• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a compound of formula (I) below: in which: PAr denotes a polyaromatic group comprising at least two fused aromatic hydrocarbon rings, each of said fused aromatic rings being optionally substituted with one or more carbon chains, which are identical or different, aliphatic or aromatic, linear, branched or cyclic, optionally substituted or interrupted by one or more heteroatoms; - Sp represents an atom or a group of atoms.
    公开号:FR3068694A1
    申请号:FR1756300
    申请日:2017-07-04
    公开日:2019-01-11
    发明作者:Anne-Frederique SALIT；Etienne Fleury；Sergey Ivanov；Francois Jean-Baptiste-Dit-Dominique；Oleg Ugolnikov
    申请人:Compagnie Generale des Etablissements Michelin SCA；Arkema France SA；
    IPC主号:
    专利说明:

    Polyaromatic molecule carrying a nitrile oxide function
    The present invention relates to the field of nitrogenous associative molecules comprising at least one motif making them capable of associating with each other or with a charge by non-covalent bonds, and comprising a function capable of reacting with a polymer comprising unsaturations to form a covalent bond with said polymer.
    More specifically, the present invention relates to molecules carrying a nitrile oxide function and an imidazolidinone function. The application also relates to a process for the synthesis of such molecules.
    In the industrial field, mixtures of polymers with fillers are often used. In order for such mixtures to have good properties, means are constantly being sought to improve the dispersion of the charges within the polymers. One of the means to achieve this result is the use of coupling agents capable of establishing interactions between the polymer and the filler.
    Coupling agents of a polymer with a filler comprising nitrogenous dipoles are described in the documents published under the numbers US7186845B2 and JP2008208163.
    These documents describe the modification of polymers comprising diene units with nitrogenous dipolar compounds further comprising a heterocycle, said heterocycle comprising itself a nitrogen atom, and an oxygen and / or sulfur atom.
    More particularly, the compounds described are nitrones carrying the oxazoline, thiazoline function, such as for example ((2oxazolyl) -phenyl-N-methylnitrone):
    When diene polymers are reacted with such compounds, the resulting polymers will carry the oxazoline or thiazoline rings.
    These cycles present on the polymer are capable of reacting in their turn, with surface functions of the fillers, such as carbon black or silica, with which the polymers are mixed. This reaction leads to the establishment of covalent bonds between the polymer modified by the coupling agent and the charge due to the opening of the oxazoline or thiazoline ring. Indeed, as described in document US7186845B2, the oxazoline and / or thioazoline rings are capable of opening in the presence of a nucleophile which may for example be present on the surface of the charge.
    The establishment of such covalent bonds nevertheless has drawbacks when preparing mixtures comprising these polymers modified by coupling agents with fillers. In particular, the existence of these precociously established covalent bonds, between the polymer and the fillers, makes these mixtures very viscous in the non-crosslinked state, which makes all the operations prior to crosslinking (vulcanization) of the base formulations difficult of rubber, in particular the preparation of mixtures of the components, and their shaping. These drawbacks have a strong impact on industrial productivity.
    It is therefore desirable to propose new molecules which do not have the above drawbacks, that is to say molecules which are capable, after reaction with a polymer and mixture with a filler, of not forming covalent bonds with the load and therefore not to cause an excessive increase in the viscosity of the mixture.
    Thus, patent application WO 2012/007684 relates to a compound comprising at least one group Q, and at least one group A linked together by at least and preferably a spacer group Sp in which:
    - Q comprises a dipole containing at least and preferably a nitrogen atom;
    - A comprises an associative group comprising at least one nitrogen atom;
    - Sp is an atom or a group of atoms forming a bond between Q and A.
    When a polymer grafted with a compound as defined above is mixed with fillers, the latter only establishes labile connections with the fillers, which makes it possible to ensure a good polymer-filler interaction, beneficial for the final properties. of the polymer, but without the disadvantages that too strong polymer charge interaction could cause.
    An example of such a compound is 2- (2- (2oxoimidazolidin-1 -yl) ethoxy] benzonitrile oxide:
    NH
    Furthermore, in application WO 2016/207263, various compounds are exemplified, including in particular 2,4,6trimethyl-3- [2- (2-oxoimidazolidin-1-yl) ethoxy] benzonitrile oxide:
    NH
    It turns out that the rubber compositions, which can be used in particular for the manufacture of tires, comprising this molecule have advantageous properties in terms of rigidity, tensile strength or even hysteresis. However, there is still a constant need for rubber compositions with improved properties.
    In this context, the Applicant has discovered that a particular polyaromatic compound, once integrated into rubber compositions, which can be used in particular for the manufacture of tires, leads to obtaining excellent properties of rigidity, tensile strength and hysteresis.
    The subject of the invention is therefore a compound of the following formula (I):
    +
    Sp — N NH in which:
    PAr denotes a polyaromatic group comprising at least two condensed aromatic hydrocarbon rings, each of said condensed aromatic cycles being optionally substituted by one or more carbon chains, identical or different, independent of each other, aliphatic or aromatic, linear, branched or cyclic, optionally substituted or interrupted by one or more heteroatoms;
    Sp represents an atom or a group of atoms.
    Another subject of the invention is a process for the synthesis of the compound of formula (I) according to the invention.
    For the purposes of the present invention, the term “carbon chain” means a chain comprising one or more carbon atoms.
    In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by mass. On the other hand, any range 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 range of values designated by the expression from a to b signifies the range of values going from a to b (that is to say including the strict limits a and b).
    The invention and its advantages will be easily understood in the light of the description and examples of embodiments which follow.
    The compounds mentioned in the description can be of fossil origin or bio-based. In the latter case, they can be, partially or totally, from biomass or obtained from renewable raw materials from biomass.
    In accordance with formula (I), the compound according to the invention comprises a group PAr denoting a polyaromatic group comprising at least two condensed aromatic hydrocarbon rings.
    For the purposes of the present invention, the term "aromatic hydrocarbon cycle" means an aromatic cycle the skeleton of which is made up of carbon atoms. In other words, there is no heteroatom in the skeleton of the cycle.
    For the purposes of the present invention, the term “at least two condensed aromatic hydrocarbon rings” is understood to mean two or more aromatic hydrocarbon rings having at least two successive carbon atoms.
    Said at least two condensed aromatic hydrocarbon rings can be ortho-condensed or ortho- and peri-condensed.
