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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0255—Phosphorus containing compounds
  • B01J31/0257—Phosphorus acids or phosphorus acid esters
  • B01J31/0259—Phosphorus acids or phosphorus acid esters comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H
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  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2265—Carbenes or carbynes, i.e.(image)
  • B01J31/2269—Heterocyclic carbenes
  • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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  • B01J31/22—Organic complexes
  • B01J31/2265—Carbenes or carbynes, i.e.(image)
  • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
  • C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
  • C07C13/16—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring
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  • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
  • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
  • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
  • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
  • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
  • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
  • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
  • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/82—Metals of the platinum group
  • B01J2531/821—Ruthenium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/06—Halogens; Compounds thereof
  • B01J27/08—Halides
  • B01J27/10—Chlorides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • C07C2531/22—Organic complexes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/11—Homopolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
  • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
  • C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/40—Polymerisation processes
  • C08G2261/41—Organometallic coupling reactions
  • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

• the present invention relates to a process for metathesis of olefins, using a particular metathesis catalyst, in the presence of a retarding agent consisting of at least one phosphite and of an activator chosen from Lewis acids, peroxides and their mixtures . It also relates to a kit for implementing this process.
• Olefinic units, or carbon-carbon double bonds, are present in many chemical compounds of interest, such as pharmaceutical compounds, flavorings, perfumes or polymers.
• the development of new reactions making it possible to form these motifs is therefore crucial for access to new synthetic routes for these compounds.
• the metathesis of olefins is among those most exploited by the chemical industry. This reaction consists in cutting a carbon-carbon double bond of an olefin and in redistributing the two alkylidene fragments obtained, with those of another olefin which undergoes the same reaction. In the case where the two double bonds are on the same molecule, a cyclic compound may result from this reaction.
• the substrate is a cyclic molecule, it will be possible to form a polyunsaturated non-cyclic molecule capable of polymerizing. In this case, we speak of metathesis polymerization with cycle opening (or ROMP).
• the ruthenium complexes used in metathesis generally have two neutral ligands, and two anionic ligands such as chlorides.
• neutral ligands of the N-heterocyclic diaminocarbene or NHC type confer on ruthenium complexes catalytic properties.
• Patent application WO2014 / 091157 describes in particular complexes of ruthenium alkylidene coordinated by one or two unsaturated and asymmetric NHC ligands.
• the catalyst can allow a sufficiently rapid and otherwise complete reaction (with a conversion rate of the starting olefin close to 100%) in order to avoid as much as possible the presence of residual monomers liable to affect the mechanical properties of the material obtained.
• the Applicant has demonstrated, against all expectations, that the metathesis reactions catalyzed by ruthenium complexes coordinated by two asymmetric unsaturated NHC ligands can be slowed down or even blocked for several hours by the use of specific retarding agents and that they can be reactivated on demand by adding a specific chemical activator. It also demonstrated that these retarding agents made it possible to extend the storage time of these catalysts at ambient temperature.
• the subject of the invention is therefore a process for metathesis of olefins, comprising contacting:
• a metathesis catalyst comprising at least one ruthenium alkylidene complex comprising two identical or different N-heterocyclic diaminocarbene ligands, at least one of which is l-aryl-3-cycloalkyl-imidazoline-2-ylidene ligand,
• a retarding agent consisting of at least one phosphite
• kit for implementing this process characterized in that it comprises:
• the subject of the invention is also a process for delaying the metathesis of olefins in the presence of a catalyst comprising at least one ruthenium alkylidene complex comprising two identical or different N-heterocyclic diaminocarbene ligands, including at least one l-aryl- ligand.
• 3-cycloalkyl-imidazoline-2-ylidene comprising bringing said catalyst into contact with a retarding agent consisting of at least one phosphite, followed by activation of the catalyst using an activator chosen from Lewis acids , peroxides and their mixtures.
• halogen is meant fluorine, chlorine, bromine or iodine.
