1,3-dipolar compound comprising an epoxy group and its synthetic intermediates.
Patent Information
- Application Number
- FR2021014414
- Authority / Receiving Office
- FR · FR
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2021-12-23
- Publication Date
- 2025-02-21
- Estimated Expiration
- 2041-12-23
Abstract
Description
Title of the invention: 1,3-dipolar compound comprising an epoxy group and its synthetic intermediates.
[0001] The field of the present invention is that of modifying agents for functionalizing unsaturated polymers, that is, polymers bearing unsaturated carbon-carbon bonds in their chains. More specifically, these modifying agents are 1,3-dipolar compounds bearing an epoxy group. The invention also relates to a process for synthesizing these compounds and their synthetic intermediates, as well as the use of such modifying agents.
[0002] Modifying the structure of a polymer is particularly desirable when combining a polymer and a reinforcing filler to form a composition. This modification can, for example, improve the dispersion of the reinforcing filler within a polymer matrix, thus resulting in a more homogeneous material and ultimately enhancing the properties of the composition.
[0003] The modification of polymer structure can be achieved, in particular, by means of functionalizing agents (or modifying agents), coupling or star-forming agents, or post-polymerization, notably with the aim of obtaining good interaction between the modified polymer and the reinforcing filler, whether carbon black or an inorganic reinforcing filler. Numerous functionalizing agents have been proposed to improve this interaction.
[0004] For example, from document WO2019 / 102128A1, an aromatic nitrile oxide compound comprising an epoxy ring is known as a functionalizing agent. The epoxy ring is linked to the aromatic ring bearing the nitrile oxide function by a divalent group -OCH2- in the meta position relative to the nitrile oxide function. The aromatic ring bearing the nitrile oxide function is also substituted in the ortho-, meta-, and para- positions by a methyl group. This functionalizing agent, 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzonitrile oxide, when grafted onto a styrene-butadiene copolymer, improves the hysteresis of an elastomeric composition containing such a modified copolymer compared to an elastomeric composition comprising an unmodified styrene-butadiene copolymer.
[0005] Since fuel economy and the need to protect the environment have become a priority, it has become necessary to produce tires with the lowest possible rolling resistance, i.e. comprising elastomeric compositions with the lowest possible hysteresis.
[0006] Obtaining an elastomeric compound with the lowest possible hysteresis, while maintaining good performance for other properties such as reinforcement and stiffness, is an ongoing challenge for tire manufacturers. Indeed, it is known that a decrease in the hysteresis of elastomeric compounds is accompanied by a decrease in curing stiffness. However, a tread must be sufficiently stiff to ensure good tire handling.
[0007] There is therefore a constant need for new functionalizing agents to modify the structure of polymers, in particular diene elastomers, in order to obtain elastomeric compositions with hysteresis properties that are further improved compared to prior art elastomeric compositions without this improvement being at the expense of stiffness properties.
[0008] One aim of the present invention is therefore to propose new polymer modification agents which, once grafted to these polymers, make it possible to obtain elastomeric compositions exhibiting an improved compromise of performance, rolling resistance / stiffness.
[0009] Continuing its research, the Applicant made a surprising discovery that an aromatic nitrile oxide bearing an epoxy ring in the para- or meta- position relative to the nitrile oxide function and lacking a substituent in the ortho- position of this nitrile oxide function, when grafted onto a polymer containing unsaturated carbon-carbon bonds, particularly an elastomer, yielded elastomeric compositions exhibiting an improved rolling resistance / stiffness trade-off. Advantageously, this new modifying agent also improves the reinforcement properties of these compositions.
[0010] Thus, a first object of the present invention relates to a compound of the following formula (I): [Chem 1]
[0011] in which: - T represents a chemical group chosen from the group consisting of -CHO, -CH=NOH and -CN+-0; - Ri represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3 and -OR3; - R2 represents a chemical group chosen from the group consisting of -OCH3 and -OR3; - provided that Ri or R2 is -OR3; - R3 represents a chemical group of formula (II) [Chem 2] • in which E represents a divalent C1-C12 hydrocarbon group possibly comprising one or more heteroatoms; • Xb X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; • The symbol * represents the attachment of the group of formula (II) to the oxygen atom.
[0012] Preferably, in the compound of formula (I), the group T is -CHO.
[0013] Preferably, in the compound of formula (I), the group T is -CH=NOH.
[0014] Preferably, in the compound of formula (I), the group T is -CN+-0.
[0015] Preferably, in the compound of formula (I), the group E represents a C1-C12 alkanediyl, preferably a C1-C10 alkanediyl, more preferably a C1-C9 alkanediyl, even more preferably E is chosen from the group consisting of methanediyl, ethanediyl and propanediyl.
[0016] Preferably, in the compound of formula (I), Xb X2, X3, identical or different, are chosen from the group consisting of the hydrogen atom, the C1-C6 alkyls and the phenyl.
[0017] Preferably, in the compound of formula (I), Xb X2, X3, identical, are a hydrogen atom.
[0018] Advantageously, a preferred compound of formula (I) is a compound of formula (la) [Chem 3]
[0019] in which: - Ri represents a chemical group chosen from the group formed by - OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group chosen from the group consisting of -OCH3 and -OR3; - provided that Ri or R2 is -OR3; - R3 represents a chemical group of formula (II) [Chem 4] • in which E represents a divalent C1-C12 hydrocarbon group possibly comprising one or more heteroatoms; • Xb X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; • The symbol * represents the attachment of the group of formula (II) to the oxygen atom.
[0020] Another object of the present invention relates to a process for preparing a compound of formula (la), said process 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: [Chem 5]
[0021] with: - Ri represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group chosen from the group consisting of -OCH3 and -OR3; - provided that Ri or R2 is -OR3; - R3 represents a chemical group of formula (II) [Chem 6] • in which E represents a divalent C1-C12 hydrocarbon group possibly comprising one or more heteroatoms; • Xb X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; • The symbol * represents the attachment of the group of formula (II) to the oxygen atom.
[0022] Preferably, 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 hydrogen peroxide in the presence of a catalyst.
[0023] Preferably, the organic solvent SL1 is chosen from among chlorinated solvents and ester, ether and alcohol type solvents.
[0024] Preferably, the process further comprises a step of reacting a compound of formula (le) with hydroxylamine according to the following reaction scheme: [Chem 7] (THE)
[0025] with Riet R2 as defined above.
[0026] Preferably, hydroxylamine is brought into contact with the compound of formula (the) in the form of a hydroxylamine salt in the presence of a base.
[0027] Preferably, the process further comprises 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 and at a temperature ranging from 10°C to 120°C, preferably 30°C to 100°C according to the following reaction scheme: [Chem 8] - with the compound having formula (IV): • R4 represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3 and -OH; • R5 represents a chemical group chosen from the group consisting of -OCH3 and -OH; and • provided that R4 or R5 is -OH; - with the compound of formula (III): • E represents a divalent hydrocarbon group in Cl-Cl2, possibly comprising one or more heteroatoms; and • Xi, X2, X3, whether identical or different, represent a hydrogen atom, a C1-C6 alkyl group, or a C6-C14 aryl group; and • Z represents a leaving group; - with the compound having formula (the): Ri and R2 as defined above.
[0028] Preferably, the phase-transfer agent is among the phosphonium salts, Ammonium salts and their mixtures.
[0029] As mentioned above, a first object of the present invention relates to a compound of the following formula (I): [Chem 9]
[0030] in which: - T represents a chemical group chosen from the group consisting of -CHO, -CH=NOH and -CN+-0; - Ri represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group chosen from the group consisting of -OCH3, and -OR3; - provided that Ri or R2 is -OR3; - R3 represents a chemical group of formula (II) [Chem 10] • in which E represents a divalent C1-C12 hydrocarbon group possibly comprising one or more heteroatoms; • Xb X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; • The symbol * represents the attachment of the group of formula (II) to the oxygen atom.