    Advantageously, the polyaromatic group comprising at least two condensed aromatic hydrocarbon rings is chosen from a group formed by two aromatic rings condensed according to a rectilinear arrangement and a group formed by three aromatic rings condensed according to a rectilinear arrangement, preferably a group formed by two rings aromatic condensed in a straight arrangement. These structures are similar to the compounds of naphthalene and anthracene.
    In accordance with formula (I), the polyaromatic group comprising at least two condensed aromatic hydrocarbon rings is at least substituted by the nitrile oxide function and the group Sp. In other words, the first cycle of said at least two aromatic hydrocarbon rings is at least substituted by the nitrile oxide function, said first cycle or the second cycle of said at least two aromatic hydrocarbon rings being at least substituted by the group Sp, said group Sp making it possible to link the imidazolidinone function to at least one of said at least two aromatic hydrocarbon cycles.
    Advantageously, each of the condensed aromatic hydrocarbon cycles is optionally substituted by one or more carbon chains, identical or different, aliphatic or aromatic, linear, branched or cyclic, optionally substituted or interrupted by one or more heteroatoms, and inert with respect to one or other of the functions that are the imidazolidinone function and the nitrile oxide function.
    For the purposes of the present invention, the expression “carbon chain inert with respect to one or other of the functions that are the imidazolidinone function and the nitrile oxide function” is understood to mean a carbon chain which does not react with either of these functions. Thus, said carbon chain inert with respect to one or other of these functions is for example a carbon chain which does not have alkenyl or alkynyl functions, capable of reacting with the nitrile oxide function.
    Preferably, said carbon chains are saturated.
    Preferably, each of the condensed aromatic hydrocarbon rings is optionally substituted by one or more carbon chains, identical or different, saturated, more preferably one or more alkyl groups, identical or different, preferably one or more alkyl groups, identical or different, in C1 -C12, more preferably C1-C6, even more preferably C1-C4, or a group chosen from -OR ', -NHR', SR ', R' being an alkyl group, preferentially a C1-C12 alkyl group, more preferentially in Ci-Cô, even more preferentially in C1-C4.
    Even more preferably, each of the condensed aromatic rings is optionally substituted by one or more groups, identical or different, methyl, ethyl or one or more och 3 groups.
    The group Sp is preferably a linear, branched or cyclic C1-C24 hydrocarbon chain, which may contain one or more aromatic radicals, and / or one or more heteroatoms. Said chain can optionally be substituted, provided that the substituents do not react with one or other of the functions which are the imidazolidinone function and the nitrile oxide function.
    For the purposes of the present invention, the term “hydrocarbon chain” means a chain comprising one or more carbon atoms and one or more hydrogen atoms.
    For the purposes of the present invention, the term “hydrocarbon chain which may contain one or more heteroatoms” means the fact that the chain may be substituted or interrupted by one or more heteroatoms. When the chain is interrupted by a heteroatom, this can be at the end of the chain or in the middle of the chain.
    Advantageously, the group Sp is a linear or branched C1-C24, preferably C1-C10, more preferably C1-C10 alkylene chain, optionally interrupted by one or more nitrogen, sulfur or oxygen atoms.
    Preferably, the group Sp contains a motif chosen from (CH 2 ) y i-, - [NH- (CH 2 ) y2 ] xi- and - [O- (CH 2 ) y3 ] x2 -, [-S- ( CH 2 ) y2 ] xb y b y 2 and y 3 representing, independently of each other, an integer ranging from 1 to 6, and x 3 and x 2 representing, independently of one another, an integer ranging from 1 to 4.
    Preferably, the compound of formula (I) according to the invention has the following formula (II):
    sp
    in which :
    - a grouping chosen formula (III) below:
    among denotes the group of different, an aromatic atom, substituted or (III), in which Sp is as defined above, the other six groups, identical or representing, independently of one another, hydrogen or a carbon chain, aliphatic or linear, branched or cyclic, possibly interrupted by one or more heteroatoms.
    Advantageously, said carbon chain is inert with respect to one or other of the functions that are the imidazolidinone function and the nitrile oxide function.
    Preferably, said carbon chain is saturated.
    Said carbon chain can be a C1-C12 alkyl group, more preferentially C1-C6, even more preferentially C1-C4, or a group chosen from -OR ', -NHR', -SR ', R' being a group alkyl, preferably a C1-C12 alkyl group, more preferably a C1-C6 group, even more preferably a C1-C4 group.
    Preferably, R 1 or R 7 denotes the group of formula (III).
    According to a particular embodiment, Ri denotes the group of formula (III) and R2 to R7 represent a hydrogen atom.
    According to another particular embodiment, R 7 denotes the group of formula (III) and Ri to Re represent a hydrogen atom.
    Preferably, the group Sp denotes the group -O-CH 2 -CH 2 -.
    According to a particular embodiment, the compound of formula (I) according to the invention is chosen from a compound of formula (IV) below:
    (IV), and a compound of the following formula (V):
    (V), preferably the compound of formula (IV).
    The subject of the invention is also a process for the synthesis of the compound of formula (I) according to the invention, comprising the following successive stages:
    (bl) the reaction of a compound of the following formula (VI):
    % - PAr - Y (VI), in which PAr is as defined above represents a nucleophilic group, with a compound of formula (VII) below:
    and Y
    in which Sp is such represents a nucleofuge group;
    in the presence of at least one as defined above, and Z polar solvent Si, of at least one base, at a temperature Ti ranging from 70 to 150 ° C, to form a compound of formula (VIII) below:
    (VIII);
    (b2) reacting said compound of formula (VIII) with an aqueous solution of hydroxylamine at a temperature T 2 ranging from 30 to 70 ° C, to obtain an oxime compound of formula (IX) below:
    ^ PAr A
    N Sp — N NH
    OH _ ^ (IX);
    (c) a step of recovering said oxime compound of formula
    (d) a step of oxidizing the oxime compound of formula (IX) with an oxidizing agent, in the presence of at least one organic solvent
    For the purposes of the present invention, the term “polar solvent” means a solvent having a dielectric constant greater than
    For the purposes of the present invention, the term “nucleofuge group” means a leaving group which carries its bond doublet.
    For the purposes of the present invention, the term "nucleophilic group" means a compound comprising at least one atom carrying a free doublet or a negatively charged atom.
    As explained above, the process for synthesizing the compound of formula (I) according to the invention notably comprises the successive steps (b1) and (b2).
    According to a particular embodiment, the two steps (b1) and (b2) are separated by a step of isolation and purification of the compound of formula (VIII).