• Cycloalkyl means a cyclic aliphatic hydrocarbon group, which can be monocyclic or polycyclic. When the group is polycyclic, that is to say that it comprises more than one cyclic nucleus, the cyclic nuclei can advantageously be condensed two by two or attached two by two by bonds.
• the cycloalkyl group is preferably a monocyclic hydrocarbon group having a number of carbon atoms greater than 2, preferably from 3 to 24, more preferably from 4 to 12 , or a polycyclic group (bi- or tricyclic) having a number of carbon atoms greater than 4, preferably from 6 to 18, such as for example the norbomyl or isopinocamphyle groups.
• alkyl is meant a saturated, linear or branched aliphatic hydrocarbon group containing from 1 to 20 carbon atoms, in particular a methyl, ethyl, isobutyl, octyl or dodecyl group.
• the alkyl group preferably has from 1 to 10 carbon atoms, and even more preferably from 1 to 4 carbon atoms.
• Examples of preferred alkyl groups are in particular methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl groups.
• heteroalkyl group is meant a linear or branched hydrocarbon chain having from 2 to 20 carbon atoms interrupted by one or more heteroatoms such as N, S or O.
• the heteroalkyl group can in particular be chosen from polyalkyleneoxy, alkoxy groups (alkyl-O-), alkylamino (alkyl-NH-), dialkylamino ((alkyl) (alkyl) N-), alkoxycarbonyl (alkyl-O-CO-), alkylcarbonyloxy (alkyl-CO-O-), alkylcarbonyl (alkyl -CO-), alkylaminocarbonyl (alkyl-NH-CO-) and alkylamido (alkyl-CO-NH-).
• alkenyl is meant an unsaturated, linear or branched aliphatic hydrocarbon group containing from 2 to 14 carbon atoms, in particular an ethenyl, vinyl, isopropenyl or butenyl group.
• aryl is meant a 6 to 20-membered aromatic, monocyclic or polycyclic carbocyclic group. Examples of aryl groups are phenyl and naphthyl.
• heteroaryl is meant an aromatic mono- or polycyclic group, each cycle of which contains 3 to 6 members and at least one member of which contains a heteroatom, in particular a thiophenyl, pyridinyl, pyrrolyl, furanyl, indolyl, thiophenyl, benzofuranyl group. , benzothiophenyl, imidazolyle, oxazolyle, thiazolyle, pyrazolyle, isoxazolyle, isothiazolyle, quinolinyle, isoquinolinyle.
• Carbocycle or “hydrocarbon cycle” means a mono- or polycyclic hydrocarbon group optionally unsaturated, aliphatic or aromatic, containing from 5 to 20 carbon atoms, in particular an indenyl group.
• the process according to the invention is a process for metathesis of olefins, comprising contacting:
• a metathesis catalyst consisting of at least one ruthenium alkylidene complex comprising two identical or different N-heterocyclic diaminocarbene ligands, at least one of which is l-aryl-3-cycloalkyl-imidazoline-2-ylidene ligand,
• a retarding agent consisting of at least one phosphite
• olefin is meant a compound having at least one carbon-carbon double bond.
• the olefin can be functionalized or not, that is to say contain one or more functional groups chosen from the group consisting of a hydroxyl, a thiol, a ketone, an aldehyde, an ester, an ether, an amine, a nitro group, a carboxylic acid, a sulfide, a disulfide, a carbonate, an isocyanate, a carbodiimide, a halogen, a cyano group and a sulfonate.
• the olefin can be cyclic (constrained cycle or not) or acyclic, a diene, or even an unsaturated polymer.
• none of the olefins comprise a conjugated double bond, in particular an oxo function conjugated to a double bond. It is particularly preferred that the olefin is distinct from an a, b-unsaturated ketone or aldehyde. Thus, the olefin is advantageously distinct from acrolein or crotonaldehyde, for example.
• the term "olefin” is used to denote both a single olefin and a mixture of several different olefins. It should therefore be understood as equivalent to "one or more olefins”.