[0031] The invention and its advantages will be readily understood in light of the following description and embodiments. In this document, unless expressly stated otherwise, all percentages (%) indicated are percentages (%) by mass.
[0032] On the other hand, any interval of values designated by the expression "between a and b" represents the domain of values going from more than a to less than b (that is to say, bounds a and b excluded) while any interval of values designated by the expression "from a to b" means the domain of values going from a to b (that is to say, including the strict bounds a and b).
[0033] The compounds mentioned in the description may be of fossil origin or bio-based. In the latter case, they may be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. Obviously, the compounds mentioned can also come from the recycling of materials already in use; that is, they can be partially or totally derived from a recycling process, or even obtained from raw materials themselves derived from a recycling process. This includes, in particular, polymers, plasticizers, fillers, etc.
[0034] The expression "composition based on" means a composition comprising the mixture and / or the in situ reaction product of the different constituents used, some of these constituents being able to react and / or being intended to react with each other, at least partially, during the different phases of manufacturing the composition; the composition can thus be in a totally or partially crosslinked state or in a non-crosslinked state.
[0035] By the expression "part by weight per hundred parts by weight of elastomer" (or pce), it is to be understood in the context of the present invention as the part, by mass per hundred parts by mass of elastomer.
[0036] The term 1,3-dipolar compound is understood according to the definition given by IUP AC. By definition, a 1,3-dipolar compound comprises a dipole. When T is CN+-0, the dipole is a nitrile oxide.
[0037] For the purposes of the present invention, "hydrocarbon chain" means a chain comprising one or more carbon atoms and one or more hydrogen atoms.
[0038] The expression "Ci-Cj alkyl" designates a linear, branched or cyclic hydrocarbon group comprising i to j carbon atoms; i and j being integers.
[0039] The expression "Ci-Cj aryl" designates an aromatic group comprising i to j carbon atoms; i and j being integers.
[0040] By "Ci-Cj alkanediyl" is meant a hydrocarbon group, derived from a Ci-Cj alkane as defined above, in which two hydrogen atoms have been removed. An alkanediyl is therefore a divalent group.
[0041] The invention and its advantages will be readily understood in the light of the description and embodiment examples that follow.
[0042] In the compound of formula (I), the chemical group T is chosen from the group consisting of -CN+-0; -CH=NOH and -CHO, also represented in the following way [Chem 11] ** ?-----C ----OHs ----- HH
[0043] with the symbol (**) representing attachment to the aromatic cycle.
[0044] Advantageously, among the compounds of formula (I), the compounds of formula (la) are particularly preferred because they are polymer modifying agents: [Chem 12] Ri
[0045]
[0046] in which: - Ri represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group chosen from the group consisting of -OCH3 and -OR3; - provided that Ri or R2 is -OR3; - R3 represents a chemical group of formula (II) [Chem 13] • in which E represents a divalent C1-C12 hydrocarbon group possibly comprising one or more heteroatoms; • Xb X2, X3, whether identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; • The symbol * represents the attachment of the group of formula (II) to the oxygen atom. More advantageously, among the compounds of formula (la), the compounds most particularly preferred are those of formula (lal): [Chem 14] X3
[0047] in which: Ri represents a chemical group chosen from the group consisting of -OCH3 and -OCH2CH3; more preferably Ri represents -OCH3; E represents a divalent C1-C12 hydrocarbon group possibly comprising one or more heteroatoms; and - Xb X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl.
[0048] Advantageously, among the compounds of formula (I), the compounds of formula (Ib) are particularly preferred because they are synthetic intermediates of the compounds of formula (la): [Chem 15] (Ib) HO
[0049] in which: - Ri represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3 and -OR3; - R2 represents a chemical group chosen from the group consisting of -OCH3 and -OR3; - provided that Ri or R2 is -OR3; - R3 represents a chemical group of formula (II) [Chem 16] • in which E represents a divalent C1-C12 hydrocarbon group possibly comprising one or more heteroatoms; • Xi, X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; • The symbol * represents the attachment of the group of formula (II) to the oxygen atom.
[0050] More advantageously, among the compounds of formula (Ib), the compounds most particularly preferred are those of formula (Ibl) [Chem 17]
[0051] in which: - Ri represents a chemical group chosen from the group formed by - OCH3 and -OCH2CH3; more preferably Ri represents -OCH3; - E represents a divalent C1-C12 hydrocarbon group possibly comprising one or more heteroatoms; and - Xb X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl.
[0052] The compounds of formula (Ib 1 ) above are also of particular interest because they are synthetic intermediates of preferred compounds of formula (lal ).
[0053] Advantageously, among the compounds of formula (I), the compounds of formula (le) are particularly preferred because they are synthetic intermediates of the compounds of formula (Ib): [Chem 18] R-, (THE)
[0054] in which: - Ri represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3 and -OR3; - R2 represents a chemical group chosen from the group consisting of -OCH3 and -OR3; - provided that Ri or R2 is -OR3; - R3 represents a chemical group of formula (II) [Chem 19] • in which E represents a divalent C1-C12 hydrocarbon group possibly comprising one or more heteroatoms; • Xb X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; • The symbol * represents the attachment of the group of formula (II) to the oxygen atom.
[0055] More advantageously, among the compounds of formula (le), the compounds most particularly preferred are those of formula (Ici) [Chem 20]
[0056] in which: - Ri represents a chemical group chosen from the group consisting of -OCH3 and -OCH2CH3; more preferably Ri represents -OCH3; - E represents a divalent C1-C12 hydrocarbon group possibly comprising one or more heteroatoms; and - Xb X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl.
[0057] The compounds of formula (Ici) above are also of particular interest because they are synthetic intermediates of preferred compounds of formula (Ib 1).
[0058] Thus, a particularly preferred group of compounds of formula (I) are those for which Ri represents a chemical group chosen from the group consisting of -OCH3 and -OCH2CH3; and R2 is -OR3. In other words, this group of compounds is that corresponding to the set formed by the compounds of preferred formula (I1), (Ib1) and (Ici).
[0059] Preferably, in the compounds of formula (I), (la), (Ib) and (le), the condition "Ri or R2 is -OR3" means that if Ri is -OCH3 or -OCH2CH3 then R2 is -OR3; or if Ri is -OR3 then R2 is -OCH3. There is necessarily one (1) (and only one) -OR3 group in these compounds, either by substituting Ri or by substituting R2.
[0060] In the compounds of formula (I), (la), (lal), (Ib), (Ib 1 ), (le) and (Ici), E represents a divalent hydrocarbon group in Cl-Cl2 which may optionally contain one or more heteroatom(s). By “divalent hydrocarbon group” is meant, for the purposes of the present invention, a spacer group (or a bonding group) forming a bridge between the oxygen atom attached to the aromatic ring and the epoxy ring bearing the groups Xi, X2, X3; This spacer group E comprises from 1 to 12 carbon atoms and may optionally contain one or more heteroatoms such as, for example, N, O, and S. This spacer group may be a C1-C12 hydrocarbon chain, preferably saturated, linear or branched, and may optionally contain one or more heteroatoms such as, for example, N, O, and S. This hydrocarbon chain may optionally be substituted, provided that the substituents do not react with the chemical group T and the epoxy ring as defined above.
[0061] Preferably, in the compounds of formula (I), (la), (lal), (Ib), (Ibl), (le) and (Ici), E represents a divalent hydrocarbon group in C1-C10, preferably in C1-C9, which may optionally contain one or more heteroatom(s) such as, for example, N, O and S.
[0062] More preferably, in the compounds of formula (I), (la), (lal), (Ib), (Ibl), (le) and (Ici), E represents a Cl-Cl2 alkanediyl, preferably a C1-C10 alkanediyl, more preferably a C1-C9 alkanediyl. Even more preferably, E is chosen from the group consisting of methanediyl, ethanediyl and propanediyl.
[0063] Preferably, in the compounds of formula (I), (la), (lal), (Ib), (Ibl), (le) and (Ici), Xi, X2, X3, identical or different, are chosen from the group consisting of the hydrogen atom, the alkyls in C1-C6 and the aryls in C6-C14.
[0064] Preferably, in the compounds of formula (I), (la), (lal), (Ib), (Ibl), (le) and (Ici), Xi, X2, X3, identical or different, are chosen from the group consisting of the hydrogen atom, the C1-C6 alkyls and the phenyl.
[0065] Preferably, in the compounds of formula (I), (la), (lal), (Ib), (Ibl), (le) and (Ici), Xi, X2, X3, identical or different, are chosen from the group consisting of the hydrogen atom, the C1-C3 alkyls and the phenyl.
[0066] According to a preferred embodiment of the invention, in the compounds of formula (I), (la), (lal), (Ib), (Ibl), (le) and (Ici), Xb X2, X3, identical, represent a hydrogen atom.
[0067] According to another preferred embodiment of the invention, in the compounds of formula (I), (la), (lal), (Ib), (Ibl), (le) and (Ici), Xi and X2 represent a hydrogen atom and X3 represents a phenyl.
[0068] According to another embodiment of the invention, in the compounds of formula (I), (la), (lal), (Ib), (Ibl), (le) and (Ici), X3 is a hydrogen atom, and Xi and X2, identical or different, represent a hydrogen atom or a methyl.
[0069] As stated above, among the compounds of formula (I), the compounds of formula (la) are particularly preferred [Chem 21] Ri
[0070] in which: - Ri represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group chosen from the group consisting of -OCH3 and -OR3; - provided that Ri or R2 is -OR3; - R3 represents a chemical group of formula (II) [Chem 22] • in which E represents a divalent hydrocarbon group in C1-C12 possibly comprising one or more heteroatoms; preferably a C1-C12 alkanediyl, preferably a C1-C10 alkanediyl, more preferably a C1-C9 alkanediyl; • Xb X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; • the symbol * represents the attachment of the group of formula (II) to the oxygen atom;
[0071] and more preferably those for which E represents a C1-C9 alkanediyl, more preferably chosen from the group consisting of methanediyl, ethanediyl and propanediyl; and Xb X2, X3, identical or different, are chosen from the group consisting of hydrogen atom, C1-C3 alkyls and phenyl, more preferably an Xb X2, X3, identical, are a hydrogen atom.
[0072] Surprisingly, compounds of formula (la) lacking an ortho- substitution relative to the nitrile oxide function and possessing, in addition to the epoxy group, an -OCH3 or -OCH2CH3 group in the meta- or para- position, when grafted onto a polymer, preferably a diene elastomer, confer improved reinforcement properties to compositions based on said grafted polymer compared to prior art elastomeric compositions. Surprisingly, this improvement in properties does not compromise the rolling resistance / stiffness trade-off. This trade-off is even advantageously improved.Among the compounds of formula (la), those that are preferred are those of formula (lal) in which Ri represents a chemical group chosen from the group consisting of -OCH3 and -OCH2CH3; E represents a C1-C12 alkanediyl, preferably a Cl-CIO alkanediyl, more preferably a C1-C9 alkanediyl; and Xi, X2, X3, identical or different, are chosen from the group consisting of the hydrogen atom, the C1-C3 alkyls and the phenyl, more preferably Xb X2, X3, identical, are a hydrogen atom. Even more preferably, the compounds of formula (lal) most particularly preferred are those in which Ri represents -OCH3; E represents a C1-C12 alkanediyl, preferably a C1-C10 alkanediyl, more preferably a Cl-C9 alkanediyl and Xb X2, X3, . Identical or different, are chosen from the group consisting of the hydrogen atom, C1-C3 alkyls, and phenyl, more preferably an identical Xb X2, X3, are a hydrogen atom. Even more preferably, the compounds of formula (lal) most particularly preferred are those in which Ri represents -OCH3; E represents a Cl-C9 alkanediyl; and Xb X2, X3, identical, are a hydrogen atom. Even more preferably, the compounds of formula (lal) most particularly preferred are those in which Ri represents -OCH3; E represents is chosen from the group consisting of methanediyl, ethanediyl, and propanediyl; and Xb X2, X3 are identical and are a hydrogen atom. Among the compounds of formula (lal), the one that is most particularly preferred is that of formula (Ia2): [Chem 23] (Ia2) ..............N~--O
[0073] Another object of the present invention relates to a process for preparing a compound of formula (la) 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: [Chem 24] HO Ri (there)
[0074] with : Ri represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3, and -OR3; R2 represents a chemical group chosen from the group consisting of -OCH3 and -OR3; provided that Ri or R2 is -OR3; R3 represents a chemical group of formula (II) [Chem 25] • in which E represents a divalent C1-C12 hydrocarbon group possibly comprising one or more heteroatoms; • Xb X2, X3, whether identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; • The symbol * represents the attachment of the group of formula (II) to the oxygen atom.
[0075] The preferred modes of Rb R2, E, Xb X2 and X3 as described above, also apply to the process of preparing a compound of formula (la) from a compound of formula (Ib).
[0076] Preferably, the process for preparing a compound of formula (lal) comprises at least one reaction (dl) of a compound of formula (Ibl) with an oxidizing agent in the presence of at least one organic solvent SL1 according to the following reaction scheme: [Chem 26]
[0077] with E, Xb X2 and X3 as described above including their preferred modes, and Ri represents a chemical group selected from the group consisting of -OCH3 and -OCH2CH3, preferably Ri is -OCH3.
[0078] Preferably in these processes, 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 hydrogen peroxide in the presence of a catalyst. More preferably, the oxidizing agent is selected from the group consisting of sodium hypochlorite and N-bromosuccinimide, with or without a base. Preferably, the base may be triethylamine. Even more preferably, the oxidizing agent is sodium hypochlorite.
[0079] Advantageously, the amount of oxidizing agent is 1 to 5 molar equivalents, preferably 1 to 2 molar equivalents relative to the molar amount of the compound of formula (Ib), preferably of the compound of formula (Ibl).
[0080] Preferably, the organic solvent SL1 is chosen from chlorinated solvents and ester, ether and alcohol type solvents, more preferably chosen from dichloromethane, trichloromethane, ethyl acetate, butyl acetate, diethyl ether, isopropanol and ethanol, even more preferably is chosen from ethyl acetate, trichloromethane, dichloromethane and butyl acetate.
[0081] Preferably, the compound of formula (Ib), more preferably the compound of formula (Ibl), represents from 1 to 30% by weight, preferably from 1 to 20% by weight, per ratio to the total weight of the assembly comprising said compound of formula (Ib), preferably the compound of form (Ibl), said organic solvent SL1 and said oxidizing agent.
[0082] Preferably, the process of the invention comprises after reaction (d), (preferably after reaction (dl)), a step of recovering the compound of formula (la) (preferably of the compound of formula (lal)).
[0083] The compound of formula (Ib) can in particular be obtained from a preparation process comprising at least one reaction (c) of a compound of formula (le) with hydroxylamine NH2OH according to the following reaction scheme: [Chem 27]
[0084] with: - Ri represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group chosen from the group consisting of -OCH3 and -OR3; - provided that Ri or R2 is -OR3; - R3 represents a chemical group of formula (II) [Chem 28] • in which E represents a divalent C1-C12 hydrocarbon group possibly comprising one or more heteroatoms; • Xi, X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; • The symbol * represents the attachment of the group of formula (II) to the oxygen atom.
[0085] The preferred modes of Rb R2, E, Xb X2 and X3 as described above, also apply to the process of preparing a compound of formula (Ib) from a compound of formula (le).
[0086] Preferably, the compound of formula (Ibl) can in particular be obtained from a preparation process comprising at least one reaction (cl) of a compound of formula (Ici) with hydroxylamine NH2OH according to the following reaction scheme: [Chem 29]
[0087] with E, Xb X2 and X3 as described above, including their preferred modes and Ri represents a chemical group chosen from the group consisting of -OCH3 and -OCH2CH3, preferably Ri is -OCH3.