    According to another embodiment, the two stages (bl) and (b2) are carried out according to a monotope synthesis, that is to say that the stages (bl) and (b2) are “one pot” (synthesis process monotope in two stages), or without isolation of the intermediate compound of formula (VIII).
    The method according to the invention comprises a step (b1) of reacting a compound of formula (VI), as mentioned above, carrying a group Y, with a compound of formula (VII), as mentioned above above, carrying a group Z.
    Preferably, the group Y is chosen from the hydroxyl, thiol and primary or secondary amine functions.
    The group Z can be chosen from chlorine, bromine, iodine, the mesylate group, the tosylate group, the acetate group and the trifluoromethylsulfonate group.
    Said step (b1) of the method according to the invention is carried out in the presence of at least one polar solvent Si, and at least one base, at a temperature Ti ranging from 70 to 150 ° C.
    According to a particular embodiment of the invention, the polar solvent Si is a polar solvent miscible in water, preferably a protic solvent.
    Dimethylformamide (DMF), dimethylsulfoxide (DMSO), 1,3-dimethyl-2-imidazolidinone (DMI), 1,3-dimethyl-3,4,5,6tetrahydro-2 (1H) -pyrimidinone (DMPU) , isopropanol, acetonitrile, ethanol, n-butanol and n-propanol are examples of Si solvents which can be used in the process according to the invention.
    Preferably, the protic solvent is alcoholic.
    Advantageously, the compound of formula (VI) represents from 5 to 40% by weight, preferably from 10 to 30% by weight, relative to the weight of the solvent.
    The base can be chosen from alkali alcoholates, alkali carbonates, alkaline earth carbonates, alkali hydroxides, alkaline earth hydroxides and mixtures thereof.
    Advantageously, it is possible to add:
    - one or more catalysts chosen from a catalyst of the silver salt type (I), a phase transfer catalyst of the quaternary ammonium type, and their mixtures;
    - one or more ionic liquids.
    Preferably, the base is chosen from sodium methanolate, potassium carbonate and soda, more preferably potassium carbonate.
    According to a particular embodiment of the invention, the molar amount of base is 1.5 to 8 molar equivalents, preferably 2 to 6 molar equivalents, relative to the molar amount of compound of formula (VI).
    As explained above, step (b1) of the process according to the invention is carried out at a temperature Ti ranging from 70 to 150 ° C.
    Preferably, the temperature Ti is a temperature ranging from 70 to 120 ° C, more preferably from 80 to 110 ° C.
    As explained above, step (b1) of the process according to the invention is followed by step (b2) of adding to the reaction medium containing the compound of formula (VIII) an aqueous solution of hydroxylamine to a temperature T 2 ranging from 30 to 70 ° C.
    Preferably, the addition of the aqueous hydroxylamine solution is carried out when the conversion of the compound of formula (VI) is at least 70% by weight.
    Advantageously, the temperature T 2 varies from 40 to 60 ° C.
    The method according to the invention also comprises a step (c) of recovery, as mentioned above, of the oxime compound of formula (IX).
    Preferably, the oxime compound of formula (IX) is recovered by precipitation with water, optionally followed by washing with water.
    The method according to the invention also comprises a step (d) of oxidation of the oxime compound of formula (IX) with an oxidizing agent, in the presence of at least one organic solvent S 2 .
    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, preferably sodium hypochlorite.
    Advantageously, the amount of oxidizing agent is from 1 to 5 molar equivalents, preferably from 1 to 2 molar equivalents, relative to the molar amount of oxime compound of formula (IX).
    Preferably, the organic solvent S2 is an organic solvent chosen from chlorinated solvents and of the ester, ether and alcohol type, more preferably chosen from dichloromethane, ethyl acetate, butyl acetate, diethyl ether, l isopropanol and ethanol, even more preferably chosen from ethyl acetate and butyl acetate.
    Preferably, the oxime compound of formula (IX) represents from 1 to 30% by weight, preferably from 1 to 20% by weight, relative to the total weight of the assembly comprising said oxime compound of formula (IX), said organic solvent S2 and said oxidizing agent.
    Preferably, the method according to the invention comprises, after step (d), a step (e) of recovery of the compound of formula (I) ·
    According to a particular embodiment of the invention, the method according to the invention comprises a step (a2) for manufacturing the compound of formula (VII), prior to step (b1), by reacting a compound with the following formula (X):
    NH (X), in which Sp is as defined above, with an agent allowing the formation of the nucleofuge group Z. Preferably, said agent is thionyl chloride.
    Preferably, step (a2) is carried out in the absence or in the presence of at least one solvent S4, preferably a chlorinated solvent, more preferably dichloromethane.
    Advantageously, step (a2) is immediately followed by a step (a3) for recovering the compound of formula (VII), preferably by purification with toluene, more preferably by crystallization of the compound of formula (VII) in toluene.
    As explained above, the compound of formula (I) can be incorporated into rubber compositions which can be used in particular for the manufacture of tires. These rubber compositions can be based on at least one diene elastomer, a reinforcing filler and a chemical crosslinking agent.
    In the following text, the term “composition based on a composition comprising the mixture and / or the reaction product of the various constituents used” means, some of these basic constituents being capable of, or intended to react with each other, at least in part, during the various stages of manufacturing the composition, in particular during its crosslinking or vulcanization.
    By diene elastomer (or indistinctly rubber), whether natural or synthetic, must be understood in known manner an elastomer consisting at least in part (ie; a homopolymer or a copolymer) of diene monomer units (monomers carrying two double carbon-carbon bonds, conjugated or not).
    The compound of formula (I) can be used to graft one or more diene elastomers present (s) in the rubber composition. The diene elastomer can be grafted with the compound of formula (I) prior to its introduction into the rubber composition, or else can be grafted by reaction with the compound of formula (I) during the manufacture of the composition.
    The rubber composition which can be included in the tire can therefore contain a single diene elastomer grafted with the compound of formula (I) (either grafted prior to its introduction into the composition, or grafted by reaction with the compound of formula (I) during the manufacture of the composition), or a mixture of several diene elastomers all grafted, or some of which are grafted and the others not.
    The grafted diene elastomer (s) can be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers.
    The rubber composition can also include a reinforcing filler.
    The reinforcing filler can be of any type of so-called reinforcing filler, known for its capacity to reinforce a rubber composition which can be used for the manufacture of tires, for example an organic filler such as carbon black, an inorganic reinforcing filler such as silica with which a coupling agent is associated in known manner, or else a mixture of these two types of filler.
