point of attachment of the group of formula (II) to the oxygen atom)
[0030] More advantageously, among the compounds of formula (Ic), the more particularly preferred compounds are those of formula (Ic1). [ka] (In the formula: - R1 represents a chemical group selected from the group consisting of -OCH3 and -OCH2CH3; more preferentially R1 represents -OCH3; - E represents a divalent C1-C12 hydrocarbon group, which may contain one or more heteroatoms; - X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl.
[0031] The above compounds of formula (Ic1) are also of particular interest as they are synthetic intermediates for the preferred compounds of formula (Ib1). Thus, a particularly preferred group of compounds of formula (I) are those in which R1 represents a chemical group selected from the group consisting of -OCH3 and -OCH2CH3 and R2 is -OR3, in other words, this group of compounds corresponds to the set constituted by the preferred compounds of formula (Ia1), (Ib1) and (Ic1). Preferentially, in the compounds of formula (I), (Ia), (Ib) and (Ic), the condition "R1 or R2 is -OR3" means that R1 is -OCH3 or -OCH2CH3 and R2 is -OR3, or R1 is -OR3 and R2 is -OCH3. In these compounds, there is necessarily one (1) type (and only one) -OR3, either as the substituent R1 or as the substituent R2.
[0032] In the compounds of formula (I), (Ia), (Ia1), (Ib), (Ib1), (Ic) and (Ic1), E represents a divalent C1-C12 hydrocarbon group, which may contain one or more heteroatoms. In the present invention, the term "divalent hydrocarbon group" is understood to mean a spacer group (or linking group) that forms a bridge between the oxygen atom attached to the aromatic ring and the epoxy ring carrying the X1, X2 and X3 groups; this spacer group E contains 1 to 12 carbon atoms and may contain one or more heteroatoms, such as, for example, N, O and S. This spacer group may be, for example, a saturated, linear or branched C1-C12 hydrocarbon chain, which may contain one or more heteroatoms, such as, for example, N, O and S. The hydrocarbon chain may be optionally substituted, provided that the substituents do not react with the chemical group T defined above and the epoxy ring. Preferentially, in the compounds of formula (I), (Ia), (Ia1), (Ib), (Ib1), (Ic) and (Ic1), E represents a divalent C1-C10 hydrocarbon group, preferably a divalent C1-C9 hydrocarbon group, which may contain one or more heteroatoms such as, for example, N, O and S.
[0033] More preferentially, in the compounds of formula (I), (Ia), (Ia1), (Ib), (Ib1), (Ic) and (Ic1), E represents C1-C12 alkanediyl, preferably C1-C10 alkanediyl, more preferentially C1-C9 alkanediyl. Even more preferentially, E is selected from the group consisting of methanediyl, ethanediyl and propanediyl. Preferentially, in the compounds of formula (I), (Ia), (Ia1), (Ib), (Ib1), (Ic) and (Ic1), X1, X2, X3 may be the same or different and are selected from the group consisting of a hydrogen atom, a C1-C6 alkyl and a C6-C14 aryl. Preferentially, in the compounds of formula (I), (Ia), (Ia1), (Ib), (Ib1), (Ic) and (Ic1), X1, X2, X3, which may be the same or different, are selected from the group consisting of a hydrogen atom, a C1-C6 alkyl and a phenyl.
[0034] Preferentially, in the compounds of formula (I), (Ia), (Ia1), (Ib), (Ib1), (Ic) and (Ic1), X1, X2, X3, which may be identical or different, are selected from the group consisting of a hydrogen atom, a C1-C3 alkyl and a phenyl. According to a preferred embodiment of the present invention, in the compounds of formula (I), (Ia), (Ia1), (Ib), (Ib1), (Ic) and (Ic1), X1, X2 and X3 are the same and represent a hydrogen atom. According to another preferred embodiment of the present invention, in the compounds of formula (I), (Ia), (Ia1), (Ib), (Ib1), (Ic) and (Ic1), X1 and X2 represent a hydrogen atom and X3 represents a phenyl. According to another embodiment of the present invention, in the compounds of formula (I), (Ia), (Ia1), (Ib), (Ib1), (Ic) and (Ic1), X3 is a hydrogen atom, and X1 and X2, which may be the same or different, represent a hydrogen atom or a methyl.
[0035] As mentioned above, among the compounds of formula (I), particularly preferred are compounds of formula (Ia). [ka] (In the formula: - R1 represents a chemical group selected from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group selected from the group consisting of -OCH3 and -OR3; - with the proviso that R1 or R2 is -OR3; R3 represents a chemical group of formula (II)
[0036] [ka] (wherein E represents a divalent C1-C12 hydrocarbon group, which may contain one or more heteroatoms; preferably C1-C12 alkanediyl, preferably C1-C10 alkanediyl, more preferentially C1-C9 alkanediyl; X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; The symbol * represents the point of attachment of the group of formula (II) to the oxygen atom; More preferentially, E represents a C1-C9 alkanediyl, more preferentially selected from the group consisting of methanediyl, ethanediyl and propanediyl; X1, X2 and X3 may be identical or different and are selected from the group consisting of a hydrogen atom, a C1-C3 alkyl and a phenyl, more preferentially X1, X2 and X3 are identical and are a hydrogen atom).