• the catalyst used according to the invention comprises at least one ruthenium alkylidene complex as described below. It can thus be made up of at least one such complex and at least one complex distinct from those described below. Alternatively, it can consist of at least two complexes as described below. In the following description, all of these variants will be included in the definition of the "catalyst" according to the invention.
• alkylidene ruthenium complex means a pentacoordinated ruthenium complex comprising a monodentate or bidentate alkylidene ligand.
• the ruthenium complex according to the invention also comprises two identical or different N-heterocyclic diaminocarbene ligands, at least one l-aryl-3-cycloalkyl-imidazoline-2-ylidene ligand, which are coordinated to the ruthenium atom and whose aryl and cycloalkyl groups may optionally be substituted.
• This complex can thus comprise two identical or different l-aryl-3-cycloalkyl-imidazoline-2-ylidene ligands or else a l-aryl-3-cycloalkyl-imidazoline-2-ylidene ligand (unsaturated heterocycle) and a l-aryl ligand.
• -3-cycloalkyl-imidazolidine-2-ylidene (saturated heterocycle) in which the aryl and cycloalkyl groups, respectively, may be the same or different.
• the additional ligands carried by the ruthenium complex used according to the invention can for example be chosen from the group consisting of anionic ligands, such as the halides, in particular the chlorides.
• the ruthenium complex can thus comprise one or two anionic ligands, in addition to the monodentate or bidentate alkylidene ligand and two l-aryl-3-cycloalkyl-imidazoline-2-ylidene ligands.
• it does not contain any other ligand.
• the ruthenium complex used according to the invention thus preferably corresponds to formula (1) below:
• X denotes a hydrogen or halogen atom or an alkyl or aryl group
• Y denotes a halogen atom, such as chlorine, fluorine, bromine or iodine,
• B denotes a cycloalkyl group
• Ar represents an aryl group optionally substituted by at least one substituent chosen from: halogen atoms, and in particular chlorine or fluorine, trifluoromethyl, nitro, alkyl, heteroalkyl or alkylammonium groups and aryl groups which are unsubstituted or substituted by one or more alkyl groups,
• Al represents a hydrogen atom
• A2 represents an alkyl or alkenyl group, an aryl group or a heteroaryl group, or else A1 and A2 together form a carbocycle optionally substituted by at least one group chosen from alkyl, heteroalkyl and aryl groups.
• A2 represents a vinyl, methyl, thiophenyl or phenyl group.
• A1 and A2 together form an optionally substituted indenyl group.
• the complex of formula (1) corresponds to the following formula (1-1):
• B is a cycloalkyl group
• Ar is an aryl group unsubstituted or substituted by at least one group chosen from halogen atoms and trifluoromethyl, nitro, alkyl, heteroalkyl, alkylammonium and aryl groups, unsubstituted or substituted by one or more alkyl groups
• the groups X are independently selected from the group consisting of a hydrogen atom, a halogen atom, an aryl group and an alkyl group
• a, b, c, d, e and f are chosen independently of one another from the group consisting of a hydrogen atom, an alkyl group, a heteroalkyl group and a phenyl group, or a and b can together form a hydrocarbon ring optionally substituted by at least one group chosen from alkyl, halo and alkoxy groups.
• B is chosen from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl and cyclopentadecyl. More preferably, B is cyclohexyl.
• Ar is a phenyl group substituted by at least one group chosen from halogen atoms, and in particular chlorine or fluorine, trifluoromethyl, nitro, alkyl, in particular methyl or isopropyl, and alkoxy groups. . More preferably, Ar is chosen from the group consisting of 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, 2,4,6-tris (trifluoromethyl) phenyl, 2,4,6-trichlorophenyl and l 'hexafluorophenyl. Better still, Ar is 2,4,6-trimethylphenyl, also designated by "mesityl".
• the groups X preferably each represent a hydrogen atom. Furthermore, it is preferred that a, c, d, e and f represent a hydrogen atom and b a phenyl group.