    Such a reinforcing filler typically consists of nanoparticles whose average size (by mass) is less than a micrometer, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm.
    Another component of the rubber composition, as mentioned previously, is the chemical crosslinking agent.
    The crosslinking agent allows the formation of covalent bonds between the elastomeric chains, which gives them elastic properties. The crosslinking agent can be based either on sulfur or on donors of sulfur and / or peroxide and / or bismaleimides, preferably based on sulfur.
    The rubber composition as mentioned above may also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tires, in particular treads, such as for example plasticizers, pigments, protective agents such as antioxidants, non-reinforcing fillers.
    The present invention is further illustrated by the following nonlimiting examples.
    EXAMPLES
    molecules
    The structural analysis and the determination of the molar purities of the synthesis molecules are carried out by NMR analysis. Spectra are acquired on an Avance 3400 MHz spectrometer
    BRUKER equipped with a 5 mm wide BBFO-zgrad probe. Experience NMR quantitative X H, uses a simple pulse sequence 30 ° and a repeating time of 3 seconds between each 64 acquisitions. The samples are dissolved in a deuterated solvent, deuterated dimethyl sulfoxide (DMSO) unless otherwise indicated. Deuterated solvent is also used for the lock signal. For example, the calibration is performed on the proton signal of the DMSO deuterated at 2.44 ppm relative to a TMS reference at Oppm. The NMR spectrum Χ Η coupled with 2D experiments HSQC 'H / ^ C and HMBC' H / ^ C allow the structural determination of molecules (see attribution tables). The molar quantifications are carried out from the quantitative NMR ID Χ Η spectrum.
    Mass spectrometry analysis is performed by direct injection by an electrospray ionization mode (ID / ESI). The analyzes were carried out on a Bruker HCT spectrometer (flow 600 μΕ / ιηΐη, nebulizer gas pressure 10 psi, nebulizer gas flow 4 L / min).
    Molecule grafted on SBR or IR
    The determination of the molar level of 2- (2- (2oxoimidazolidin-1-yl) ethoxy] -1-naphtonitrile oxide grafted onto SBR (styrene-butadiene rubber) or IR (isoprene rubber) is carried out by NMR analysis. The spectra are acquired on a 500 MHz BRUKER spectrometer equipped with a “BBFOzgrad-5 mm CryoSonde.” The quantitative NMR X H experiment uses a 30 ° single pulse sequence and a repetition delay of 5 seconds between each acquisition. samples are solubilized in deuterated chloroform (CDCI3) in order to obtain a “lock” signal 2D NMR experiments have made it possible to verify the nature of the grafted motif thanks to the chemical shifts of carbon and proton atoms.
    Tensile tests
    These tensile tests make it possible to determine the elasticity stresses and the breaking properties. Unless otherwise indicated, they are carried out in accordance with French standard NF T 46-002 of September 1988.
    The stresses at break (in MPa) and the elongations at break (base 100) are measured at 23 ° C ± 2 ° C and at 100 ° C ± 2 ° C, according to standard NF T 46-002.
    Dynamic properties
    The dynamic properties AG * and tan (ô) max are measured on a viscoanalyzer (Metravib VA4000), according to standard ASTM D 599296. The response of a sample of vulcanized composition is recorded (cylindrical test tube 4 mm thick and 400 mm 2 cross section), subjected to a sinusoidal stress in alternating single shear, at the frequency of 10 Hz, under normal temperature conditions (23 ° C) according to standard ASTM D 1349-99, or as the case may be at a temperature different (100 ° C). A deformation amplitude sweep is carried out from 0.1% to 100% (outward cycle), then from 100% to 0.1% (return cycle). The exploited results are the complex dynamic shear modulus (G *) and the loss factor tan (ô). For the return cycle, we indicate the maximum value of tan (ô) observed, denoted tan (ô) max.
    I. Synthesis of 2- [2- (2-oxoimidazolidin-1-yl) ethoxy] -l-naphtonitrile oxide
    2- [2- (2-oxoimidazolidin-l-yl) ethoxy] -l-naphtonitrile oxide is synthesized in six steps, called step a1, step a2, step b2, step b2, step c and step d.
    Step a1 is performed according to protocol 1, step a2 according to protocol 2, step b1 according to protocol 3. Steps b2 and c are performed according to protocol 4. Step d is performed according to protocol 5.
    Step a1: preparation of 2-hydroxy-1-naphthhaldehyde
    Protocol 1
    This compound can be obtained from napthol by a formylation reaction according to the so-called Reimer-Tiemann protocol described in Organic Syntheses, 22, 63-4; 1942 by Russell, Alfred and Lockhart, Luther B. or in Organic Reactions (Hoboken, NJ, United States), 28, 1982 by Wynberg, Hans and Meijer, Egbert W., or according to the procedure described by Casiraghi, Giovanni et al. in Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), (9), 1862-5, 1980 or again by a Vilsmeier reaction described by Jones, Gurnos and Stanforth, Stephen P. in Organic Reactions (Hoboken, NJ, United States), 49, 1997.
    2-hydroxy-1-napthaldehyde is commercially available. It can for example be obtained from Aldrich (CAS 708-06-5).
    Step a2: preparation of 1- (2-chloroethyl) imidazolidin-2-one
    Protocol 2:
    This compound can be obtained according to a protocol described in patent application WO 2012/007684.
    Step b1: preparation of 2- (2- (2-oxoimidazolidin-1-yl) ethoxy) -lnaphthadehyde
    Protocol 3:
    A mixture of 2-hydroxy-1-naphthhaldehyde (20.0 g, 0.116 mol), potassium carbonate (24.08 g, 0.174 mol), and l- (2chloroethyl) imidazolidin-2-one (25.9 g, 0.174 mol) in DMF (20 mL) is heated to 75 ° C (Tbain) for 3.0-3.5 hours. Then a second portion of 1- (2-chloroethyl) imidazolidin-2-one (17.26 g, 0.116 mol) is added and the reaction medium is stirred for 9 to 10 hours at 75 ° C (Tbain) · After returning to 40-45 ° C, the reaction medium is poured into a solution of sodium hydroxide (10g, 0.25 mol) in water (700 mL). The mixture is stirred for 10 to 15 minutes. The precipitate is filtered and washed on the filter with water (3 times 400 mL).