[0037] Surprisingly, the compounds of formula (Ia) which have no ortho substitution to the nitrile oxide functional group and which carry, in addition to the epoxy group, -OCH3 or -OCH2CH3 groups in meta or para positions, when grafted onto polymers, preferably elastomers, especially diene elastomers, give compositions based on said graft polymers with improved reinforcing properties compared to the elastomer compositions of the prior art. Surprisingly, the improvement in these properties is not realized at the expense of the rolling resistance / stiffness trade-off, which is further advantageously improved. Among the compounds of formula (Ia), preference is given to compounds of formula (Ia1) in which R1 represents a chemical group selected from the group consisting of -OCH3 and -OCH2CH3, E represents a C1-C12 alkanediyl, preferably a C1-C10 alkanediyl, more preferentially a C1-C9 alkanediyl, and X1, X2, X3, which may be identical or different, are selected from the group consisting of a hydrogen atom, a C1-C3 alkyl and a phenyl, more preferentially X1, X2, X3 are identical and are a hydrogen atom. More preferentially, more particularly preferred compounds of formula (Ia1) are those in which R1 represents -OCH3, E represents C1-C12 alkanediyl, preferably C1-C10 alkanediyl, more preferentially C1-C9 alkanediyl, and X1, X2, X3 may be the same or different and are selected from the group consisting of hydrogen, C1-C3 alkyl and phenyl, more preferentially X1, X2, X3 are the same and are hydrogen. More preferentially, particularly preferred compounds of formula (Ia1) are those in which R1 represents -OCH3, E represents C1-C9 alkanediyl, and X1, X2, X3 are the same and are hydrogen. More preferentially, more particularly preferred compounds of formula (Ia1) are those in which R1 represents -OCH3, E is selected from the group consisting of methanediyl, ethanediyl and propanediyl, and X1, X2 and X3 are identical and are hydrogen atoms. Among the compounds of formula (Ia1), particularly preferred are compounds of formula (Ia2).
[0038] [ka]
[0039] Another subject of the invention relates to a process for preparing a compound of formula (Ia), comprising at least one reaction (d) of a compound of formula (Ib) with an oxidizing agent in the presence of at least one organic solvent SL1, according to the following reaction scheme: [ka] (In the formula: - R1 represents a chemical group selected from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group selected from the group consisting of -OCH3 and -OR3; - with the proviso that R1 or R2 is -OR3; R3 represents a chemical group of formula (II)
[0040] [ka] (wherein E represents a divalent C1-C12 hydrocarbon group which may contain one or more heteroatoms; X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; The symbol * represents the point of attachment of the group of formula (II) to the oxygen atom) As described above, the preferred forms of R1, R2, E, X1, X2, and X3 also apply to the process for preparing a compound of formula (Ia) from a compound of formula (Ib).
[0041] Preferentially, the method for preparing a compound of formula (Ia1) comprises at least one reaction (d1) of a compound of formula (Ib1) with an oxidizing agent in the presence of at least one organic solvent SL1 according to the following reaction scheme: [ka] (wherein E, X1, X2, and X3 are as defined above, including preferred forms thereof, and R1 represents a chemical group selected from the group consisting of -OCH3 and -OCH2CH3, preferably R1 is -OCH3).
[0042] Preferably, in these methods, the oxidizing agent is selected from sodium hypochlorite, N-bromosuccinimide in the presence of a base, N-chlorosuccinimide in the presence of a base, and aqueous hydrogen peroxide in the presence of a catalyst. More preferentially, the oxidizing agent is selected from the group consisting of sodium hypochlorite and N-bromosuccinimide in the presence or absence of a base. Preferentially, the base may be triethylamine. Even more preferentially, the oxidizing agent is sodium hypochlorite. Advantageously, the amount of oxidizing agent ranges from 1 to 5 molar equivalents, preferentially from 1 to 2 molar equivalents, relative to the molar amount of the compound of formula (Ib) and preferably to the molar amount of the compound of formula (Ib1). Preferentially, the organic solvent SL1 is selected from chlorinated solvents and solvents of the ester, ether and alcohol types, more preferentially from dichloromethane, trichloromethane, ethyl acetate, butyl acetate, diethyl ether, isopropanol and ethanol, and even more preferentially from ethyl acetate, trichloromethane, dichloromethane and butyl acetate. Preferably, the compound of formula (Ib), more preferentially the compound of formula (Ib1), represents from 1% to 30% by weight, preferably from 1% to 20% by weight, relative to the total weight of the combination comprising said compound of formula (Ib), preferably in form (Ib1), said organic solvent SL1 and said oxidizing agent.
[0043] Preferentially, the process of the invention comprises a step of recovering the compound of formula (Ia), preferably the compound of formula (Ia1), after reaction (d), preferably after reaction (d1). The compound of formula (Ib) can notably be obtained from a process for preparation comprising at least one reaction (c) of a compound of formula (Ic) with hydroxylamine NHOH according to the following reaction scheme: [ka] (In the formula: - R1 represents a chemical group selected from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group selected from the group consisting of -OCH3 and -OR3; - with the proviso that R1 or R2 is -OR3; R3 represents a chemical group of formula (II)
[0044] [ka] (wherein E represents a divalent C1-C12 hydrocarbon group which may contain one or more heteroatoms; X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; The symbol * represents the point of attachment of the group of formula (II) to the oxygen atom) As described above, the preferred forms of R1, R2, E, X1, X2, and X3 also apply to the process for preparing a compound of formula (Ib) from a compound of formula (Ic).
[0045] Preferentially, the compound of formula (Ib1) can be obtained from a method of preparation which notably comprises at least one reaction (c1) of a compound of formula (Ic1) with hydroxylamine NH2OH according to the following reaction scheme: [ka] (wherein E, X1, X2, and X3 are as defined above, including preferred forms thereof, and R1 represents a chemical group selected from the group consisting of -OCH3 and -OCH2CH3, preferably R1 is -OCH3).