[0088] Preferably, the addition of hydroxylamine in reaction (c), preferably in reaction (cl), is carried out at a temperature ranging from 1°C to 100°C, more preferably between 20°C and 70°C.
[0089] Hydroxylamine is added either in aqueous solution or as a salt. When hydroxylamine is in salt form, it may be selected from the group consisting of hydroxylamine sulfate, hydroxylamine chloride, and mixtures thereof. When using hydroxylamine as a salt, a base may preferably be added to the reaction medium. Examples of bases include sodium acetate and triethylamine. The amount of base added may be in the range of 1 to 2 molar equivalents relative to the hydroxylamine generated, preferably 1 to 1.2 molar equivalents relative to the hydroxylamine generated. "Hydroxylamine generated" refers to the (NH3+OH) cation of the hydroxylamine salt that is released upon contact of said salt with water. When using a base, the base is mixed with the hydroxylamine salt, and then the mixture is dissolved in water.Preferably, hydroxylamine is brought into contact with the compound of formula (the) in the form of a hydroxylamine salt in the presence of a base, such as sodium acetate or triethylamine.
[0090] Preferably, the process of the invention may include after reaction (c), (preferably after reaction (cl)), a step of recovering the product of formula (Ib) (preferably of the product of formula (Ibl)).
[0091] The compound of formula (le) can be obtained by a preparation process comprising at least one reaction (b) of the compound of formula (IV) with a compound of formula (III) in the presence of at least one phase transfer agent and at a temperature ranging from 10°C to 120°C, preferably from 20°C to 100°C, according to the following reaction scheme: [Chem 30] - with the compound having formula (IV): • R4 represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3 and -OH; • R5 represents a chemical group chosen from the group consisting of -OCH3 and -OH; and • provided that R4 or R5 is -OH; - with the compound of formula (III): • E represents a divalent hydrocarbon group in Cl-Cl2, possibly comprising one or more heteroatoms; and • Xi, X2, X3, whether identical or different, represent a hydrogen atom, a C1-C6 alkyl group, or a C6-C14 aryl group; and • Z represents a leaving group; - with for the compound of formula (the): Ri and R2 as defined above.
[0092] The preferred modes of Rb R2, E, Xb X2 and X3 also apply to the process of preparing a compound of formula (the) from compounds of formula (IV) and compounds of formula (III).
[0093] Preferably, the compound of formula (Ici) can be obtained by a preparation process comprising at least one reaction (bl) of the compound of formula (IV) with a compound of formula (III) in the presence of at least one phase transfer agent and at a temperature from 10°C to 120°C, preferably from 20°C to 100°C, according to the following reaction scheme: [Chem 31] nm (JO) l!V)
[0094] with for: - the compound of formula (Here), E, Xb X2, X3, as defined above, and Ri represents a chemical group chosen from the group consisting of -OCH3 and -OCH2CH3; preferably Ri is -OCH3; - the compound with formula (IV): • R4 is -OCH3 or -OCH2CH3, preferably -OCH3, and • R5 is -OH, - the compound with formula (III): • E represents a divalent hydrocarbon group in Cl-Cl2, possibly comprising one or more heteroatoms; and • Xb, X2, X3, whether identical or different, represent a hydrogen atom, a C1-C6 alkyl group, or a C6-C14 aryl group; and • Z represents a leaving group.
[0095] The term "nucleofuge group" means a leaving group. Group Z can be selected from chlorine, bromine, iodine, fluorine, the mesylate group, the tosylate group, the acetate group, and the trifluoromethylsulfonate group. Preferably, Z is bromine or chlorine.
[0096] The phase transfer agent can be chosen from phosphonium salts, ammonium salts and mixtures thereof. Preferably, the phase transfer agent is tetrabutylammonium bromide.
[0097] Preferably, the molar amount of phase transfer agent is 0.01 to 1 molar equivalent, preferably 0.05 to 0.5 molar equivalents, relative to the molar amount of compound of formula (III).
[0098] Preferably, the process of the invention may include after reaction (b), (preferably after reaction (bl)) a step of recovering the product of formula (le) (preferably of the product of formula (Ici)).
[0099] The compounds of formula (IV) as defined above are commercially available from suppliers such as Sigma-Aldrich, Merk, etc. They can be obtained by chemical synthesis, or in the case of vanillin by extraction from the vanilla pod or in the case of iso-vanillin by extraction from cassava or even from fermentation by microorganisms, in particular by fermentation from ferulic acid.
[0100] The compounds of formula (III) may be commercially available or may be obtained by epoxidation of the corresponding haloalkene of formula (V) according to the reaction scheme below. The synthesis of a compound comprising an epoxide ring from its corresponding alkene is well known. For example, this epoxidation can be carried out in the presence of a peracid such as metachloroperbenzoic acid, peracetic acid, or performic acid. Another well-known technique is the use of dimethyldioxirane.
[0101] [Chem.32] X3 X! (III)
[0102] The compounds of formula (V) are commercially available from suppliers such as Sigma Aldrich, ABCR.
[0103] As explained previously, the compounds of formula (la) and its preferred embodiments, in particular the compounds of formula (lal), and more particularly the compound of formula (Ia2), are used as polymer modifying agents. They can be grafted onto one or more polymers comprising at least one unsaturated carbon-carbon bond, in particular this polymer may be an elastomer and more particularly a diene elastomer. The compounds of the invention advantageously allow the production of grafted polymers (also called modified polymers), in particular grafted diene elastomers, regardless of the initial microstructure of the polymer, the only condition being that the polymer comprises at least one unsaturated carbon-carbon bond, preferably a carbon-carbon double bond.
[0104] The grafting of the polymer comprising at least one unsaturated carbon-carbon bond can be carried out by reacting the initial polymer with the compound of formula (la) and its preferred embodiments, in particular the compounds of formula (lal), and more particularly the compound of formula (Ia2). The grafting of these compounds is carried out by [3+2] cycloaddition of the nitrile oxide function of said compounds onto an unsaturated carbon-carbon bond of the polymer chain. The mechanism of this cycloaddition is illustrated in particular in document WO2012 / 007441.
[0105] The grafting of the compound of formula (la) and its preferred embodiments, in particular the compounds of formula (lal), and more particularly the compound of formula (Ia2), can be carried out in bulk, for example in an internal mixer or in an external mixer such as a roller mixer, or in solution. The grafting process can be carried out in solution continuously or batchwise. The modified polymer can be separated from its solution by any type of means known to those skilled in the art, and in particular by a steam stripping operation.
[0106] The compounds of formula (la) and its preferred embodiments, in particular the compounds of formula (lal), and more particularly the compound of formula (Ia2), can be incorporated into elastomeric compositions. These elastomeric compositions can be based on at least one diene elastomer, a reinforcing filler, and at least one crosslinking agent. The grafting of the compounds of formula (la) and its preferred embodiments, in particular the compounds of formula (lal), and more particularly the compound of formula (Ia2), onto the diene elastomer can be carried out prior to the introduction of said elastomer into the composition or can be grafted by reaction with said compound of formula (la) during the manufacture of the composition. The elastomeric composition may further comprise an additive.The additives that can be used may be plasticizers (such as plasticizing oils and / or plasticizing resins), non-reinforcing fillers, pigments, protective agents such as ozone-suppressing waxes, chemical ozone detoxifiers, antioxidants, anti-fatigue agents, and reinforcing resins (as described, for example, in application WO 02 / 10269). These elastomeric compositions may be used for the manufacture of semi-finished tires or for the manufacture of tires.
[0107] The following examples illustrate the invention, but the latter cannot be limited to these examples alone.