    A gray solid (31.51 g, mass yield of 95%) is obtained.
    The molar purity is greater than 85% (1 H NMR).
    NOT δ 1 H (ppm) δ 13 C (ppm) 1 10.86 191.6 2 / 116.7 3 / 131.5 4 9.19 124.9 5 7.56 130 6 737 124.9 7 7.71 128.3 8 / 128.6 9 7.99 137.7 10 7.2 113.1 11 / 162.9 12 431 68.7 13 3.63 13.4 14 3.59 16.8 15 3.72 38.3 16 / 162.6
    Solvent: CDCI3
    Steps b2 and c: preparation of the oxime of 2- (2- (2-oxoimidazolidin-lyl) ethoxy) -1-naphthhadehyde
    The product isolated at the end of protocol 3 is used in the following protocol 4. 10
    Protocol 4:
    To a solution of 2- (2- (2-oxoimidazolidin-1-yl) ethoxy) -lnaphthhaldehyde (6.3 g, 22.2 mmol) in ethanol (30 mL) at 45 ° C (Tbain), is added a solution of hydroxylamine (2.05 g, 31.0 mmol, 50% in water, Aldrich) in ethanol (5 mL). The reaction medium is stirred for 4 hours at 55 ° C (Tbain) · After returning to 40 ° C, ethyl acetate (30 mL) is added dropwise for 15 minutes. The precipitate is filtered, washed on the filter with an ethanol / ethyl acetate mixture.
    A white solid (4.00 g, mass yield of 60%) is obtained.
    The molar purity estimated by NMR X H is greater than 95%.
    TLC: Rf = 0.10 (S1O2; EtOAc); revelation by UV and U.
    NOT" δ 1 H (ppm) δ 13 C (ppm) 1 8.75 147.5 2 / 115.9 3 / 133 4 8.78 127 5 7.46 128.5 6 7.35 125.2 7 7.88 132.8 8 / 130.9 9 7.79 129.4 10 7.36 115.2 11 / 157.1 12 4.28 69.3 13 3.59 44.4 14 3.64 47.6 15 3.40 39.3 16 / 165.3
    Solvent: MeOH
    Step d: Preparation of 2- [2- (2-oxoimidazolidin-lyl) ethoxy] -1 -naphtonitrile oxide
    Protocol 5:
    To a solution of oxime of 2- (2- (2-oxoimidazolidin-lyl) ethoxy) -l-naphthhaldehyde (7.5 g, 25.06 mmol) in dichloromethane (300 mL) cooled to 4 ° C (Tbain = 0 ° C) is added dropwise an aqueous solution of NaOCl (78% g Cl / L, 35 mL) for 15 minutes. The reaction medium is stirred for 60 to 70 minutes at a temperature of 4-5 ° C. The organic phase is separated. The aqueous phase is extracted with dichloromethane (25 mL). The combined organic solutions are washed with water (2 times per 25 mL). The solvent is evaporated under reduced pressure up to 40-50 mL. 40/60 petroleum ether (60 mL) is added for crystallization. The precipitate obtained is filtered and washed with petroleum ether 40/60 (2 times per 30 mL).
    A white solid (6.46 g, mass yield of 87%) is obtained.
    The molar purity estimated by NMR X H is greater than 99%.
    ο l +
    Η
    No. δ 1 H (ppm) δ II. * 13 C (ppm) 1 / - 2 / 96.7 3 / 134.1 4 7.92 124 5 7.56 128.9 6 7.39 125.2 7 7.77 128.6 8 / 128.5 9 7.89 133 10 7.18 112.7 11 / 160.5 12 4.31 69.4 13 3.64 43.4 14 3.76 47.3 15 3.42 38.5 16 / 162.5
    Solvent: CDCI3
    II. Manufacture of an SBR grafted with 2- (2- (2oxoimidazolidin-l-yl) ethoxy] -l-naphtonitrile oxide
    The 2- [2- (2-oxoimidazolidin-1-yl) ethoxy] -lnaphtonitrile oxide obtained previously (at the end of protocol 5) is used.
    2- [2- (2-oxoimidazolidin-110 yl) ethoxy] -1-naphtonitrile oxide (0.88 g; 2.97 mmol) is incorporated into 20 g of SBR (containing 26.5% by weight of styrene and 25% by weight of 1,2-butadiene unit, of Mn = 150,000 g / mol and Ip = 1.84) on a cylinder tool (external mixer at 23 ° C). The mixture is homogenized in 15 portfolio passes. This mixing phase is followed by a heat treatment at 120 ° C for 10 minutes in a press at 10 bar pressure.
    The X H NMR analysis demonstrated a molar grafting rate of 0.81% with a molar yield of grafting of 80%.
    No. δ X H (ppm) δ 13 C (ppm) 1 / - 2 / - 3 / - 4 7.70 129.5 5 7.61 126.7 6 7.77 123.7 7 7.29 125.9 8 / - 9 7.21 123.0 10 7.10 112.3 11 / - 12 4.11 66.5 13 3.33 44.6 14 3.34 + 3.49 (H non eq *) 42.0 15 3.18 37.2 16 / -
    (*) X H not equivalent: protons carried by the same carbon atom not having the same chemical shift
    III. Manufacture of an IR grafted with 2- [2- (210 oxoimidazolidin-l-yl) ethoxy] -l-naphtonitrile oxide
    The 2- [2- (2-oxoimidazolidin-1-yl) ethoxy] -lnaphtonitrile oxide obtained previously (at the end of protocol 5) is used.
    2- [2- (2-oxoimidazolidin-lyl) ethoxy] -1-naphtonitrile oxide (0.26 g; 0.88 mmol) is incorporated into 20 g of IR (containing 98% by weight of isoprene unit) 1.4 cis and Mn = 375,000 g / mol and
    Ip = 3.6) on a cylinder tool (external mixer at 23 ° C). The mixture is homogenized in 15 portfolio passes. This mixing phase is followed by a heat treatment at 120 ° C for 10 minutes in a press at 10 bar pressure.
    NMR analysis IV. * * * * * X H made it possible to demonstrate a molar grafting rate of 0.26% with a molar grafting yield of 90%.
    No. δ X H (ppm) δ 13 C (ppm) 1 / - 2 / - 3 / - 4 7.83 131.2 5 7.72 128.1 6 7.86 124.3 7 7.42 127.5 8 / - 9 7.30 124.2 10 7.20 113.3 11 / - 12 4.23 68.3 13 3.53 46.5 14 3.56 43.6 15 3.33 38.4 16 / -
    IV. Rubber compositions
    1) Preparation of the rubber compositions
    Four rubber compositions are prepared.