• the ruthenium complex used according to the invention corresponds to the following formula (2):
• A is an organic or inorganic anion, in particular an acetate, trifluoroacetate, chloride, tetrafluoroborate, hexafluorophosphate or sulfonate anion such as a triflate.
• the ruthenium complexes used according to the invention have the advantage of being highly stable, in the sense that they can be stored for several months in air without degrading.
• the ruthenium complex used according to the invention can in particular be prepared according to the process described in patent application WO2014 / 091157, from a 1,3-disubstituted imidazolium salt and a precursor ruthenium complex , such as the complexes PI, P2 or P3 represented below.
• the synthesis of the imidazolium salt can itself be carried out as described in application WO2014 / 091156, by bringing an aniline Ar-NH2 into contact with an amine B-NH2 in the presence of a Bronsted acid such as l acetic acid, then adding this mixture to a solution containing a dicarbonyl compound, at a temperature of 80 ° C., followed by the addition of an inorganic salt, in particular a tetrafluoroborate salt, and of a solvent such as dichloromethane, extraction using water / organic solvent, evaporation of the organic solvent and then precipitation of the imidazolium salt with a polar organic solvent.
• a Bronsted acid such as l acetic acid
• the catalyst used in the metathesis process according to the invention can be used in the absence or in the presence of a solvent which can be any organic solvent, such as aliphatic hydrocarbons, in particular n-hexane and paraffin liquid; alicyclic hydrocarbons, such as cyclohexane or dimethylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; oxygenated compounds, in particular alcohols such as methanol and ethanol, ketones such as acetone, ethers such as diethyl ether, esters such as ethyl acetate, dimethyl carbonate and heterocycles oxygenates such as tetrahydrofuran or dioxane; halogenated compounds such as dichloromethane, in particular perfluorinated, such as hexafluorobenzene and hexafluorotoluene; and their mixtures.
• a solvent which can be any organic solvent, such as aliphatic hydro
• the concentration of the catalyst in the solvent can be between 0.005 mol / 1 and 100 mol / 1, preferably between 0.01 and 0.5 mol / 1, better still, between 0.01 and 0.1 mol / 1.
• the catalyst is dissolved in an organic solvent.
• the catalyst is dissolved in the olefin and the process does not use an organic solvent.
• the retarding agent used according to the invention consists of at least one phosphite.
• the phosphites which can be used correspond to the formula P (OR) 3 where the groups R are identical or different and independently denote H, an alkyl, a cycloalkyl, a heteroaryl, and an aryl optionally substituted by one or more groups, chosen in particular from halogens and alkyl groups.
• two groups R can join to form a ring optionally substituted by a group - (R'0) 2 POR 'where the groups R' are identical or different and independently denote H, an alkyl, a cycloalkyl, a heteroaryl, and an aryl optionally substituted by one or more groups, chosen in particular from halogens and alkyl groups.
• R is an alkyl group, in particular an ethyl, or a phenyl substituted by an alkyl group, in particular methyl, ethyl, isopropyl or nonyl.
• the molar ratio of the retarding agent to the catalyst is advantageously between 1: 10 and 10: 1, preferably between 1: 1 and 5: 1. In any event, the skilled person will be able to adjust the amount of l delaying agent used depending on the nature of the delaying agent.
• the catalyst is reactivated using an activator chosen from Lewis acids, peroxides and their mixtures.
• Lewis acids are in particular the halides of copper, silver, manganese, iron, ruthenium, magnesium or aluminum or the compounds of formula Zn (R ') 2, Sn (R') 2, Sn (R ') 4 and Si (R') 4 where the groups R 'denote, independently of each other, a halogen atom or an alkyl, cycloalkyl, alkenyl, aryl group such as a phenyl, or benzyl.
• the Lewis acid is chosen from: CuCl, SiCL and PhSiCh where Ph denotes a phenyl group.