[0108] Examples:
[0109] 1. Methods
[0110] 1.1 Measurement of average molar masses by number (Mn), by weight (Mw) and of the polydispersity index of elastomers
[0111] Size exclusion chromatography (SEC) is used. SEC allows the separation of macromolecules in solution according to their size through columns filled with a porous gel. The macromolecules are separated according to their hydrodynamic volume, with the largest being eluted first.
[0112] While not an absolute method, SEC allows for the determination of the molar mass distribution of an elastomer. Using commercial standard products, the various number-average (Mn) and weight-average (Mw) molar masses can be determined, and the polymolecularity index (Ip = Mw / Mn) calculated via a Moore calibration.
[0113] Preparation of the elastomer sample to be tested
[0114] No special treatment of the elastomer sample is required prior to analysis. It is simply solubilized to a concentration of approximately 1 g / L in chloroform or in the following mixture: tetrahydrofuran + 1% vol. diisopropylamine + 1% vol. triethylamine + 1% vol. distilled water (% vol. = % vol.). The solution is then filtered through a 0.45 µm pore size filter before injection.
[0115] SEC Analysis
[0116] The apparatus used is a WATERS alliance chromatograph. The elution solvent is the following mixture: tetrahydrofuran + 1 vol. diisopropylamine + 1 vol. triethylamine or chloroform, depending on the solvent used to dissolve the elastomer. The flow rate is 0.7 mL / min, the system temperature is 35°C, and the analysis time is 90 min. A set of four WATERS columns in series is used, with the trade names "STYRAGEL HMW7", "STYRAGEL HMW6E", and two "STYRAGEL HT6E".
[0117] The injected volume of the elastomer sample solution is 100 pL. The detector is a WATERS 2410 differential refractometer with a wavelength of 810 nm. The chromatographic data processing software is the WATERS EM POWER system. The calculated average molar masses are relative to a calibration curve prepared using commercially available PSS READY CAL-KIT polystyrene standards.
[0118] 1.2. Characterization of molecules
[0119] Structural analysis and determination of the molar purities of the synthetic molecules are performed by NMR analysis. Spectra are acquired on a Bruker Avance 3400 MHz spectrometer equipped with a 5 mm BBFO-zgrad broadband probe. The quantitative ¹H NMR experiment uses a single 30° pulse sequence and a 3-second repetition delay between each of the 64 acquisitions. Samples are solubilized in a deuterated solvent, deuterated dimethyl sulfoxide (DMSO), unless otherwise specified. The deuterated solvent is also used for the lock signal. For example, calibration is performed on the proton signal of deuterated DMSO at 2.44 ppm relative to a TMS reference at 0 ppm. The 1H NMR spectrum coupled with the 2D HSQC 'H / 13C and HMBC 'H / 13C experiments allows for the structural determination of molecules (see allocation tables). Molar quantifications are performed using the quantitative 1D 1H NMR spectrum.
[0120] Mass spectrometry analysis is performed by direct injection using an electrospray ionization (ID / ESI) mode. The analyses were performed on a Bruker HCT spectrometer (flow rate 600 pL / min, nebulizer gas pressure 10 psi, nebulizer gas flow rate 4 L / min).
[0121] 1.3. Characterization of compounds grafted onto diene elastomers
[0122] The molar content of compounds grafted onto diene elastomers is determined by NMR analysis. Spectra are acquired on a 500 MHz BRUKER spectrometer equipped with a CryoSonde BBFO-zgrad-5 mm. The quantitative ¹H NMR experiment uses a single 30° pulse sequence and a 5-second repetition delay between each acquisition. The samples are solubilized in deuterated chloroform (CDC13) to obtain a lock signal. 2D NMR experiments made it possible to verify the nature of the grafted motif through the chemical shifts of carbon and proton atoms.
[0123] 1.4. Dynamic properties of elastomeric compositions
[0124] The dynamic properties G* and tan(ô)max are measured on a viscoanalyzer (Metravib VA4000), according to ASTM D5992-96. The response of a vulcanized composition sample (cylindrical specimen 4 mm thick and 400 mm² cross-section) subjected to sinusoidal loading in alternating simple shear, at a frequency of 10 Hz, at a temperature of 60°C, is recorded. A strain amplitude sweep is performed from 0.1% to 100% peak-to-peak (forward cycle) and then from 100% to 0.1% peak-to-peak (reverse cycle).
[0125] The results used are the complex dynamic shear modulus G* at 50% strain (G*50%return), the dynamic loss factor tan(φ) at 60°C. For the return, the value of the complex dynamic shear modulus G* at 50% strain, denoted G*50%returnat60°C, and the maximum value of the observed dynamic loss factor tan(φ), denoted tan(φ)maxat60°C, are recorded.
[0126] The results are given on a base of 100; the arbitrary value 100 being assigned to the control to calculate and then compare tan(θ)maxa6θc and G*50% return to 6θc-
[0127] For tan(ô)maxa6œc, the value in base 100 for the sample to be tested is calculated according to the operation: (value of tan(ô)maxa60«c of the sample to be tested / value of tan(ô)maxa60 c of the control) x 100. In this way, a result less than 100 indicates a decrease in hysteresis which corresponds to an improvement in rolling resistance performance.
[0128] For G*50%returnto60°c, the value in base 100 for the sample to be tested is calculated according to the operation: (value of G*50%returnto60°c of the sample to be tested / value of G*50%returnto60°c of the control) x 100. In this way, a result greater than 100 indicates an improvement in the complex dynamic shear modulus G*50%returnto60°c, which corroborates an improvement in the stiffness of the material.
[0129] 1.5. Tensile test.
[0130] These tensile tests determine the elastic stresses. Unless otherwise specified, they are carried out in accordance with French standard NF T46-002 of September 1988. Processing the tensile recordings also allows the modulus curve to be plotted as a function of elongation. The nominal secant modulus, calculated by reducing the measurement to the initial cross-section of the specimen (or apparent stress, in MPa), is measured at 100% elongation (MSA100) and at 300% elongation (MSA300). All these tensile measurements are carried out under normal temperature conditions (23 ± 2 °C) according to standard NF T46-002 and at a temperature of 100°C.
[0131] The MSA300 / MSA100 ratio is the reinforcement index. The value is based on 100 for the sample to be tested is calculated according to the operation: (value of MSA300 / MSA100 of the sample to be tested / value of MSA300 / MSA100 of the control) x 100. In this way, a result greater than 100 indicates an improvement in the reinforcement index.
[0132] 2. Synthesis of compounds
[0133] 2.1. Synthesis of 3-methoxy-4-(oxiran-2-ylmethoxy)benzonitrile oxide (Compound A, compound according to the invention)
[0134] The synthesis of compound A is carried out according to the following reaction scheme: [Chem 33]
[0135] The vanillin comes from the company Sigma-Aldrich which markets it under the reference “W310700-1 KG”.
[0136] 2.1.1. Step 1: Synthesis of 3-methoxy-4-(oxiran-2-ylmethoxy)benzaldehyde
[0137] A solution of vanillin (20 g; 131 mmol) in epichlorohydrin (278 mL; 3.56 mol, or 27 eq. (eq. = molar equivalent), is added tetrabutylammonium bromide (4.24 g; 13.15 mmol, or 0.1 eq.). The reaction mixture is then stirred for 60–70 minutes at 90°C. After returning to room temperature, the reaction mixture is diluted with ethyl acetate (150 mL), washed with brine (3 x 75 mL), and finally with distilled water (75 mL). The organic phase is then separated, dried over sodium sulfate, and evaporated under reduced pressure (bath temperature = 50°C; 13 mbar). The resulting oil is triturated with ice-cold isopropyl alcohol (i-ProOH) (50 mL), allowing for rapid crystallization. The precipitate is filtered and washed with ice-cold i-ProH (3 x 35 ml); then air-dried.