[0046] Preferentially, the addition of hydroxylamine in reaction (c), preferably in reaction (c1), is carried out at a temperature ranging from 1°C to 100°C, more preferentially at a temperature between 20°C and 70°C. Hydroxylamine is added either in aqueous solution or in the form of a salt. When in the form of a salt, the hydroxylamine may be selected from the group consisting of hydroxylamine sulfate, hydroxylamine chloride, and mixtures thereof. In the case of the use of hydroxylamine in the form of a salt, a base may preferentially be added to the reaction medium. As examples of bases, mention may be made of sodium acetate or triethylamine. The amount of base added may be in the range ranging from 1 to 2 molar equivalents relative to the hydroxylamine generated, and preferentially in the range ranging from 1 to 1.2 molar equivalents relative to the hydroxylamine generated. The term "hydroxylamine generated" refers to the cation (NH3 + (OH). When a base is used, said base is mixed with the hydroxylamine salt and then the mixture is dissolved in water. Preferentially, the hydroxylamine is contacted with the compound of formula (Ic) in the form of a hydroxylamine salt in the presence of a base, for example sodium acetate or triethylamine.
[0047] Preferentially, the process of the invention may comprise a step of recovering the product of formula (Ib), preferably the product of formula (Ib1), after reaction (c), preferably after reaction (c1). The compounds of formula (Ic) can be obtained by a process for preparation comprising at least one reaction (b) of a compound of formula (IV) with a compound of formula (III) in the presence of at least one phase transfer agent at a temperature ranging from 10° C. to 120° C., preferentially from 20° C. to 100° C., according to the following reaction scheme:
[0048] [ka] (- for compounds of formula (IV): R4 represents a chemical group selected from the group consisting of -OCH3, -OCH2CH3, and -OH; R5 represents a chemical group selected from the group consisting of -OCH3 and -OH; provided that R4 or R5 is -OH; for compounds of formula (III): E represents a divalent C1-C12 hydrocarbon group, which may contain one or more heteroatoms; X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; Z represents a nucleofugic group; for compounds of formula (Ic): R1 and R2 are as defined above
[0049] The preferred forms of R1, R2, E, X1, X2, and X3 also apply to the process for preparing a compound of formula (Ic) from a compound of formula (IV) and a compound of formula (III). Preferentially, the compound of formula (Ic1) can be obtained by a preparation process comprising at least one reaction (b1) of a compound of formula (IV) with a compound of formula (III) in the presence of at least one phase transfer agent at a temperature ranging from 10° C. to 120° C., preferentially from 20° C. to 100° C., according to the following reaction scheme:
[0050] [ka] (In the formula, - for the compounds of formula (Ic1), E, X1, X2, X3 are as defined above and R1 represents a chemical group selected from the group consisting of -OCH3 and -OCH2CH3; preferably, R1 is -OCH3; for compounds of formula (IV): R4 is -OCH3 or -OCH2CH3, preferably -OCH3; R5 is -OH; for compounds of formula (III): E represents a divalent C1-C12 hydrocarbon group, which may contain one or more heteroatoms; X1, X2, and X3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; Z represents a nucleofugic group.
[0051] The term "nucleofugic group" is understood to mean a leaving group. The Z group may be selected from chlorine, bromine, iodine, fluorine, mesylate, tosylate, acetate and trifluoromethylsulfonate groups. Preferably, Z is bromine or chlorine. The phase transfer agent may be selected from phosphonium salts, ammonium salts, and mixtures thereof. Preferentially, the phase transfer agent is tetrabutylammonium bromide. Preferentially, the molar amount of the phase transfer agent is between 0.01 and 1 molar equivalent, preferably between 0.05 and 0.5 molar equivalent, relative to the molar amount of the compound of formula (III). Preferentially, the process of the invention may comprise a step of recovering the product of formula (Ic) (preferably the product of formula (Ic1)) after reaction (b) (preferably after reaction (b1)). The compounds of formula (IV) defined above are commercially available from suppliers such as Sigma-Aldrich, Merck, etc. The compounds of formula (IV) may be obtained by chemical synthesis or, in the case of vanillin, by extraction from vanilla pods or, in the case of isovanillin, by extraction from cassava, or by microbial fermentation, in particular proceeding from ferulic acid.
[0052] Compounds of formula (III) may be commercially available or may be obtained by epoxidation of the corresponding haloalkene of formula (V) according to the following reaction scheme. The synthesis of compounds containing an epoxide ring from their corresponding alkenes is well known. For example, the epoxidation may be carried out in the presence of a peracid, such as meta-chloroperbenzoic acid, peracetic acid, or performic acid. Another well-known technique is the use of dimethyldioxirane. [ka]
[0053] Compounds of formula (V) are commercially available from sources such as Sigma-Aldrich and ABCR. As explained above, the compounds of formula (Ia) and their preferred embodiments, in particular the compounds of formula (Ia1) and even more particularly the compounds of formula (Ia2), are used as polymer modifiers. They can be grafted onto one or more polymers that contain at least one unsaturated carbon-carbon bond; in particular, this polymer may be an elastomer, more particularly a diene elastomer. The compounds of the present invention advantageously make it possible to obtain grafted polymers (also called modified polymers), in particular elastomers, especially diene elastomers, regardless of the initial microstructure of the polymer, the only condition being that the polymer contains at least one unsaturated carbon-carbon bond, preferably a carbon-carbon double bond.
[0054] The grafting of polymers containing at least one unsaturated carbon-carbon bond can be carried out by reaction of the original polymer with compounds of formula (Ia) and its preferred embodiments, in particular with compounds of formula (Ia1) and even more particularly with compounds of formula (Ia2). The grafting of these compounds is carried out by [3+2] cycloaddition of the nitrile oxide functional groups of said compounds to the unsaturated carbon-carbon bond of the polymer chain. The mechanism of this cycloaddition is explained, inter alia, in the document WO 2012 / 007441. The grafting of the compounds of formula (Ia) and its preferred embodiments, in particular the compounds of formula (Ia1) and even more particularly the compounds of formula (Ia2), can be carried out in bulk, for example in an internal or external mixer, for example in an open mill, or in solution. The grafting process can also be carried out in solution, continuously or batchwise. The modified polymer can be separated from the solution by any kind of means known to the skilled person, in particular by a steam stripping operation.