    Rubber compositions comprising SBR or IR grafted with 2- [2- (2-oxoimidazolidin-1-yl) ethoxy] -l15 naphtonitrile oxide (compound of formula (IV) according to the invention, called in the following compound A) are prepared. Rubber compositions comprising SBR or IR grafted with 2,4,6-trimethyl-3- [226 (2-oxoimidazolidin-1-yl) ethoxy] benzonitrile oxide (hereinafter called compound B; compound are also prepared.
    The following tests are carried out as follows in two cases:
    - Case A: we introduce into an internal Polylab mixer of 85cm 3 , filled to 70% and whose initial tank temperature is around 110 ° C, the diene elastomer (s) grafted as described in point II or in point III.
    - Case B: one introduces into an internal Polylab mixer of 85 cm 3 , filled to 70% and whose initial tank temperature is around 110 ° C., the non-grafted diene elastomers. For the mixtures concerning compound A and compound B, compound A or compound B is introduced at the same time as the diene elastomer and thermomechanical work is carried out for one minute at 120 ° C.
    Then, for each of the four compositions, the reinforcing filler (s), the optional coupling agent, are introduced, then, after one to two minutes of kneading, the various other ingredients with the exception of the vulcanization system. Thermomechanical work is then carried out (non-productive phase) in one step (total mixing time equal to approximately 5 minutes), until a maximum drop temperature of 160 ° C. is reached. The mixture thus obtained is recovered, it is cooled and then the vulcanization system (sulfur) is added to an external mixer (homo-finisher) at 25 ° C, mixing the whole (productive phase) for approximately 5 to 6 minutes.
    The compositions thus obtained are then calendered either in the form of plates (thickness of 2 to 3 mm) or of thin sheets of rubber for the measurement of their physical or mechanical properties, or in the form of profiles which can be used directly, after cutting and / or assembly to the desired dimensions, for example as semi-finished products for tires, in particular as tire treads.
    a) SBR rubber compositions
    The rubber compositions relating to the SBR are given in Table 1. The rubber composition comprising the SBR grafted with the compound A according to the invention is called composition 1. The rubber composition comprising the SBR grafted by the comparative compound B is called composition 2. The contents are expressed in pce. The molar level of compound grafted onto the SBR is 0.3% for both the SBR-g-A and the SBR-g-B. Thus, there is 0.3 mole of grafted compound per 100 moles of units of the polymer (moles of monomer units constituting the polymer, including those which carry the grafted compound).
    Table 1
    compositions 1 2 SBR-g-A (1) 101.4 - SBR-g-B (2) - 101.3 Silica (3) 55 55 Silane TESPT (4) 5.5 5.5 N234 (5) 3 3 6PPD (6) 1.5 1.5 TMQ (7) 1 1 Paraffin 6266 (8) 1 1 ZnO (9) 2.7 2.7 Stearic acid (10) 2.5 2.5 CBS (11) 1.8 1.8 Sulfur (12) 1.5 1.5
    (1) SBR grafted with compound A (2) SBR grafted with compound B (3) Silica "Zeosil 1165MP" - Rhodia company in the form of microbeads (BET and CTAB of approximately 150-160 m 1 2 3 4 5 6 / g) (4) TESPT ("S169" - Degussa company) (5) Carbon black N234 (6) Antioxidant "Santoflex 6PPD" - Solutia company (7) 2,2,4-trimethyl-1,2-dihydroquinoline - Flexys company (8) Paraffin (9) Zinc oxide (industrial grade - Umicore company) (10) Stearin (“Pristerene 4031” - Uniquema company) (11) CBS: N-cyclohexyl-2-benzothiazyl-sulfenamide (“Santocure CBS "- Flexys Company)
    b) IR rubber compositions
    The rubber compositions relating to the IR are given in Table 2. The rubber composition comprising the IR grafted with the compound A according to the invention is called composition 3. The rubber composition comprising the IR grafted by the compound B comparative is called composition 4. The contents are expressed in phr. The molar level of compound grafted onto the IR is 0.6% for both IR-g-A and IR-g-B. Thus, there are 0.6 mole of grafted compound per 100 moles of units of the polymer (moles of monomer units constituting the polymer, including those which carry the grafted compound).
    Table 2
    compositions 3 4 IR-g-A (1) 102.6 - IR-g-B (2) - 103.5 Silica (3) 55 55 Silane TESPT (4) 5.5 5.5 N234 (5) 3 3 6PPD (6) 1.5 1.5 TMQ (7) 1 1 Paraffin 6266 (8) 1 1 ZnO (9) 2.7 2.7 Stearic acid (10) 2.5 2.5 CBS (11) 1.8 1.8 Sulfur 1.5 1.5
    (1) IR grafted with compound A (2) IR grafted with compound B (3) Silica "Zeosil 1165MP" - Rhodia company in the form of microbeads (BET and CTAB of approximately 150-160 m 2 / g) (4 ) TESPT (“S169” - Degussa company) (5) Carbon black N234 (6) Antioxidant “Santoflex 6PPD” - Solutia company (7) 2,2,4-trimethyl-1,2-dihydroquinoline (8) Paraffin (9 ) Zinc oxide (industrial grade - Umicore company) (10) Stearin (“Pristerene 4031” - Uniquema company) (11) CBS: N-cyclohexyl-2-benzothiazyl-sulfenamide (“Santocure CBS” - Company Flexys)
    2) Characterization tests - Results
    a) SBR rubber compositions
    The properties of compositions 1 and 2 are compared. The results are reported in Table 3:
    compositions 1 2 Elongation properties at 23 ° C (base 100) Breaking stress 100 100 Elongation properties at 100 ° C (base 100) Breaking stress 106 100 Dynamic properties at 23 ° C G * 10% (MPa) 3.41 3.32 Tan δ max 0.17 0.17 Dynamic properties at 100 ° (G * 10% (MPa) 2.18 2.05 Tan δ max 0.11 0.12
    Table 3
    Composition 1 has a better breaking stress than composition 2 at 100 ° C. Furthermore, composition 1 has better rigidity than composition 2, accompanied by a conservation of hysteresis properties.