[0138] A white solid (23.16 g; 111 mmol) is obtained with a yield of 85%. The molar purity is greater than 90% (H-NMR). [Chem 34]
[0139] 7 A'2' 11—"■ 10 O 4 \ / 1 o O. 5CH3 [Tables 1] No. ô 'H (ppm) ô 13C (ppm) 1 9.80 190.9 2 / 130.6 3 7.36 109.4 4 / 149.9 5 3.88 56.0 6 / 153.3 7 6.97 112.2 8 7.38 126.5 9 4.04 and 4.33 69.9 10 3.37 49.8 11 2.73 and 2.88 44.7
[0140] CDC13 Solvent
[0141] 2.1.2 Step 2: Synthesis of the oxime 3-methoxy-4-(oxiran-2-ylmethoxy)benzaldehyde
[0142] A suspension of 3-methoxy-4-(oxiran-2-ylmethoxy)benzaldehyde (4.253g; A solution of sodium acetate (2.51 g; 30.6 mmol, or 1.5 eq.) and hydroxylamine hydrochloride (2.129 g; 30.6 mmol, or 1.5 eq.) in distilled water (100 mL) is added at room temperature (23°C). After complete solubilization in 40–50 seconds, slight exothermicity is observed in the reaction mixture. A new precipitate forms within a few minutes. The reaction mixture is then stirred at room temperature for 90 minutes. Crushed ice (100 g) is then added, and the mixture is stirred until the crushed ice has completely melted. The precipitate is finally filtered, washed with excess water, and air-dried.
[0143] A white solid (3.604 g; 16.14 mmol; yield 79%) is obtained. The purity molar is greater than 89% (H-NMR). [Chem 35]
[0144] [Tables2] No. ô 'H (ppm) ô 13C (ppm) 1 8.00 150.2 2 / 126.0 3 6.95 121.5 4 6.86 113.6 5 / 149.9 6 / 150.0 7 7.17 108.9 8 3.84 56.0 9 4.00 and 4.22 70.2 10 3.33 50.1 11 2.69 and 2.84 44.9
[0145] Solvent: CDC13
[0146] 2.1.3 Step 3: Synthesis of 3-methoxy-4-(oxiran-2-ylmethoxy) ben- zonitrile
[0147] 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 is dropwise added a bleach solution (98.5 mL; 4% active chlorine) (bleach = sodium hypochlorite) over 20-25 minutes. The reaction mixture is then stirred for 80-90 minutes at 0-5°C. The organic phase is then separated, washed with water (2 x 50 mL), and finally evaporated under reduced pressure (bath temperature = 25°C; 10 mbar) to yield a beige solid. This solid is then resolubilized in dichloromethane (-100 mL). The previously obtained solution is then filtered through a SiO2 layer (approximately 4-5 cm thick) by eluting with dichloromethane (2 x 30 ml). The permeate is then concentrated under reduced pressure (T bath = 25°C; 10 mbar) to produce a white solid obtained with a yield of 71% (7.126 g; 32.2 mmol). The molar purity is 95% (¹H NMR).
[0148] [Chem.36] [Tables 3]
[0149] No. ô 'H (ppm) ô 13C (ppm) 1 / / 2 / 106.1 3 7.04 125.8 4 6.87 114.0 5 / 150.7 6 / 150.0 7 6.92 115.0 8 3.82 56.2 9 3.98 and 4.27 70.2 10 3.32 49.9 11 2.69 and 2.85 44.7 Solvent: CDC13
[0150]
[0151]
[0152] 2.2. Synthesis of 2-(glycidyloxy)-l-naphtonitrile oxide (Compound B, prior art compound) 2-(glycidyloxy)-l-naphtonitrile oxide, compound B, is synthesized according to the procedure described in US patent application 2012 / 0046418A1 paragraphs
[0033] to
[0037] , [Chem 37]
[0153] 2.3 Synthesis of 2,4,6-trimethyl-3-(oxiran-2-ylmthoxy)benzonitrile oxide (Compound C, compound of prior art)
[0154] 2,4,6-Trimethyl-3-(oxiran-2-ylmthoxy)benzonitrile oxide, compound C, is synthesized according to the reaction scheme and synthesis process described below and taken from the examples in document WO2019102128: [Chem 38]
[0155] 2.3.1. Synthesis of 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzaldehyde:
[0156] Potassium carbonate (50.50 g; 0.365 mol) is added 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). The reaction mixture is stirred for 3 hours at 60°C and then for 2.5–3 hours at 70°C. After cooling to 40–50°C, the reaction mixture is diluted with a mixture of water (250 mL) and ethyl acetate (250 mL) and then stirred for 10 minutes. The organic phase is separated and washed with water (4 times per 125 mL). The solvent is evaporated under reduced pressure (bath temperature 37°C; 40 mbar). A red oil (66.43 g) is obtained.
[0157] The by-product of the reaction, the 3,3'-((2-hydroxypropane-1,3-diyl)bis(oxy))bis(2,4,6-trimethylbenzaldehyde) is separated 2,4,6-Trimethyl-3-(oxiran-2-ylmethoxy)benzaldehyde was measured by silica column chromatography (eluent: ethyl acetate / petroleum ether = 1 / 4 by volume). After recovering the fractions containing 2,4,6-Trimethyl-3-(oxiran-2-ylmethoxy)benzaldehyde, the solvents were evaporated under reduced pressure (bath temperature 36°C; 21 mbar). Petroleum ether (120 mL) was added to the residue, and the suspension was maintained under stirring at -18°C for 2 hours. The precipitate was filtered and washed with petroleum ether (40 / 60) (3 x 25 mL) and finally dried for 10–15 hours under atmospheric pressure at room temperature. A white solid (40.04 g; mass yield 75%) with a melting point of 52°C was obtained. The molar purity is greater than 99% (H NMR). [Chem 39]
[0158] [Tables4] ô 1H (ppm) ô 13C (ppm) 1 10.37 193.3 2 / 131.1 3 / 132.8 4 2.4 19.2 5 6.94 131.3 6 / 136.3 7 2.2 16.1 8 / 153.4 9 / 135.7 10 2.4 11.7 11 3.50 / 4.00 73.4 12 3.29 49.6 13 2.60 / 2.76 42.9
[0159] DMSO Solvent
[0160] 2.3.2 Synthesis of the oxime 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzaldehyde:
[0161] To a solution of 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzaldehyde (46.70 g; A solution of hydroxylamine (16.81 g; 0.254 mol, 50% in water, Aldrich) in ethyl alcohol (75 mL) is added at room temperature to 0.212 mol in ethyl alcohol (75 mL). The reaction mixture is stirred for 3 hours at 23°C (bath temperature). After evaporation of the solvent (bath temperature = 24°C; 35 mbar), petroleum ether (40 / 60) (150 mL) is added. The precipitate is filtered and washed through a filter with petroleum ether (100 mL). The crude product is dissolved in a mixture of ethyl acetate (650 mL) and petroleum ether (650 mL) at room temperature, and this solution is filtered through a silica gel layer (0.9 cm, 2.0 cm SiO2).
[0162] The solvents are evaporated (bath temperature = 22-24°C) and the 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzaldehyde oxime is dried under atmospheric pressure at room temperature. A white solid (43.81 g; mass yield of 88%) with a melting point of 77°C is obtained. The molar purity is greater than 99% (H NMR). [Chem 40] H3C^ A"
[0163] [Tables5] ô 1H (ppm) ô 13C (ppm) 1 8.2 147.3 2 / 129.1 3 / 129.2 4 2.18 20.1 5 6.85 130.2 6 / 130.3 7 2.15 15.7 8 / 153.1 9 / 131.7 10 2.18 13.1 11 3.48 / 3.96 73.3 12 3.27 49.6 13 2.60 / 2.76 42.8
[0164] DMSO Solvent
[0165] 2.3.3 Synthesis of 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzonitrile oxide (compound C):
[0166] 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 in water (62.9 g active Cl / L) (126 mL) is added dropwise over 10-15 minutes. The temperature of the reaction medium is maintained between 3 and 5°C. The reaction medium is then stirred for 1 hour at 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 at reduced pressure (bath temperature = 22°C, 35 mbar). Petroleum ether (40 / 60) (90 ml) is added to this residue, and the suspension is stirred at room temperature for 10-12 hours. The precipitate is filtered and washed with petroleum ether (3 times per 30 ml) and finally dried for 10-15 hours under atmospheric pressure at room temperature.A white solid (15.12 g, mass yield of 90%) with a melting point of 63°C is obtained. The molar purity is greater than 99% (¹H NMR). [Chem 41] . 10
[0167] [Tableauxô] ô 1H (ppm) ô 13C (ppm) 1 2.59 / 2.76 43.0 2 3.28 49.6 3 3.51 / 4.03 73.5 4 / 153.0 5 / 136.3 6 2.27 14.3 7 / 111.7 8 / / 9 / 134.4 10 2.18 15.9 11 7.01 129.9 12 / 134.0 13 2.27 19.5
[0168] 3. Obtaining modified diene elastomers
[0169] 3.1 Natural rubber modified with compound A
[0170] 0.98 part of the oxide is incorporated 3-Methoxy-4-(oxiran-2-ylmethoxoy)benzonitrile (i.e., a molar fraction of 0.3 mol%), compound A, obtained according to the process described in section 2.1, with an NMR purity greater than 89 mol, was mixed with 100 g of natural rubber on a roller tool (external mixer at 30°C). The mixture was homogenized fifteen times on this tool, then formed into plates, before undergoing heat treatment at 100°C for 10 min under a press at 10 bar pressure. ¹H NMR analysis determined a molar grafting rate of less than 0.100 mol with a molar grafting yield of less than 33%.
[0171] 3.2 Natural rubber modified with compound B
[0172] 1.06 parts per million of 2-(glycidyloxy)-l-naphtonitrile oxide (i.e., a molar fraction of 0.3 mol%), of 95 mol NMR purity, compound B obtained according to the process of paragraph 2.2, is incorporated into 100 g of natural rubber on a roller tool (external mixer at 30°C). The mixture is homogenized fifteen times on this tool, then formed into plates before undergoing heat treatment at 100°C for 10 min under a press at 10 bar pressure. ¹H NMR analysis determined a molar grafting rate of 0.162 mol with a molar grafting yield of 54%.
[0173] 3.3 Natural rubber modified with compound C
[0174] 1.03 parts per annum of 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzonitrile oxide (i.e., a mole fraction of 0.3 mol%), of 99 mol NMR purity, compound C obtained according to the process of paragraph 2.3, is incorporated into 100 g of natural rubber on a roller tool (external mixer at 30°C). The mixture is homogenized fifteen times on this tool, then formed into plates before undergoing heat treatment at 100°C for 10 min under a press at 10 bar pressure. ¹H NMR analysis determined a molar grafting rate of 0.070 mol with a molar grafting yield of 23%.
[0175] 3.4 Synthetic polyisoprene modified with compound A
[0176] 0.98 part of the oxide is incorporated 3-Methoxy-4-(oxiran-2-ylmethoxoy)benzonitrile (i.e., a mole fraction of 0.3 mol%), compound A, obtained according to the process described in paragraph 2.1, with an NMR purity greater than 89 mol, is mixed with 100 g of synthetic polyisoprene (containing 99.35 wt% cis-1,4-isoprene units and 0.65 wt% cis-3,4-isoprene units; Mn = 375,000 g / mol and Ip = 3.6, measured according to the method described above) on a roller tool (external mixer at 30°C). The mixture is homogenized fifteen times on this tool, then formed into plates before undergoing heat treatment at 100°C for 10 min under a press at 10 bar pressure. 'H NMR analysis determined a molar grafting rate of 0.150 mol% with a molar grafting yield of 50%.
[0177] 3.5 Synthetic polyisoprene modified with compound B
[0178] 1.06 parts per liter of 2-(glycidyloxy)-1-naphtonitrile oxide (i.e., a mole fraction of 0.3 mol%), of 95 mol NMR purity, compound B obtained according to the process of paragraph 2.2, is incorporated into 100 g of synthetic polyisoprene (containing 99.35 wt% of cis-1,4-isoprene units and 0.65 wt% of 3,4-isoprene units; Mn = 375,000 g / mol and Ip = 3.6 measured according to the method described above) on a roller tool (external mixer at 30°C). The mixture is homogenized fifteen times on this tool, then formed into plates before undergoing heat treatment at 100°C for 10 min under a press at 10 bar pressure. ¹H NMR analysis made it possible to determine a molar grafting rate of 0.145 mol% with a molar grafting yield of 48%.
[0179] 3.6 Synthetic polyisoprene modified with compound C
[0180] 1.03 parts per liter of 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzonitrile oxide (i.e., a mole fraction of 0.3 mol%), of 99 mol NMR purity, compound C obtained according to paragraph 2.3, is incorporated into 100 g of synthetic polyisoprene (containing 99.35 wt% of cis-1,4-isoprene units and 0.65 wt% of 3,4-isoprene units; Mn = 375,000 g / mol and Ip = 3.6 measured according to the method described above) on a roller tool (external mixer at 30°C). The mixture is homogenized fifteen times on this tool, then formed into plates before undergoing heat treatment at 100°C for 10 min under a press at 10 bar pressure. 'H NMR analysis determined a molar grafting rate of 0.200 mol% with a molar grafting yield of 67%.
[0181] 4. Ingredients used in elastomeric compositions
[0182] (1) Silica “Zeosil 1165MP” marketed by Solvay;
[0183] (2) Bis[3-(triethoxysilyl)propyl] tetrasulfide silane (TESPT) marketed by Evonik under the reference "Si69";
[0184] (3) N234 grade carbon black marketed by Cabot Corporation;
[0185] (4) Nl,3-dimethylbutyl-N-phenyl-para-phenylenediamine marketed by Flexys under the reference “Santoflex 6-PPD”;
[0186] (5) 2,2,4-trimethyl-l,2-dihydroquinoline marketed by the company Flexys;
[0187] (6) Zinc Oxide (industrial grade) marketed by the company Umicore;
[0188] (7) Stearine “Pristerene 4031” marketed by the company Uniquema;
[0189] (8) N-cyclohexyl-2-benzothiazyl-sulfenamide marketed by Flexys under the reference “Sancure CBS”;
[0190] (9) natural rubber modified by compound B, obtained according to the process described in paragraph 3.2;
[0191] (10) natural rubber modified by compound C, obtained according to the process described in paragraph 3.3;
[0192] (11) natural rubber modified by compound A of the invention, obtained according to the process described in paragraph 3.1;
[0193] (12) synthetic polyisoprene modified by compound B, obtained according to the process described in paragraph 3.5;
[0194] (13) synthetic polyisoprene modified by compound C, obtained according to the process described in paragraph 3.6;
[0195] (14) synthetic polyisoprene modified by compound A of the invention, obtained according to the procedure described in paragraph 3.4.
[0196] 5. Test 1
[0197] The purpose of this test is to show the compromise improvement in performance of an elastomeric composition comprising natural rubber modified by the compound of the invention (composition C3) compared to a control elastomeric composition (composition Tl) and to two comparative elastomeric compositions (composition Cl and C2).
[0198] The proportions of the different constituents of these compositions, expressed in parts per cent parts per cent of elastomer, are presented in Table 5.
[0199] [Tables?] Tl Cl C2 C3 Unmodified natural rubber 100 (-) (-) (-) Modified natural rubber with compound B (9) (-) 100 (-) (-) Modified natural rubber with compound C (10) (-) (-) 100 (-) Modified natural rubber with compound A (11) (-) (-) (-) 100 Reinforcing filler (1) 55 55 55 55 Coupling agent (2) 5.5 5.5 5.5 5.5 Carbon black (3) 3 3 3 3 Antioxidant (4) 1.5 1.5 1.5 1.5 TMQ (5) 1 1 1 1 Paraffin 1 1 1 1 ZnO (6) 2.7 2.7 2.7 2.7 Stearic acid (7) 2.5 2.5 2.5 2.5 CBS (8) 1.63 1.63 1.63 1.63 Sulfur 1.33 1.33 1.33 1.33
[0200] The elastomeric compositions Tl, Cl to C3 are prepared in the following manner: natural rubber modified by compound B or modified by compound C or modified by compound A or unmodified natural rubber is introduced into an internal "Polylab" mixer of 85 cm3, filled to 70% and whose initial tank temperature is about 100°C.
[0201] Next, for each of the elastomeric compositions, the reinforcing filler(s), the filler coupling agent with the diene telastomer, and then, after one to two minutes of mixing, the various other ingredients, with the exception of the vulcanization system, are introduced. A thermomechanical process (non-productive phase) is then carried out in a single step, lasting approximately 5 to 6 minutes in total, until a maximum drop temperature of 160°C is reached.
[0202] The mixture thus obtained is recovered, cooled, and then the vulcanization system (sulfur and sulfenamide-type accelerator) is added to an external mixer (homo-finisher) at 25°C, mixing the whole (productive phase) for about 5 to 6 minutes.
[0203] The elastomeric compositions thus obtained are then calendered into plates (thickness of 2 to 3 mm) for the measurement of their physical or mechanical properties.
[0204] The rubbery properties of these compositions are measured after heating at 150°C for 30 minutes. The results obtained are shown in Table 6.
[0205] [Tables8] Compositions Tl Cl C2 C3 MA300 / MA100 at 23°C (base 100) 100 125 99 133 MA300 / MA100 at 100°C (base 100) 100 125 107 129 Tan(θ)max at 60°C (base 100) 100 74 93 65 G*50% return to 60°C (base 100) 100 101 99 104
[0206] The elastomeric composition of the invention C3 simultaneously exhibits, compared to the control elastomeric compositions Tl and comparative Cl and C2, a significant improvement in the reinforcement index (MA300 / M100) and an improvement in the performance trade-off rolling resistance / stiffness (decrease in tan(ô)maxa60 c» and increase in G*50% back to 6o»c).
[0207] 5. Test 2
[0208] The purpose of this test is to show the compromise improvement in performance of an elastomeric composition comprising a synthetic polyisoprene modified by the compound of the invention (composition C6) compared to a control elastomeric composition (composition T2) and to two comparative elastomeric compositions (composition C4 and C5).
[0209] The proportions of the different constituents of these elastomeric compositions, expressed in parts per cent parts per cent of elastomer, are presented in Table 7.
[0210] [Tables9] T2 C4 C5 C6 Unmodified synthetic polyisoprene 100 (-) (-) (-) Synthetic polyisoprene modified with compound B (12) (-) 100 (-) (-) Synthetic polyisoprene modified with compound C (13) (-) (-) 100 (-) Synthetic polyisoprene modified with compound A (14) (-) (-) 100 Reinforcing filler (1) 55 55 55 55 Coupling agent (2) 5.5 5.5 5.5 5.5 Carbon black (3) 3 3 3 3 Antioxidant (4) 1.5 1.5 1.5 1.5 TMQ (5) 1 1 1 1 Paraffin 1 1 1 1 ZnO (6) 2.7 2.7 2.7 2.7 Stearic acid (7) 2.5 2.5 2.5 2.5 CBS (8) 1.63 1.63 1.63 1.63 Sulfur 1.33 1.33 1.33 1.33
[0211] Elastomeric compositions T2, C4 to C6 are prepared according to the process described above for elastomeric compositions T1, Cl to C3.
[0212] The rubbery properties of these elastomeric compositions are measured after baking at 150°C for 30 minutes. The results obtained are shown in Table 8.
[0213] [TableauxlO] Compositions T2 C4 C5 C6 MA300 / MA100 at 23°C (base 100) 100 124 124 154 MA300 / MA100 at 100°C (base 100) 100 116 112 152 Tan(θ)max at 60°C (base 100) 100 60 90 60 G*50% return to 60°C (base 100) 100 87 87 93
[0214] The elastomeric composition of the invention C6 simultaneously exhibits, in relation to the control elastomeric compositions T2 and comparative compositions C4 and C5, an improvement significant improvement in the reinforcement index (MA300 / M100) and an improvement in the rolling resistance / stiffness performance trade-off (decrease in tan(φ)max at 60°C and increase in G*50% return to eoec)-
Claims
Claims
1. Compound of the following formula (I): [Chem 42] œ in which: - T represents a chemical group chosen from the group consisting of -CH=NOH and -CN+-O; - Ri represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3 and -OR3; - R2 represents a chemical group chosen from the group consisting of -OCH3 and -OR3; - provided that only one of the groups Ri or R2 is -OR3; - R3 represents a chemical group of formula (II): [Chem 43] (II) in which E represents a C1-C9 alkanediyl; Xi, X2, X3, identical or different, represent a hydrogen atom, a C1-C3 alkyl or a phenyl; the symbol * represents the attachment of the group of formula (II) to the oxygen atom.
2.
3.
4.
5.
6.
7. A compound of formula (I) according to claim 1, wherein R 1 represents a chemical group selected from the group consisting of -OCH 3 and -OCH 2 CH 3 ; and R 2 is -OR 3. A compound of formula (I) according to claim 1 or 2, wherein T is -CH=NOH. A compound of formula (I) according to claim 1 or 2, wherein T is -CN+-O. A compound of formula (I) according to any one of the preceding claims, wherein E is selected from the group consisting of methanediyl, ethanediyl and propanediyl. A compound of formula (I) according to any one of the preceding claims, wherein Xb, X2, X3, which are identical, are a hydrogen atom. A process for preparing a compound of formula (Ia), said process 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 following reaction scheme: [Chem 44] with - Ri represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3, and -OR3; - R2 represents a chemical group chosen from the group consisting of -OCH3 and -OR3; - provided that only one of the groups Ri or R2 is -OR3; - R3 represents a chemical group of formula (II) [Chem 45] X1 X2 E-——X3 0 (II) • in which E represents a C1-C9 alkanediyl; • Xb X2, X3, identical or different, represent a hydrogen atom, a C1-C3 alkyl or phenyl; • the symbol * represents the attachment of the group of formula (II) to the oxygen atom.
8. The method of claim 7, wherein said oxidizing agent is selected from sodium hypochlorite, N-bromosuccinimide in the presence of a base, N-chlorosuccinimide in the presence of a base, and hydrogen peroxide in the presence of a catalyst.
9. Method according to claim 7 or 8, in which the organic solvent SL1 is chosen from chlorinated solvents and ester, ether and alcohol type solvents.
10. A process according to any one of claims 7 to 9, further comprising a step of reacting a compound of formula (Ic) with hydroxylamine according to the following reaction scheme: [Chem 46] Va » H R3---\ / ---=¾¾ / ____________ / / \____ \ / ^0 ■> H“NH ** r2---\ / --- (Ic) \ (IW OH with Riet R2 as defined in claim 7.
11. A method according to claim 10, wherein the hydroxylamine is contacted with the compound of formula (Ic) in the form of a hydroxylamine salt in the presence of a base.
12. Process according to claim 10 or 11 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 and at a temperature ranging from 10°C to 120°C, preferably 30°C to 100°C according to the following reaction scheme: [Chem 47] with for the compound of formula (IV): • R4 represents a chemical group chosen from the group consisting of -OCH3, -OCH2CH3 and -OH; • R5 represents a chemical group chosen from the group consisting of -OCH3 and -OH; and • provided that only one of the R4 or R5 groups is -OH. with for the compound of formula (III): • E represents a C1-C9 alkanediyl; and • Xb X2, X3, identical or different, represent a hydrogen atom, a C1-C3 alkyl or phenyl; and • / represents a nucleofugal group; with for the compound of formula (Ic): R1 and R2 as defined in claim 7.
13. The method of claim 12, wherein the phase transfer agent is among phosphonium salts, ammonium salts and mixtures thereof.