[0055] The compounds of formula (Ia) and their preferred embodiments, in particular the compounds of formula (Ia1), and even more particularly the compounds of formula (Ia2), may be integrated into elastomeric compositions. These elastomeric compositions may be based on at least one diene elastomer, on a reinforcing filler, and on at least one crosslinking agent. The grafting of the compounds of formula (Ia) and its preferred embodiments, in particular the compounds of formula (Ia1), and even more particularly the compounds of formula (Ia2), onto the diene elastomer may be carried out before the introduction of said elastomer into the composition, or it may be grafted by reaction with said compounds of formula (Ia) during the preparation of the composition. The elastomeric compositions may also comprise additives. Additives that may be used may be plasticizers (for example plasticizing oils and / or plasticizing resins), non-reinforcing fillers, pigments, protective agents, such as ozone-resistant waxes, chemical antiozonants, antioxidants, antifatigue agents, reinforcing resins (as described, for example, in patent application WO 02 / 10269). These elastomeric compositions can be used for the manufacture of tire semi-finished products or for the manufacture of tires. The present invention can be explained by the following examples, but the present invention is not limited to these examples. EXAMPLES
[0056] 1. Method 1.1. Determination of the number average molecular weight (Mn) and mass average molecular weight (Mw) and polydispersity index of elastomers Size exclusion chromatography (SEC) is used, which allows the separation of macromolecules in solution according to their size through a column packed with a porous gel. Macromolecules are separated according to their hydrodynamic volume, with the bulkiest eluting first. Although not an absolute method, SEC makes it possible to understand the distribution of molecular weights of elastomers. The various number average molecular weights (Mn) and weight average molecular weights (Mw) can be determined from commercially available standards, and the polydispersity index (PDI=Mw / Mn) can be calculated via a "Moore" calibration.
[0057] Preparation of the elastomer samples to be tested There is no special treatment of the elastomer samples before analysis. The elastomer samples are easily dissolved in chloroform at a concentration of approximately 1 g / l or in the following mixture: tetrahydrofuran + diisopropylamine 1 vol% + triethylamine 1 vol% + distilled water 1 vol% (vol% = volume%). The solution is then filtered through a filter with a porosity of 0.45 μm before injection. SEC analysis The equipment used is a Waters Alliance chromatograph. The elution solvent is the following mixture: tetrahydrofuran + diisopropylamine 1 vol% + triethylamine or chloroform 1 vol%, according to the solvent used in the dissolution of the elastomer. The flow rate is 0.7 ml / min, the temperature of the system is 35°C and the analysis time is 90 min. A set of four Waters columns in series is used, trade names Styragel HMW7, Styragel HMW6E and two Styragel HT6E. The volume of the injected elastomer sample solution is 100 μl. The detector is a Waters 2410 differential refractometer with a wavelength of 810 nm. The software for processing the chromatographic data is the Waters Empower system. The calculated average molecular weights are compared to a calibration curve generated from PSS Ready Cal-Kit commercial polystyrene standards.
[0058] 1.2. Molecular characterization The structural characterization and molar purity of the synthesized molecules are carried out by NMR analysis. The spectra are acquired on a Bruker Avance3 400mHz spectrometer equipped with a "5mm BBFO Z-grad broadband" probe. 1H NMR experiments use a 30° single pulse sequence and a repetition time of 3 seconds between each of 64 acquisitions. Samples are dissolved in a deuterated solvent, deuterated dimethylsulfoxide (DMSO), unless otherwise indicated. A deuterated solvent is also used for the "lock" signal. For example, calibration is performed at the signal of the proton of deuterated DMSO at 2.44 ppm against a TMS standard at 0 ppm. 2D 1 H / 13 C HSQC experiment and 1 H / 13 C HMBC experiments 1 The H NMR spectrum allows the structural determination of the molecule (see assignment table). Molar quantification allows quantitative 1D 1 This is carried out from the H NMR spectrum. Mass spectrometric analysis was performed by direct injection electrospray ionization (DI / ESI) on a Bruker HCT spectrometer (flow rate 600 μl / min, nebulizer gas pressure 10 psi, nebulizer gas flow rate 4 l / min).
[0059] 1.3. Characterization of compounds grafted onto diene elastomers The determination of the molar content of compounds grafted onto the diene elastomer is carried out by NMR analysis. The spectra are acquired on a Bruker 500 mHz spectrometer equipped with a "5 mm BBFO Z-grad Cryoprobe" probe. Quantitative 1 The H NMR experiments use a 30° single pulse sequence and a repetition time of 5 seconds between each acquisition. To obtain a "lock" signal, the samples are dissolved in deuterated chloroform (CDCl3). The 2D NMR experiments make it possible to ascertain the nature of the grafted units by the chemical shifts of the carbon atoms and protons.
[0060] 1.4. Dynamic properties of elastomer compositions Dynamic properties G * and tan(δ) maxis measured on a viscosity analyzer (Metravib VA4000) according to standard ASTM D5992-96. Samples of the vulcanized composition (cylindrical test specimens, 4 mm thick and 400 mm cross-sectional area) are subjected to a simple alternating sinusoidal shear stress at a frequency of 10 Hz and at a temperature of 60° C. 2 ) response is recorded. A strain amplitude sweep is performed from 0.1% to 100% peak-peak (outward cycle) and then from 100% to 0.1% peak-peak (return cycle). The results used are the complex dynamic shear modulus at 50% strain, G * (G * 50% Return run) and dynamic loss coefficient tan(δ) at 60℃. * 50%復路60℃ The complex dynamic shear modulus G at 50% strain * The value of tan(δ) max60℃ The maximum observed dynamic loss factor tan(δ) is recorded, which indicates The results are expressed as a standard of 100 and tan(δ) max60℃ and G * 50%復路60℃ For subsequent comparison, an arbitrary value of 100 is associated with the control group. tan(δ) max60℃ The value of the sample to be tested at a standard value of 100 is calculated as follows: (tan(δ) of the sample to be tested) max60℃ Value / tan(δ) of control group max60℃ The rolling resistance is calculated according to the coefficient of friction (Rp) × 100. Thus, a result less than 100 indicates reduced hysteresis, which corresponds to improved rolling resistance performance. G * 50%復路60℃ The value of the sample to be tested at the standard 100 is calculated as follows: (G of the sample to be tested) * 50%復路60℃ Value / G of control group * 50%復路60℃ The complex dynamic shear modulus G is calculated according to the following formula: * 50%復路60℃ This suggests an increase in the stiffness of the material, which ensures an increase in stiffness.
[0061] 1.5. Tensile Test These tensile tests make it possible to measure the elastic stresses. If not otherwise indicated, they are carried out according to the French standard NF T46-002 of September 1988. By processing the tensile records it is also possible to plot a curve of the modulus in function of elongation. The nominal secant modulus (or apparent stress (MPa)), calculated by normalizing to the initial cross-sectional area of the specimen at the initial elongation, is measured at an elongation of 100%, which indicates MSA100, and at an elongation of 300%, which indicates MSA300. All these tensile measurements are carried out under standard temperature conditions (23±2°C) and at a temperature of 100°C, according to the standard NF T46-002. The MSA300 / MSA100 ratio is the reinforcement index. The value of the tested sample at a reference of 100 is calculated according to the following formula: (MSA300 / MSA100 value of the tested sample / MSA300 / MSA100 value of the control group) x 100. Thus, a result above 100 indicates an improvement in the reinforcement index.
[0062] 2. Compound Synthesis 2.1. Synthesis of 3-methoxy-4-(oxiran-2-ylmethoxy)benzonitrile oxide (compound A, compound according to the invention) Compound A is synthesized according to the following reaction scheme. [ka] Vanillin is obtained from the company Sigma-Aldrich and sold under the reference "W310700-1KG".
[0063] 2.1.1. Step 1: Synthesis of 3-methoxy-4-(oxiran-2-ylmethoxy)benzaldehyde To a solution of vanillin (20 g; 131 mmol) in epichlorohydrin (278 ml; 3.56 moles, i.e. 27 eq. (eq. = molar equivalents)), tetrabutylammonium bromide (4.24 g; 13.15 mmol, i.e. 0.1 eq.) is added. The reaction medium is then stirred for 60-70 minutes at a temperature of 90 ° C. After returning to room temperature, the reaction mixture is diluted with ethyl acetate (150 ml), washed with brine (3 × 75 ml) and finally with distilled water (75 ml). The organic phase is then separated, dried over sodium sulfate and evaporated under reduced pressure (T bath = 50 ° C; 13 mbar). The oil obtained is triturated with ice-cold isopropyl alcohol (i-PrOH) (50 ml) and allowed to crystallize rapidly. The precipitate is filtered and washed with ice-cold i-PrOH (3 × 35 ml); it is then dried in air.
[0064] A white solid (23.16 g; 111 mmol) was obtained in 85% yield. The molar purity was higher than 90% ( 1 1H NMR). [ka]
[0065] [Table 1]
[0066] 2.1.2. Step 2: Synthesis of 3-methoxy-4-(oxiran-2-ylmethoxy)benzaldehyde oxime To a suspension of 3-methoxy-4-(oxiran-2-ylmethoxy)benzaldehyde (4.253 g; 20.43 mmol) in ethanol (100 ml), at room temperature (23 ° C), is added a solution of sodium acetate (2.51 g; 30.6 mmol, i.e. 1.5 eq.) and hydroxylamine hydrochloride (2.129 g; 30.6 mmol, i.e. 1.5 eq.) in distilled water (100 ml). After complete dissolution in 40-50 seconds, a slight exothermicity is observed in the reaction medium. A new precipitate forms within a few minutes. The reaction mixture is then stirred for 90 minutes at room temperature. Crushed ice (100 g) is then added and the medium is kept stirred until the crushed ice has completely melted. Finally, the precipitate is filtered, washed with excess water and dried in air.
[0067] A white solid (3.604 g; 16.14 mmol; 79% yield) is obtained. The molar purity is greater than 89% ( 1 1H NMR). [ka]
[0068] [Table 2]
[0069] 2.1.3. Step 3: Synthesis of 3-methoxy-4-(oxiran-2-ylmethoxy)benzonitrile N-oxide To a suspension of 3-methoxy-4-(oxiran-2-ylmethoxy)benzaldehyde oxime (10.15 g; 45.5 mmol) in dichloromethane (100 ml) cooled to 0-3 ° C, a solution of bleach (98.5 ml; active chlorine 4%) (bleach = sodium hypochlorite) is added dropwise over 20-25 min. The reaction medium is then stirred between 0-5 ° C for 80-90 min. The organic phase is then separated, washed with water (2 × 50 ml) and finally evaporated under reduced pressure (T bath = 25 ° C; 10 mbar) to give a beige solid. This solid is then redissolved in dichloromethane (about 100 ml). The above obtained solution is then filtered through a layer of SiO2 (about 4-5 cm thick) and eluted with dichloromethane (2 × 30 ml). Finally, the permeate is concentrated under reduced pressure (T bath = 25 °C; 10 mbar) resulting in a white solid obtained in 71% yield (7.126 g; 32.2 mmol). The molar purity is 95% ( 1 1H NMR).
[0070] [ka]
[0071] [Table 3]
[0072] 2.2. Synthesis of 2-(glycidyloxy)-1-naphthonitrile oxide (compound B, prior art compound) 2-(glycidyloxy)-1-naphthonitrile oxide, compound B, is synthesized according to the procedure described in patent application US Patent Application Publication No. 2012 / 0046418, paragraphs
[0033] to
[0037] . [ka]
[0073] 2.3. Synthesis of 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzonitrile oxide (Compound C, prior art compound) 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzonitrile oxide, compound C, is synthesized according to the reaction scheme and synthesis method described below and taken from the examples of the document WO2019102128.