• peroxides which can be used according to the invention, mention may be made of the peroxides represented by the formula R 1 -0-0- (R 2 -0-0) n -R 3 in which:
• R 1 and R 3 are identical or different, and denote a hydrogen, an alkyl, a cycloalkyl, an aryl or a group of formula R 4 C (0) - in which R 4 denotes an alkyl, a cycloalkyl, an alkoxy, or aryl;
• R 2 denotes an alkyl
• - n 0, 1, or 2.
• peroxides examples include alkyl peroxyacetates, alkyl peroxypropionates, alkyl peroxyisobutyrates, alkyl peroxypivalates, alkyl peroxycarbonates, dialkyl peroxyadipates and alkyl peroxybenzoates. These compounds are available from Akzo Nobel under the name Trigonox ® or from Arkema under the name Luperox ®.
• R 1 and R 2 may be, independently of one another, hydrogen, tert-butyl, tert-amyl, [bis (acetyl)] -methyl, or a group of formula R 4 C (0) - in which R 4 denotes a phenyl, an undecyl, or a 2-ethylhexyloxy.
• R 2 groups are in particular those represented by the formulas (R 2a ), (R 2b ), (R 2c ) and (R 2d ):
• n is 0.
• the molar ratio of the activator to the catalyst is advantageously between 1: 10 and 10: 1, preferably between 1: 1 and 5: 1. In any event, those skilled in the art will be able to adjust the amount of activator used depending on the nature of the activator.
• the molar ratio of the activator to the retarder is between 1: 100 and 10: 1.
• the retarding agent and the activator used according to the invention may, independently of one another, be in the form of a pure solid, such as a powder or granules, of a pure liquid, a dilute solution, suspension, or dispersion.
• the process according to the invention is a process for metathesis of olefins.
• the olefin metathesis can be a cross olefin metathesis, a cyclizing olefin metathesis, ring opening metathesis polymerization, terminal olefin homometathesis or acyclic diene polymerization (ADMET).
• a single terminal olefin (or ⁇ -olefin) is used, or a mixture of terminal olefins such as those resulting from the Fischer-Tropsch process. It is thus preferred that the metathesis reaction is applied to linear ⁇ -olefins having from 3 to 20 carbon atoms, preferably from 4 to 14 carbon atoms and even more preferably from 5 to 10 carbon atoms. Examples include pent-l-ene, hex-l-ene, hept-l-ene, oct-1-ene, non-l-ene or dec-l-ene. These olefins can be transformed by metathesis into heavier olefins which can be used in particular in the manufacture of plasticizers or lubricants.
• two olefins are used, which are independently chosen from terminal and internal olefins and advantageously consist of two terminal olefins.
• This reaction consists of a transalkylidenation of the two olefins which is especially useful in the synthesis of ceramides, pheromones or pharmaceutical intermediates.
• an internal olefin generally functionalized, such as methyl oleate, is reacted with ethylene to form terminal olefins.
• This latter reaction which is generally carried out under pressure, is of great interest in the oleochemical industry because it makes it possible to develop the biomass (vegetable seed oil) by metathesis. It is thus possible to obtain products useful in the manufacture of surfactants or polyamides, for example.
• Each of the olefins thus produced can then optionally be subjected to a cross metathesis process.
• the metathesis of olefins with ring closure, or cyclizing metathesis consists of forming a cyclic alkene from a molecule comprising two terminal or internal vinyl groups. It is also possible, depending on this reaction, to prepare polycyclic or heterocyclic compounds (comprising one or more oxygen, nitrogen, sulfur or phosphorus atoms in their cycle (s)), optionally functionalized with one or more epoxy, alcohol, ester, ketone, amide or amine groups. The compounds obtained find in particular an application as pharmaceutical active agents or as odorous molecules.
• said metathesis process is a cyclizing metathesis process and said olefin is a terminal unsaturation olefin such as 1,7-octadiene, or exaltolide.
• Polymerization by ring opening metathesis (or ROMP for "Ring-Opening Polymerization Metathesis”) consists in forming a polymer from a cyclic olefin, or "cycloolefin", the cycle of which is advantageously constrained.
• