EP4452957A1 - Composé 1,3-dipolaire comprenant un groupe époxy et ses intermédiaires de synthèse - Google Patents

Composé 1,3-dipolaire comprenant un groupe époxy et ses intermédiaires de synthèse

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Publication number
EP4452957A1
EP4452957A1 EP22840600.5A EP22840600A EP4452957A1 EP 4452957 A1 EP4452957 A1 EP 4452957A1 EP 22840600 A EP22840600 A EP 22840600A EP 4452957 A1 EP4452957 A1 EP 4452957A1
Authority
EP
European Patent Office
Prior art keywords
formula
group
compound
chosen
och3
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22840600.5A
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German (de)
English (en)
French (fr)
Inventor
François JEAN-BAPTISTE-DIT-DOMINIQUE
Sergey Ivanov
Ruslan NASYBULLIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Compagnie Generale des Etablissements Michelin SCA
Original Assignee
Compagnie Generale des Etablissements Michelin SCA
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Publication date
Application filed by Compagnie Generale des Etablissements Michelin SCA filed Critical Compagnie Generale des Etablissements Michelin SCA
Publication of EP4452957A1 publication Critical patent/EP4452957A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
    • C07D303/23—Oxiranylmethyl ethers of compounds having one hydroxy group bound to a six-membered aromatic ring, the oxiranylmethyl radical not being further substituted, i.e.

Definitions

  • 1,3-dipolar compound comprising an epoxy group and its synthesis intermediates
  • the field of the present invention is that of modifying agents intended to functionalize unsaturated polymers, that is to say polymers carrying 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 the synthesis of these compounds and their synthesis intermediates; as well as the use of such modifying agents.
  • the modification of the structure of a polymer is particularly sought after when it is desired to bring together a polymer and a reinforcing filler to form a composition.
  • This modification can make it possible to improve, for example, the dispersion of the reinforcing filler in a polymer matrix and thus make it possible to obtain a more homogeneous material and ultimately to improve the properties of the composition.
  • the modification of the structure of the polymers can in particular be carried out by means of functionalizing agents (or modifying agents), coupling or starring agents or postpolymerization in particular with the aim of obtaining a good interaction between the polymer thus modified and the reinforcing filler, whether it is carbon black or a reinforcing inorganic filler.
  • functionalizing agents or modifying agents
  • coupling or starring agents or postpolymerization in particular with the aim of obtaining a good interaction between the polymer thus modified and the reinforcing filler, whether it is carbon black or a reinforcing inorganic filler.
  • Many functionalizing agents have been proposed to improve this interaction.
  • document W02019/102128A1 discloses, as a functionalizing agent, an aromatic nitrile oxide compound comprising an epoxy ring, the epoxy ring being connected to the aromatic ring carrying the nitrile oxide function by a divalent group -OCH2- in meta position relative to the nitrile oxide function; the aromatic ring carrying the nitrile oxide function being moreover also substituted in the ortho-, meta- and para-position by a methyl.
  • This functionalizing agent 2,4,6-trimethyl-3-(oxiran-2-ylmethoxy)benzonitrile oxide, once grafted onto a copolymer of styrene and butadiene, makes it possible to improve the hysteresis of an elastomeric composition containing such a modified copolymer with respect to an elastomeric composition comprising an unmodified styrene and butadiene copolymer. Since fuel savings and the need to protect the environment have become a priority, it has proved necessary to produce tires having as low a rolling resistance as possible, that is to say comprising elastomeric compositions having as low a hysteresis as possible.
  • An object of the present invention is therefore to propose new polymer modifying agents which, once grafted to these polymers, make it possible to obtain elastomeric compositions having an improved performance, rolling resistance/stiffness compromise.
  • an aromatic nitrile oxide bearing an epoxy ring in the para- or meta-position with respect to the nitrile oxide function and not possessing a substituent in the ortho-position of this nitrile oxide function, once grafted onto a polymer comprising unsaturated carbon-carbon bonds, in particular an elastomer, made it possible to obtain elastomeric compositions exhibiting an improvement in the rolling resistance/stiffness compromise.
  • this new modifying agent also makes it possible to improve the reinforcing properties of these compositions.
  • a first object of the present invention relates to a compound of formula (I) below:
  • - 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 R1 or R2 is -OR3;
  • R3 represents a chemical group of formula (II) o in which E represents a divalent hydrocarbon group Cl -Cl 2 optionally comprising one or more heteroatoms; o Xi, X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; o the symbol * represents the attachment of the group of formula (II) to the oxygen atom.
  • the T group is —CHO.
  • the T group is —CN + —O′.
  • 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.
  • Xi, X2, X3, identical or different are chosen from the group consisting of the hydrogen atom, C1-C6 alkyls and phenyl.
  • Xi, X2, X3, which are identical, are a hydrogen atom.
  • a preferred compound of formula (I) is a compound of formula (la) 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 R1 or R2 is -OR3;
  • R3 represents a chemical group of formula (II) o in which E represents a divalent hydrocarbon group Cl -Cl 2 optionally comprising one or more heteroatoms; o Xi, X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; o the symbol * represents the attachment of the group of formula (II) to the oxygen atom.
  • Another object of the present invention relates to a process for the preparation of 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 solvent organic SL1 according to the reaction scheme: 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 -OR 3 ;
  • - R3 represents a chemical group of formula (II) o in which E represents a divalent hydrocarbon group Cl -Cl 2 optionally comprising one or more heteroatoms; o Xi, X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; o the symbol * represents the attachment of the group of formula (II) to the oxygen atom.
  • 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.
  • the organic solvent SL1 is chosen from chlorinated solvents and solvents of the ester, ether and alcohol type.
  • the process further comprises a step of reacting a compound of formula (Ic) with hydroxylamine according to the following reaction scheme: with Ri and R2 as defined above.
  • the hydroxylamine is brought into contact with the compound of formula (Ic) in the form of a hydroxylamine salt in the presence of a base.
  • the method 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.
  • the phase transfer agent is from phosphonium salts, ammonium salts and mixtures thereof.
  • a first object of the present invention relates to a compound of formula (I) below: 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 R1 or R2 is -OR3;
  • R3 represents a chemical group of formula (II) X X 2
  • E represents a divalent Cl-Cl 2 hydrocarbon group optionally comprising one or more heteroatoms
  • Xi, X2, X3, identical or different represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl
  • * represents the attachment of the group of formula (II) to the oxygen atom.
  • any interval of values designated by the expression “between a and b” represents the range of values going from more than a to less than b (i.e. limits a and b excluded) while any interval of values denoted by the expression “from a to b” means the range of values going from a to b (that is to say including the strict limits a and b).
  • the compounds mentioned in the description can be of fossil origin or biosourced. In the latter case, they can 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 used, that is to say can be, partially or totally, from a recycling process, or even obtained from raw materials themselves from a recycling process. This concerns in particular polymers, plasticizers, fillers, etc.
  • composition based on means a composition comprising the mixture and/or the in situ reaction product of the various constituents used, some of these constituents being able to react and/or being intended to react with each other, less partially, during the various phases of manufacture of the composition; the composition thus possibly being in the totally or partially crosslinked state or in the non-crosslinked state.
  • part by weight per hundred parts by weight of elastomer (or phr), is meant within the meaning of the present invention, the part, by mass per hundred parts by mass of elastomer.
  • 1,3-dipolar compound is understood according to the definition given by IUPAC.
  • a 1,3-dipolar compound includes a dipole.
  • T is CN + -O'
  • the dipole is a nitrile oxide.
  • hydrocarbon chain means a chain comprising one or more carbon atoms and one or more hydrogen atoms.
  • Ci-Cj alkyl denotes a linear, branched or cyclic hydrocarbon group comprising from i to j carbon atoms; i and j being integers.
  • Ci-Cj aryl denotes an aromatic group comprising from i to j carbon atoms; i and j being integers.
  • 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.
  • the compounds of formula (Ia) are particularly preferred because they are polymer modifying agents: 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 R1 or R2 is -OR3;
  • R3 represents a chemical group of formula (II) o in which E represents a divalent hydrocarbon group Cl -Cl 2 optionally comprising one or more heteroatoms; o Xi, X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; o the symbol * represents the attachment of the group of formula (II) to the oxygen atom.
  • the more particularly preferred compounds are those of formula (IaI): in which :
  • - Ri represents a chemical group chosen from the group consisting of -OCH3 and -OCH2CH3; more preferably Ri represents -OCH3;
  • Xi, X2, X3, identical or different represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl.
  • the compounds of formula (Ib) are particularly preferred because they are synthesis intermediates for the compounds of formula (Ia): 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 R1 or R2 is -OR3;
  • R3 represents a chemical group of formula (II) o in which E represents a divalent hydrocarbon group Cl -Cl 2 optionally comprising one or more heteroatoms; o Xi, X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; o the symbol * represents the attachment of the group of formula (II) to the oxygen atom.
  • the more particularly preferred compounds are those of formula (Ib 1) in which :
  • - Ri represents a chemical group chosen from the group consisting of -OCH3 and -OCH2CH3; more preferably Ri represents -OCH3;
  • Xi, X2, X3, identical or different represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl.
  • the compounds of formula (Ie) are particularly preferred because they are synthesis intermediates for the compounds of formula (Ib): 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 -OR.3; provided that R1 or R2 is -OR3;
  • R3 represents a chemical group of formula (II) o in which E represents a divalent hydrocarbon group Cl -Cl 2 optionally comprising one or more heteroatoms; o Xi, X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; o the symbol * represents the attachment of the group of formula (II) to the oxygen atom.
  • the more particularly preferred compounds are those of formula (Ic) 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 hydrocarbon group Cl -Cl 2 optionally comprising one or more heteroatoms;
  • X1, X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl.
  • a particularly preferred group of compounds of formula (I) are those for which R represents a chemical group chosen from the group consisting of —OCH3 and —OCH2CH3; and R2 is -OR3.
  • this group of compounds is that corresponding to the set formed by the compounds of preferred formula (Ial), (Ibl) and (Ici).
  • the condition "R1 or R2 is -OR3" means that if R1 is -OCH3 or -OCH2CH3 then R2 is -OR3; or if R1 is -OR3 then R2 is -OCH3.
  • R1 is -OR3 then R2 is -OCH3.
  • E represents a divalent hydrocarbon-based Cl -Cl 2 group which may optionally contain one or more heteroatom(s).
  • divalent hydrocarbon group is meant within the meaning of the present invention, a spacer group (or a linking group) forming a bridge between the oxygen atom attached to the aromatic ring and the epoxy ring carrying the groups Xi, X2, X3; this spacer group E comprising from 1 to 12 carbon atoms, and possibly containing one or more heteroatom(s) such as for example N, O and S.
  • This spacer group can be a Cl -Cl 2 hydrocarbon chain , preferably saturated, linear or branched, which may optionally contain one or more heteroatom(s) such as, for example, N, O and S. Said 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.
  • E represents a divalent hydrocarbon group in Cl-CIO, preferably in C1 -C9, possibly containing one or more heteroatom(s) such as for example N, O and S.
  • E represents a Cl -Cl 2 alkanediyl, preferably an alkanediyl C1-CIO, more preferably a C1-C9 alkanediyl. Even more preferentially, E is chosen from the group consisting of methanediyl, ethanediyl and propanediyl.
  • Xi, X2, X3, which are identical or different, are chosen from the group consisting of the hydrogen atom, C1-C6 alkyls and C6-C14 aryls.
  • Xi, X2, X3, which are identical or different, are chosen from the group consisting of the hydrogen atom, C1-C6 alkyls and phenyl.
  • Xi, X2, X3, which are identical or different, are chosen from the group consisting of the hydrogen atom, C1-C3 alkyls and phenyl.
  • Xi, X2, X3, identical represent a hydrogen atom.
  • Xi and X2 represent a hydrogen atom and X3 represents a phenyl.
  • X3 is a hydrogen atom
  • Xi and X2, identical or different, represent a hydrogen atom or a methyl
  • the compounds of formula (Ia) are particularly preferred 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 R1 or R2 is -OR3;
  • R3 represents a chemical group of formula (II) o in which E represents a divalent hydrocarbon group Cl -Cl 2 optionally comprising one or more heteroatoms; preferably a C1-C12 alkanediyl, preferably a C1-C10 alkanediyl, more preferably a C1-C9 alkanediyl; o Xi, X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; o the symbol * represents the attachment of the group of formula (II) to the oxygen atom; 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 Xi, X2, X3, which are identical or different, are chosen from the group consisting of the hydrogen atom, C1-C
  • the improvement in these properties does not occur to the detriment of the rolling resistance/stiffness compromise. This compromise is even advantageously improved.
  • R represents a chemical group chosen from the group consisting of —OCH3 and —OCH2CH3
  • E represents a C1-C12 alkanediyl, preferably a C1-C10 alkanediyl, more preferably a C1-C9 alkanediyl
  • Xi, X2, X3, identical or different are chosen from the group consisting of the hydrogen atom, C1-C3 alkyls and phenyl, more preferably X1, X2, X3, which are identical, are a hydrogen atom.
  • the compounds of formula (Ial) which are more particularly preferred are those in which R represents —OCH3; E represents a Cl -Cl 2 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 atom of hydrogen, C1-C3 alkyls and phenyl, more preferably an X1, X2, X3, which are identical, are a hydrogen atom.
  • the compounds of formula (Ial) which are more particularly preferred are those in which R1 represents —OCH3; E represents a C1-C9 alkanediyl and Xi, X2, X3, which are identical, are a hydrogen atom. Even more preferentially, the compounds of formula (Ial) which are more particularly preferred are those in which R represents —OCH3, E represents is chosen from the group consisting of methanediyl, ethanediyl and propanediyl; and X1, X2, X3 are the same and are hydrogen.
  • the compounds of formula (Ia1) the one which is more particularly preferred is that of formula (Ia2):
  • Another object of the present invention relates to a process for the preparation of 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 solvent organic SL1 according to the following reaction scheme: 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 -OR 3 ; provided that R1 or R2 is -OR3;
  • R3 represents a chemical group of formula (II) o in which E represents a divalent hydrocarbon group Cl -Cl 2 optionally comprising one or more heteroatoms; o Xi, X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; o the symbol * represents the attachment of the group of formula (II) to the oxygen atom.
  • the process for preparing a compound of formula (Ial) 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 reaction scheme following : with E, Xi, 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.
  • 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.
  • the oxidizing agent is chosen from the group consisting of sodium hypochlorite and N-bromosuccinimide in the presence or absence of a base.
  • the base can be triethylamine. More preferably still, the oxidizing agent is sodium hypochlorite.
  • 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).
  • the organic solvent SL1 is chosen from chlorinated solvents and solvents of the ester, ether and alcohol type, 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.
  • 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, relative 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.
  • the process of the invention comprises, after reaction (d), (preferably after reaction (dl)), a step for recovering the compound of formula (la) (preferably the compound of formula (lal)).
  • 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 (Ic) with hydroxylamine NH2OH according to the following reaction scheme: 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 -OR 3 ; provided that R1 or R2 is -OR3;
  • R3 represents a chemical group of formula (II) o in which E represents a divalent hydrocarbon group Cl -Cl 2 optionally comprising one or more heteroatoms; o Xi, X2, X3, identical or different, represent a hydrogen atom, a C1-C6 alkyl or a C6-C14 aryl; o the symbol * represents the attachment of the group of formula (II) to the oxygen atom.
  • the compound of formula (Ibl) can be obtained in particular from a preparation process comprising at least one reaction (cl) of a compound of formula (Ici) with 1 hydroxylamine NH2OH according to the following reaction scheme: with E, X1, X2 and X3 as described above, including their preferred modes and R1 represents a chemical group chosen from the group consisting of -OCH3 and -OCH2CH3, preferably R1 is -OCH3.
  • 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.
  • the hydroxylamine is added either in solution in water or in the form of a salt.
  • the hydroxylamine may be selected from the group consisting of hydroxylamine sulphate, hydroxylamine chloride and mixtures thereof.
  • a base can preferably be added to the reaction medium.
  • a base mention may be made of sodium acetate or triethylamine.
  • the amount of base added may be within a range ranging from 1 to 2 molar equivalents relative to the hydroxylamine generated, preferably from 1 to 1.2 molar equivalents relative to the hydroxylamine generated.
  • generated hydroxylamine is meant the cation (NH3 + OH) of the hydroxylamine salt which is released when said salt is brought into contact with water.
  • a base When a base is used, said base is mixed with the hydroxylamine salt, then the whole is dissolved in water.
  • the hydroxylamine is brought into contact with the compound of formula (Ic) in the form of a hydroxylamine salt in the presence of a base, such as sodium acetate or triethylamine.
  • the process of the invention may comprise, after reaction (c), (preferably after reaction (cl)), a step for recovering the product of formula (Ib) (preferably the product of formula (Ib 1) ).
  • 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.
  • 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 transfer agent phase and at a temperature ranging from 10° C. to 120° C., preferably from 20° C.
  • nucleofuge group means a leaving group.
  • the group Z can be selected from chlorine, bromine, iodine, fluorine, the mesylate group, the tosylate group, the acetate group, and the trifluoromethylsulfonate group.
  • Z is bromine or chlorine.
  • phase transfer agent can be chosen from phosphonium salts, ammonium salts and mixtures thereof.
  • phase transfer agent is tetrabutylammonium bromide.
  • the molar quantity of phase transfer agent is from 0.01 to 1 molar equivalent, preferably from 0.05 to 0.5 molar equivalents, relative to the molar quantity of compound of formula (III).
  • the process of the invention may comprise, after reaction (b), (preferably after reaction (bl)), a step for recovering the product of formula (Ic) (preferably the product of formula (Ic)).
  • 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.
  • 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.
  • this epoxidation can be carried out in the presence of peracid such as metachloroperbenzoic acid, peracetic acid, performic acid.
  • Another well-known technique is the use of dimethyldioxirane.
  • the compounds of formula (V) are commercially available from suppliers such as Sigma Aldrich, ABCR.
  • the compounds of formula (Ia) and its preferred embodiments, in particular the compounds of formula (Ia1), more particularly still the compound of formula (Ia2), are used as polymer modifying agent. They can be grafted onto one or more polymers comprising at least one unsaturated carbon-carbon bond, in particular this polymer can be an elastomer and more particularly a diene elastomer.
  • the compounds of the invention advantageously make it possible to obtain graft polymers (also called modified polymers), in particular grafted diene elastomers in particular, whatever the initial microstructure of the polymer, the only condition being that the polymer comprises at least one bond unsaturated carbon-carbon, preferably a carbon-carbon double bond.
  • the grafting of the polymer comprising at least one unsaturated carbon-carbon bond can be done by reacting the initial polymer with the compound of formula (Ia) and its preferred embodiments, in particular the compounds of formula (IaI), more particularly still 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 on an unsaturated carbon-carbon bond of the polymer chain.
  • the mechanism of this cycloaddition is illustrated in particular in document WO2012/007441.
  • the grafting of the compound of formula (Ia) and its preferred embodiments, in particular the compounds of formula (Ia1), more particularly still 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 discontinuously.
  • 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.
  • the compounds of formula (Ia) and its preferred embodiments, in particular the compounds of formula (Ia1), more particularly still the compound of formula (Ia2) can be integrated into elastomeric compositions. These elastomeric compositions can 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), more particularly still the compound of formula (Ia2) on the diene elastomer can be carried out prior to the introduction said elastomer in the composition or can be grafted by reaction with said compound of formula (Ia) during the manufacture of the composition.
  • the elastomeric composition may further comprise an additive.
  • the additives that can be used can be plasticizers (such as plasticizing oils and/or plasticizing resins), non-reinforcing fillers, pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, antioxidants, anti-fatigue agents, reinforcing resins (as described for example in application WO 02/10269). These elastomeric compositions can be used for the manufacture of semi-finished tires or for the manufacture of tires.
  • SEC Size Exclusion Chromatography
  • the apparatus used is a “WATERS alliance” chromatograph.
  • the eluting solvent is the following mixture: tetrahydrofuran+1% vol. of 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 35°C and the analysis time 90 min.
  • 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 average molar masses calculated relate to a calibration curve produced from “PSS READY CAL-KIT” commercial polystyrene standards.
  • the structural analysis as well as the determination of the molar purities of the synthetic molecules are carried out by an NMR analysis.
  • the spectra are acquired on an “Avance 3400 MHz BRUKER” spectrometer equipped with a “broad band BBFO-zgrad 5 mm” probe.
  • the quantitative 1 H NMR experiment uses a single 30° pulse sequence and a repetition delay of 3 seconds between each of the 64 acquisitions.
  • the samples are solubilized in a deuterated solvent, deuterated dimethyl sulfoxide (DMSO) unless otherwise indicated.
  • DMSO deuterated dimethyl sulfoxide
  • the deuterated solvent is also used for the "lock" signal.
  • the calibration is carried out on the proton signal of deuterated DMSO at 2.44 ppm compared to a TMS reference at 0 ppm.
  • the 'H NMR spectrum coupled with the 2D HSQC ⁇ C and HMBC ⁇ C experiments allow the structural determination of the molecules (cf. attribution tables).
  • the molar quantifications are carried out from the quantitative 1D 'H NMR spectrum.
  • the analysis by mass spectrometry is carried out by direct injection by an electrospray ionization mode (ID/ESI). The analyzes were carried out on a Bruker HCT spectrometer (flow rate 600 pL/min, nebulizer gas pressure 10 psi, nebulizer gas flow rate 4 L/min).
  • the determination of the molar content of the compounds grafted onto the diene elastomers is carried out by an NMR analysis.
  • the spectra are acquired on a “500 MHz BRUKER” spectrometer equipped with a “CryoProbe BBFO-zgrad-5 mm”.
  • the quantitative 'H NMR experiment uses a simple 30° pulse sequence and a repetition delay of 5 seconds between each acquisition.
  • the samples are solubilized in deuterated chloroform (CDCh) in order to obtain a “lock” signal.
  • 2D NMR experiments made it possible to verify the nature of the grafted motif thanks to the chemical shifts of the carbon and proton atoms.
  • the dynamic properties G* and tan( ⁇ )max are measured on a viscoanalyzer (Metravib VA4000), according to standard ASTM D5992-96.
  • the response of a sample of vulcanized composition (cylindrical specimen 4 mm thick and 400 mm 2 in section) subjected to a sinusoidal stress in simple alternating shear, at a frequency of 10 Hz, at a temperature of 60°C.
  • a deformation amplitude sweep is performed from 0.1% to 100% peak-peak (outward cycle) then from 100% to 0.1% peak-peak (return cycle).
  • the results used are the complex dynamic shear modulus G* at 50% strain (G* 50% return), the dynamic loss factor tan( ⁇ ) at 60°C.
  • G* 50% return the value of the complex dynamic shear modulus G* at 50% deformation is recorded, note G*50% return to 60°C and the maximum value of the dynamic loss factor tan(ô) observed, noted tan( ⁇ )max at 60°C-
  • the value in base 100 for the sample to be tested is calculated according to the operation: (value of tan(ô) max at ⁇ O°C of the sample to be tested/value of tan( ⁇ ) ma x at ⁇ 0°C of the control) x 100.
  • a result below 100 indicates a decrease in hysteresis which corresponds to an improvement in rolling resistance performance.
  • the MSA300/MSA100 ratio is the reinforcement index.
  • the value in base 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.
  • Tetrabutylammonium bromide (4.24g; 13.15 mmol or 0.1 eq.).
  • the reaction medium is then stirred for 60-70 minutes at a temperature of 90° C.
  • the reaction mixture is diluted with ethyl acetate (150 ml ), washed with brine (3 x 75 ml) and finally with distilled water (75 ml).
  • T bath 50° C; 13 mbar
  • the oil obtained is triturated with ice-cold isopropyl alcohol (i-PrOH) (50 ml) allowing rapid crystallization.
  • the precipitate is filtered and washed with ice-cold T i-PrOH (3 ⁇ 35 ml); then air-dried.
  • a white solid (23.16 g; 111 mmol) is obtained with a yield of 85%.
  • the molar purity is greater than 90% ( 1 H-NMR).
  • Petroleum ether 120 ml is added to the residue and the suspension is kept under stirring at -18° C. for 2 hours.
  • the precipitate is filtered and washed on the filter with petroleum ether (40/60) (3 times 25 ml) and finally dried for 10-15 hours under atmospheric pressure at room temperature.
  • a white solid 40.04 g; 75% mass yield
  • the molar purity is greater than 99% ( 1 H NMR).
  • the mixture is homogenized fifteen times on this tool, then shaped into plates before undergoing a heat treatment at 100°C for 10 min under a press at 10 bars. depression.
  • X H NMR analysis made it possible to determine a molar degree of grafting of 0.150 mol% with a molar grafting yield of 50%.
  • composition C3 elastomeric composition comprising natural rubber modified with the compound of the invention
  • composition T1 a control elastomeric composition
  • composition C2 and C2 two elastomeric compositions comparative
  • the elastomeric compositions T1, C1 to C3 are prepared in the following manner: an 85 cm 3 "Polylab" internal mixer, filled to 70% and whose initial tank temperature is approximately 100° C., is introduced into the rubber natural rubber modified with compound B or modified with compound C or modified with compound A or unmodified natural rubber. Then, for each of the elastomeric compositions, the reinforcing filler(s), the filler coupling agent with the diene elastomer are introduced, then after one to two minutes of mixing, the various other ingredients with the exception of the vulcanization. Thermomechanical work is then carried out (non-productive phase) in one step, which lasts a total of around 5 to 6 minutes, until a maximum drop temperature of 160°C is reached.
  • the mixture thus obtained is recovered, cooled and then the vulcanization system (sulfur and the sulfenamide-type accelerator) is added to an external mixer (homo-finisher) at 25° C., while mixing the whole (productive phase) for about 5 to 6 minutes.
  • vulcanization system sulfur and the sulfenamide-type accelerator
  • the elastomeric compositions thus obtained are then calendered in the form of plates (thickness of 2 to 3 mm) for the measurement of their physical or mechanical properties.
  • the rubber properties of these compositions are measured after curing at 150° C. for 30 minutes. The results obtained are shown in Table 8.
  • the elastomeric composition of the invention C3 simultaneously exhibits, compared to the control elastomeric compositions T1 and comparative C1 and C2, a significant improvement in the reinforcement index (MA300/M100) and an improvement in the rolling resistance/stiffness performance compromise. (decrease in tan( ⁇ ) ma x at 6o c° and increase in G* 50% back to 60°c).
  • composition C6 a synthetic polyisoprene modified with the compound of the invention
  • composition T2 a control elastomeric composition
  • composition C4 and C5 two compositions comparative elastomers
  • the elastomeric compositions T2, C4 to C6 are prepared according to the process described above for the elastomeric compositions T1, C1 to C3.
  • the elastomeric composition of the invention C6 simultaneously exhibits, compared to the control T2 and comparative elastomeric compositions C4 and C5, a significant improvement in the reinforcement index (MA300/M100) and an improvement in the rolling resistance/stiffness performance compromise ( decrease in tan(ô) ma x at ⁇ O c° and increase in G* 50% back to 60°c).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Compounds (AREA)
EP22840600.5A 2021-12-23 2022-12-19 Composé 1,3-dipolaire comprenant un groupe époxy et ses intermédiaires de synthèse Pending EP4452957A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR2114414A FR3131308B1 (fr) 2021-12-23 2021-12-23 Composé 1,3-dipolaire comprenant un groupe époxy et ses intermédiaires de synthèse.
PCT/EP2022/086556 WO2023117844A1 (fr) 2021-12-23 2022-12-19 Composé 1,3-dipolaire comprenant un groupe époxy et ses intermédiaires de synthèse

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EP1311600A2 (fr) 2000-07-31 2003-05-21 Société de Technologie Michelin Bande de roulement pour pneumatique
FR2962733B1 (fr) 2010-07-13 2012-08-17 Michelin Soc Tech Polymere greffe par des molecules associatives azotees.
JP5558264B2 (ja) 2010-08-19 2014-07-23 豊田合成株式会社 架橋可能なゴム材料及び架橋ゴム材料の製造方法
EP3713924B1 (fr) 2017-11-21 2023-01-04 Compagnie Générale des Etablissements Michelin Composé 1,3-dipolaire comportant un groupe époxyde

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