    The composition comprising the compound according to the invention therefore has improved properties compared to the composition comprising a comparative compound.
    b) IR rubber compositions
    The properties of compositions 3 and 4 are compared. The results are reported in Table 4:
    compositions 3 4 Elongation properties at 23 ° C (base 100) Breaking stress 111 100 Elongation properties at 100 ° C (base 100) Breaking stress 102 100 Dynamic properties at 23 ° C G * 10% (MPa) 1.56 1.55 Tan δ max 0.11 0.10 Dynamic properties at 100 ° (G * 10% (MPa) L12 1.11 Tan δ max 0.07 0.06
    Table 4
    Composition 3 presents a better breaking stress than composition 4, accompanied by a conservation of the properties of rigidity and hysteresis, whatever the temperature.
    The composition comprising the compound according to the invention therefore has improved properties compared to the composition comprising a comparative compound.
    权利要求:
    Claims (21)
    [1" id="c-fr-0001]
    Compound of formula (I) below:
    - + O
    0-ΝΞθΡΑΓ χ
    Sp — N ^ NH (I), in which:
    PAr denotes a polyaromatic group comprising at least two condensed aromatic hydrocarbon rings, each of said condensed aromatic cycles being optionally substituted by one or more independent carbon-containing chains, identical to the others, aliphatic or different, or aromatic, linear, branched or cyclic, optionally substituted or interrupted by one or more heteroatoms;
    - Sp represents an atom or a group of atoms.
    [2" id="c-fr-0002]
    2. Compound according to claim 1, characterized in that the group Sp is a linear or branched alkylene chain in C1-C24, preferably in C1-C10, more preferably in Ci-Cô, optionally interrupted by one or more nitrogen atoms , sulfur or oxygen.
    [3" id="c-fr-0003]
    3. Compound according to claim 1 or 2, characterized in that
    that it has the following formula (II): R yNOC / R. 6 ______ 1 FV r 2* 4 R 3(II) in which :
    - a group chosen from Ri formula (III) below:
    in R7 denotes the group of (III), in which Sp is as defined in claim 1 or 2, the other six groups, identical or other, or substituted six other groups, identical representing, independently of hydrogen or a linear, branched or cyclic aliphatic carbon chain, possibly interrupted by one or more heteroatoms.
    [4" id="c-fr-0004]
    4. Compound according to the preceding, characterized in formula (IV) below:
    any of which it is selected from different, an aromatic atom, or claims a compound of and a compound of the following formula (V):
    Λη
    HN 'preferably the compound of formula (IV).
    [5" id="c-fr-0005]
    5. Process for the synthesis of the compound of formula (I) as defined in any one of the preceding claims, comprising the following successive steps:
    (bl) the reaction of a compound of the following formula (VI):
    %
    --- PA | - Y (VI), in which PAr is as defined in claim 1 and Y represents a nucleophilic group, with a compound of formula (VII) below:
    wherein Sp is as defined in claim 1 or 2, and
    Z represents a nucleofuge group;
    in the presence of at least one polar solvent Si, of at least one base, at a temperature Ti ranging from 70 to 150 ° C, to form a compound of formula (VIII) below
    H
    V PAr
    Where
    Sp — N NH (VIII);
    (b2) reacting said compound of formula (VIII) with an aqueous solution of hydroxylamine at a temperature T 2 ranging from 30 to
    70 ° C, to obtain an oxime compound of formula (IX) below ^ PAr Â
    N Sp — N NH
    OH (IX);
    (c) a step of recovering said oxime compound of formula (ix);
    (d) a step of oxidizing the oxime compound of formula (IX) with an oxidizing agent, in the presence of at least one organic solvent S 2 .
    [6" id="c-fr-0006]
    6. The method of claim 5, wherein the two steps (b1) and (b2) are separated by a step of isolation and purification of the compound of formula (VIII).
    [7" id="c-fr-0007]
    7. Method according to claim 5, in which the two stages (b1) and (b2) are carried out according to a monotope synthesis.
    [8" id="c-fr-0008]
    8. Method according to any one of claims 5 to 7, in which the group Y is chosen from hydroxyl, thiol and primary or secondary amine functions.
    [9" id="c-fr-0009]
    9. Method according to any one of claims 5 to 8, in which the group Z is chosen from chlorine, bromine, iodine, mesylate group, tosylate group, acetate group and trifluoromethylsulfonate group.
    [10" id="c-fr-0010]
    10. Method according to any one of claims 5 to 9, in which the polar solvent Si is a water-miscible polar solvent, preferably a protic solvent, more preferably an alcoholic protic solvent.
    [11" id="c-fr-0011]
    11. Method according to any one of claims 5 to 10, in which the compound of formula (VI) represents from 5 to 40% by weight, preferably from 10 to 30% by weight, relative to the weight of the solvent.
    [12" id="c-fr-0012]
    12. Method according to any one of claims 5 to 11, in which the base is chosen from alkali alcoholates, alkali carbonates, alkaline earth carbonates, alkali hydroxides, alkaline earth hydroxides and mixtures thereof.
    [13" id="c-fr-0013]
    13. Process according to any one of claims 5 to 12, in which the base is chosen from sodium methanolate, potassium carbonate and sodium hydroxide, preferably potassium carbonate.
    [14" id="c-fr-0014]
    14. Method according to any one of claims 5 to 13, in which the molar amount of base is 1.5 to 8 molar equivalents, preferably 2 to 6 molar equivalents, relative to the molar amount of compound of formula (VI).
    [15" id="c-fr-0015]
    15. Method according to any one of claims 5 to 14, in which the addition of the aqueous hydroxylamine solution is carried out when the conversion of the compound of formula (VI) is at least 70% by weight.
    [16" id="c-fr-0016]
    16. Method according to any one of claims 5 to 15, in which the oxidizing agent is chosen from sodium hypochlorite, N-bromosuccinimide in the presence of a base, Nchlorosuccinimide in the presence of a base, and hydrogen peroxide in the presence of a catalyst, preferably sodium hypochlorite.
    [17" id="c-fr-0017]
    17. Method according to any one of claims 5 to 16, in which the organic solvent S 2 is an organic solvent chosen from chlorinated solvents and of ester, ether and alcohol type, more preferably chosen from dichloromethane, acetate d ethyl, butyl acetate, diethyl ether, isopropanol and ethanol, even more preferably chosen from ethyl acetate and butyl acetate.
    [18" id="c-fr-0018]
    18. Method according to any one of claims 5 to 17, comprising a step (a2) of manufacturing the compound of formula (VII), prior to step (b1), by reacting a compound of formula ( X) following:
    NH (X), in which Sp is as defined in claim 1 or 2, with an agent allowing the formation of the nucleofuge group Z.
    [19" id="c-fr-0019]
    19. Method according to the preceding claim, wherein said agent is thionyl chloride.
    [20" id="c-fr-0020]
    20. The method of claim 18 or 19, wherein step (a2) is carried out in the absence or in the presence of at least one solvent S 4 , preferably a chlorinated solvent, more preferably dichloromethane.
    [21" id="c-fr-0021]
    21. Method according to any one of claims 18 to 20, in which step (a2) is immediately followed by a step (a3) for recovering the compound of formula (VII), preferably by purification with toluene, more preferably by crystallization of the compound of formula (VII) in toluene.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3649111B1|2021-08-25|Polyaromatic molecule having a nitrile oxide function
    EP2593485B1|2016-03-23|Polymers craftet with azotic molecules
    EP3060552B1|2020-12-02|1,3-dipolar compound bearing an imidazole function and process for modifying an unsaturated polymer by grafting
    EP3648988B1|2021-04-21|Composition on the basis of at least one specific polyaromatic compound
    EP3713924A1|2020-09-30|1,3-dipolar compound comprising an epoxide group
    EP3648989B1|2021-04-21|Polymer carrying specific pendant imidazolidinone functional groups
    WO2016207263A1|2016-12-29|Method for synthesizing molecules having a nitrile oxide function
    WO2015177105A1|2015-11-26|Method for grafting a carboxylic acid ester function onto an unsaturated polymer
    WO2018109396A1|2018-06-21|1,3-dipolar compound having a conjugated carbon-carbon double bond
    FR3099764A1|2021-02-12|Molecule carrying a nitrile oxide function
    CA3145233A1|2021-02-11|Molecule having a nitrile oxide function
    EP3713772A1|2020-09-30|Diene polymer modified by an epoxide group
    WO2021023948A1|2021-02-11|Polymer having specific n-substituted imidazolidinone pendant functional groups
    CA3144683A1|2021-02-11|Polymer having specific n-substituted imidazolidinone pendant functional groups
    FR3111894A1|2021-12-31|COMPOUND INCLUDING AN EPOXIDE GROUP
    CA3144667A1|2021-02-11|Composition based on at least one compound having an n-substituted imidazolidinone function
    FR3111898A1|2021-12-31|ELASTOMER GRAFT WITH PENDANT EPOXIDE GROUPS
    WO2020136331A1|2020-07-02|Grafted polymer bearing pendent cyclic carbonate functional groups
    WO2021023949A1|2021-02-11|Composition based on at least one compound having an n-substituted imidazolidinone function
    EP3902791A1|2021-11-03|Novel nitrogenous dipole compounds comprising cyclic carbonate functions
    同族专利:
    公开号 | 公开日
    EP3649111A1|2020-05-13|
    CA3068186A1|2019-01-10|
    WO2019007881A1|2019-01-10|
    PL3649111T3|2022-01-17|
    RU2742027C1|2021-02-01|
    EP3649111B1|2021-08-25|
    FR3068694B1|2019-07-26|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20110054134A1|2009-08-31|2011-03-03|Toyoda Gosei Co., Ltd.|Modified polymer material modified by nitrile oxide, and production method thereof|
    WO2012007441A1|2010-07-13|2012-01-19|Societe De Technologie Michelin|Graft polymer to which combined nitrogen molecules are grafted|
    WO2012007684A1|2010-07-13|2012-01-19|Arkema France|Molecules having combinable groups|
    US7186845B2|2004-10-20|2007-03-06|Bridgestone Corporation|Polymer-filler coupling additives|
    JP2008208163A|2007-02-23|2008-09-11|Bridgestone Corp|Modified polymer and rubber composition and tire using the same|
    FR3037953B1|2015-06-24|2019-01-25|Compagnie Generale Des Etablissements Michelin|PROCESS FOR THE SYNTHESIS OF MOLECULES CARRYING AN OXIDE FUNCTION OF NITRILE|FR3099767B1|2019-08-07|2021-07-09|Michelin & Cie|RUBBER COMPOSITION BASED ON AT LEAST ONE COMPOUND HAVING AN N-SUBSTITUTED IMIDAZOLIDINONE FUNCTION|
    FR3099764B1|2019-08-07|2021-07-09|Arkema France|Molecule carrying a nitrile oxide function|
    FR3099765B1|2019-08-07|2021-07-09|Michelin & Cie|POLYMER WITH SPECIAL FUNCTIONAL PENDANT GROUPS IMIDAZOLIDINONE N-SUBSTITUTES|
    FR3105238A1|2019-12-24|2021-06-25|Compagnie Generale Des Etablissements Michelin|MASTER MIXTURE BASED ON A MODIFIED POLYMER AND AN ORGANOPHOSPHORUS ADDITIVE AND ITS MANUFACTURING PROCESS|
    法律状态:
    2019-01-11| PLSC| Publication of the preliminary search report|Effective date: 20190111 |
    2019-05-22| PLFP| Fee payment|Year of fee payment: 3 |
    2020-01-31| TP| Transmission of property|Owner name: ARKEMA FRANCE, FR Effective date: 20191226 |
    2020-04-22| PLFP| Fee payment|Year of fee payment: 4 |
    2021-05-06| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1756300|2017-07-04|
    FR1756300A|FR3068694B1|2017-07-04|2017-07-04|POLYAROMATIC MOLECULE WITH AN OXIDE FUNCTION OF NITRILE|FR1756300A| FR3068694B1|2017-07-04|2017-07-04|POLYAROMATIC MOLECULE WITH AN OXIDE FUNCTION OF NITRILE|
    PL18733636T| PL3649111T3|2017-07-04|2018-07-02|Polyaromatic molecule having a nitrile oxide function|
    CA3068186A| CA3068186A1|2017-07-04|2018-07-02|Polyaromatic molecule having a nitrile oxide function|
    RU2019143068A| RU2742027C1|2017-07-04|2018-07-02|Polyaromatic molecule with nitric oxide functional group|
    EP18733636.7A| EP3649111B1|2017-07-04|2018-07-02|Polyaromatic molecule having a nitrile oxide function|
    PCT/EP2018/067766| WO2019007881A1|2017-07-04|2018-07-02|Polyaromatic molecule having a nitrile oxide function|
    [返回顶部]