[0074] [ka]
[0075] 2.3.1. Synthesis of 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzaldehyde: To a mixture of 3-hydroxy-2,4,6-trimethylbenzaldehyde (40.00 g; 0.244 mol) and epichlorohydrin (56.35 g; 0.609 mol) in acetonitrile (100 ml) potassium carbonate (50.50 g; 0.365 mol) is added. The reaction medium is stirred at 60 ° C for 3 hours and then at 70 ° C for 2.5-3 hours. After returning to 40-50 ° C, the reaction mixture is diluted with a mixture of water (250 ml) and ethyl acetate (250 ml), then maintained under stirring for 10 minutes. The organic phase is separated and washed with water (4 times with 125 ml). The solvent is evaporated under reduced pressure (T-bath 37 ° C; 40 mbar). A red oil (66.43 g) is obtained. The by-product of the reaction, 3,3'-((2-hydroxypropane-1,3-diyl)bis(oxy))bis(2,4,6-trimethylbenzaldehyde), is separated from 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzaldehyde by chromatography on a silica column (eluent: ethyl acetate / petroleum ether = 1 / 4 by volume). After recovery of the fractions containing 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzaldehyde, the solvent is evaporated under reduced pressure (T-bath 36 ° C; 21 mbar). Petroleum ether (120 ml) is added to the residue and the suspension is maintained under stirring at -18 ° C for 2 hours. The precipitate is filtered, washed on the filter with petroleum ether (40 / 60) (3 times 25 ml) and finally dried at room temperature and atmospheric pressure for 10-15 hours. A white solid (40.04 g; 75% yield) is obtained with a melting point of 52° C. The molar purity is greater than 99% ( 1 1H NMR).
[0076] [ka]
[0077] [Table 4]
[0078] 2.3.2. Synthesis of 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzaldehyde oxime: To a solution of 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzaldehyde (46.70 g; 0.212 mol) in ethyl alcohol (750 ml) is added, at room temperature, a solution of hydroxylamine (16.81 g; 0.254 mol, 50% in water, Aldrich) in ethyl alcohol (75 ml). The reaction medium is stirred at 23° C. for 3 hours (T-bath). After evaporation of the solvent (T-bath=24° C.; 35 mbar), petroleum ether (40 / 60) (150 ml) is added. The precipitate is filtered and washed on the filter with petroleum ether (100 ml). The crude product is dissolved at room temperature in a mixture of ethyl acetate (650 ml) and petroleum ether (650 ml) and the solution is filtered through a layer of silica gel (φ 9 cm, SiO2 2.0 cm).
[0079] The solvent is evaporated (T bath = 22-24 °C) and 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzaldehyde oxime is dried at room temperature and atmospheric pressure. A white solid (43.81 g; 88% yield) with a melting point of 77 °C is obtained. The molar purity is higher than 99% ( 1 1H NMR). [ka]
[0080] [Table 5]
[0081] 2.3.3. Synthesis of 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzonitrile oxide (compound C): To a solution of 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzaldehyde oxime (17.00 g; 0.072 mol) in dichloromethane (350 ml) cooled to 3 ° C, an aqueous solution of NaOCl (62.9 g active Cl / l) (126 ml) is added dropwise over 10-15 minutes. The temperature of the reaction medium is kept between 3 ° C and 5 ° C. The reaction medium is then stirred for 1 hour at a temperature of 3-5 ° C. The aqueous phase is separated and extracted with dichloromethane (25 ml). The combined organic phases are washed with water (3 times 75 ml). The solvent is evaporated under reduced pressure (T bath = 22 ° C, 35 mbar). Petroleum ether (40 / 60) (90 ml) is added to the residue and the suspension is maintained at room temperature with stirring for 10-12 hours. The precipitate is filtered, washed on the filter with petroleum ether (3 times 30 ml) and finally dried at room temperature and atmospheric pressure for 10-15 h. A white solid (15.12 g, 90% yield) with a melting point of 63 °C is obtained. The molar purity is higher than 99% ( 1 1H NMR).
[0082] [ka]
[0083] [Table 6]
[0084] 3. Preparation of modified diene elastomers 3.1. Natural rubber modified with compound A 0.98 phr (i.e. molar fraction 0.3 mol%) of compound A, 3-methoxy-4-(oxiran-2-ylmethoxy)benzonitrile oxide with an NMR purity of more than 89 mol%, obtained according to the method described in paragraph 2.1, is incorporated into 100 g of natural rubber on an open mill (external mixer at 30° C.). The mixture is homogenized 15 times on this mill, then molded into slabs, after which it is subjected to a heat treatment at 100° C. for 10 minutes under a pressure of 10 bar. 1Analysis by 1 H NMR made it possible to determine a molar degree of grafting of less than 0.100 mol % and a molar grafting yield of less than 33%. 3.2. Natural rubber modified with compound B 1.06 phr (i.e. molar fraction 0.3 mol%) of compound B, 2-(glycidyloxy)-1-naphthonitrile oxide with an NMR purity of 95 mol%, obtained according to the method of paragraph 2.2, are incorporated into 100 g of natural rubber on an open mill (external mixer at 30° C.). The mixture is homogenized 15 times on this mill, then molded into slabs, after which it is subjected to a heat treatment at 100° C. for 10 minutes under a pressure of 10 bar. 1 Analysis by 1 H NMR allowed determining a molar degree of grafting of 0.162 mol % and a molar grafting yield of 54%.
[0085] 3.3. Natural rubber modified with compound C 1.03 phr (i.e. molar fraction 0.3 mol%) of compound C, 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzonitrile oxide with an NMR purity of 99 mol%, obtained according to the method of paragraph 2.3, are incorporated in 100 g of natural rubber on an open mill (external mixer at 30° C.). The mixture is homogenized 15 times on this mill, then molded into slabs, after which it is subjected to a heat treatment at 100° C. for 10 minutes under a pressure of 10 bar. 1 Analysis by 1 H NMR allowed determining a molar degree of grafting of 0.070 mol % and a molar grafting yield of 23%. 3.4. Synthetic polyisoprene modified with compound A 0.98 phr (i.e. 0.3 mol% molar fraction) of 3-methoxy-4-(oxiran-2-ylmethoxy)benzonitrile oxide, obtained according to the method described in paragraph 2.1, with an NMR purity of more than 89 mol%, is incorporated in 100 g of synthetic polyisoprene (containing 99.35% by weight of cis-1,4-isoprene units and 0.65% by weight of 3,4-isoprene units; Mn=375000 g / mol and PDI=3.6, measured according to the method described above) on an open mill (external mixer at 30° C.). The mixture is homogenized 15 times on this mill, then molded into a slab, which is then subjected to a heat treatment at 100° C. for 10 minutes under a pressure of 10 bar. 1 Analysis by 1 H NMR allowed determining a molar degree of grafting of 0.150 mol % and a molar grafting yield of 50%.
[0086] 3.5. Synthetic polyisoprene modified with compound B Compound B, 1.06 phr (i.e. molar fraction 0.3 mol%) of 2-(glycidyloxy)-1-naphthonitrile oxide with an NMR purity of 95 mol% obtained according to the method of paragraph 2.2, is incorporated in 100 g of synthetic polyisoprene (containing 99.35% by weight of cis-1,4-isoprene units and 0.65% by weight of 3,4-isoprene units; Mn=375000 g / mol and PDI=3.6, measured according to the method described above) on an open mill (external mixer at 30° C.). The mixture is homogenized 15 times on this mill, then molded into a slab, which is then subjected to a heat treatment at 100° C. for 10 minutes under a pressure of 10 bar. 1 Analysis by 1 H NMR allowed determining a molar degree of grafting of 0.145 mol % and a molar grafting yield of 48%.
[0087] 3.6. Synthetic polyisoprene modified with compound C 1.03 phr (i.e. molar fraction 0.3 mol%) of compound C obtained according to paragraph 2.3, 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzonitrile oxide with an NMR purity of 99 mol%, is incorporated in 100 g of synthetic polyisoprene (containing 99.35% by weight of cis-1,4-isoprene units and 0.65% by weight of 3,4-isoprene units; Mn=375000 g / mol and PDI=3.6, measured according to the method described above) on an open mill (external mixer at 30° C.). The mixture is homogenized 15 times on this mill, then molded into a slab, which is then subjected to a heat treatment at 100° C. for 10 minutes under a pressure of 10 bar. 1 Analysis by 1 H NMR allowed determining a molar degree of grafting of 0.200 mol % and a molar grafting yield of 67%.
[0088] 4. Components used in the elastomer composition (1) Silica, Zeosil 1165MP, sold by Solvay; (2) Bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT) silane sold by Evonik under the reference Si69; (3) N234 grade carbon black sold by Cabot Corporation; (4) N-(1,3-dimethylbutyl)-N-phenyl-para-phenylenediamine sold by Flexsys under the reference Santoflex 6-PPD; (5) 2,2,4-trimethyl-1,2-dihydroquinoline sold by Flexsys; (6) Zinc oxide (technical grade) sold by Umicore; (7) Stearin Pristerene 4031 sold by Uniqema; (8) N-cyclohexyl-2-benzothiazole sulfenamide sold under Santocure CBS referenced by Flexsys; (9) Natural rubber modified with compound B, obtained according to the process described in paragraph 3.2; (10) Natural rubber modified with compound C, obtained according to the process described in paragraph 3.3; (11) Natural rubber modified with compound A according to the invention, obtained according to the process described in paragraph 3.1; (12) Synthetic polyisoprene modified with compound B, obtained according to the process described in paragraph 3.5; (13) Synthetic polyisoprene modified with compound C, obtained according to the process described in paragraph 3.6; (14) Synthetic polyisoprene modified with compound A of the invention, obtained according to the method described in paragraph 3.4.
[0089] 5. Test 1 The purpose of this test is to show the improvement in the performance compromise of an elastomeric composition comprising natural rubber modified with the compounds of the invention (composition C3) compared to a control elastomeric composition (composition T1) and two comparative elastomeric compositions (compositions C1 and C2).
[0090] The contents of the various constituents of these compositions, expressed in phr, parts by weight per 100 parts by weight of elastomer, are given in Table 7. [Table 7]
[0091] The elastomer composition T1 and the elastomer compositions C1 to C3 are prepared as follows: natural rubber modified with compound B, natural rubber modified with compound C, natural rubber modified with compound A, or unmodified natural rubber is added to 85 cm 3 The mixture is introduced into a Polylab internal mixer, filled to 70%, and the internal vessel temperature is approximately 100°C. Next, for each of the elastomer compositions, the reinforcing fillers, the agents for coupling the fillers with the diene elastomers, and then after mixing for 1-2 minutes, the various other components are introduced, except for the vulcanization system.The thermomechanical work (non-productive phase) is then carried out in a step lasting approximately 5-6 minutes in total, until a maximum drop temperature of 160°C is reached.
[0092] The mixture thus obtained was recovered, cooled and then the vulcanization system (sulfur and sulfenamide type accelerators) was added to an external mixer (homofinisher) at 25°C and the whole was mixed for approximately 5-6 minutes (production stage). The elastomer composition thus obtained is then calendered in the form of a slab (thickness 2-3 mm) for the measurement of its physical and mechanical properties. The rubber properties of these compositions are measured 30 minutes after curing at 150° C. The results obtained are shown in Table 8.
[0093] [Table 8]
[0094] The inventive elastomer composition C3 exhibits a significant improvement in reinforcement index (MA300 / M100) and an improvement in the rolling resistance / stiffness performance tradeoff (tan(δ)) compared to the control T1 and the elastomer compositions of Comparative Examples C1 and C2. max60℃ Decrease in G * 50%復路60℃ (increase in
[0095] 5. Test 2 The purpose of this test is to show the improved performance compromise of an elastomeric composition comprising synthetic polyisoprene modified with a compound of the invention (composition C6) compared to a control elastomeric composition (composition T2) and two comparative elastomeric compositions (compositions C4 and C5). The content of each of these components of the elastomer compositions, expressed in phr, mass per 100 parts by mass of elastomer, is given in Table 9.
[0096] [Table 9]
[0097] Elastomer composition T2 and elastomer compositions C4 to C6 are prepared according to the methods described above for elastomer composition T1 and elastomer compositions C1 to C3. The rubber properties of these elastomer compositions are measured for 30 minutes after curing at 150° C. The results obtained are shown in Table 10.
[0098] [Table 10]
[0099] The inventive elastomer composition C6 exhibited a significant improvement in reinforcement index (MA300 / M100) and an improvement in the rolling resistance / stiffness performance tradeoff (tan(δ)) compared to the control T2 and the elastomer compositions of Comparative Examples C4 and C5. max60℃ Decrease in G * 50%復路60℃ (increase in
Claims
1. A compound of formula (I): 【Chemistry 1】 (In the formula: - T is -CHO, -CH=NOH, and -CN + -O - represents a chemical group selected from the group consisting of: -R 1 is -OCH 3 , -OCH 2 CH 3 , and -OR 3 represents a chemical group selected from the group consisting of: -R 2 is -OCH 3 and -OR 3 represents a chemical group selected from the group consisting of: - However, R 1 or R 2 Ga-OR 3 provided that: -R 3 represents a chemical group of formula (II): 【Chemistry 2】 (wherein E represents a divalent C1-C12 hydrocarbon group, which may contain one or more heteroatoms; ・X 1 , X 2 , X 3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; The symbol * represents the point of attachment of the group of formula (II) to the oxygen atom)
2. R 1 But, -OCH 3 and -OCH 2 CH 3 represents a chemical group selected from the group consisting of: 2 Ga-OR 3 2. The compound of formula (I) according to claim 1, wherein:
3. 3. The compound of formula (I) according to claim 1 or 2, wherein T is -CHO.
4. 3. A compound of formula (I) according to claim 1 or 2, wherein T is -CH=NOH.
5. T is -CN + -O - 3. A compound of formula (I) according to claim 1 or 2, wherein:
6. 3. Compounds of formula (I) according to claim 1 or 2, in which E represents C1-C12 alkanediyl, preferably C1-C10 alkanediyl, more preferentially C1-C9 alkanediyl; and even more preferentially E is selected from the group consisting of methanediyl, ethanediyl and propanediyl.
7. X 1 , X 2 , X 3 The compound of formula (I) according to claim 1 or 2, wherein may be the same or different and are selected from the group consisting of a hydrogen atom, a C1-C6 alkyl, and a phenyl.
8. X 1 , X 2 , X 3 3. A compound of formula (I) according to claim 1 or 2, wherein are identical and are a hydrogen atom.
9. A method for preparing a compound of formula (Ia), said method comprising at least reacting a compound of formula (Ib) with an oxidizing agent in the presence of at least one organic solvent SL1 according to the following reaction scheme: 【Transformation 3】 (In the formula, -R 1 is -OCH 3 , -OCH 2 CH 3 , and -OR 3 represents a chemical group selected from the group consisting of: -R 2 is -OCH 3 and -OR 3 represents a chemical group selected from the group consisting of: - However, R 1 or R 2 Ga-OR 3 provided that: -R 3 represents a chemical group of formula (II) 【Chemistry 4】 (wherein E represents a divalent C1-C12 hydrocarbon group, which may contain one or more heteroatoms; ・X 1 , X 2 , X 3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; The symbol * represents the point of attachment of the group of formula (II) to the oxygen atom)
10. 10. The method of claim 9, wherein the oxidizing agent is selected from sodium hypochlorite, N-bromosuccinimide in the presence of a base, N-chlorosuccinimide in the presence of a base, and aqueous hydrogen peroxide in the presence of a catalyst.
11. 11. The method according to claim 9 or 10, wherein the organic solvent SL1 is chosen from chlorinated solvents and solvents of the ester, ether and alcohol types.
12. 11. The method of claim 9 or 10, further comprising the step of reacting the compound of formula (Ic) with hydroxylamine according to the following reaction scheme: 【Transformation 5】 (In the formula, R 1 and R 2 is as defined in claim 9)
13. 13. The method of claim 12, wherein the hydroxylamine is contacted with the compound of formula (Ic) in the form of a hydroxylamine salt in the presence of a base.
14. 13. The process according to claim 12, further comprising a step of reacting a compound of formula (IV) with a compound of formula (III) in the presence of at least one phase transfer agent at a temperature ranging from 10°C to 120°C, preferentially from 30°C to 100°C, according to the following reaction scheme: 【Transformation 6】 (--for said compound of formula (IV): ・R 4 is -OCH 3 , -OCH 2 CH 3 represents a chemical group selected from the group consisting of —OH; ・R 5 is -OCH 3 represents a chemical group selected from the group consisting of -OH; ・However, R 4 or R 5 is —OH; for said compound of formula (III): E represents a divalent C1-C12 hydrocarbon group, which may contain one or more heteroatoms; ・X 1 , X 2 , X 3 may be the same or different and represent a hydrogen atom, a C1-C6 alkyl, or a C6-C14 aryl; Z represents a nucleofugal group; For said compounds of formula (Ic): R 1 and R 2 is as defined in claim 9)
15. 15. The method of claim 14, wherein the phase transfer agent is selected from the group consisting of phosphonium salts, ammonium salts, and mixtures thereof.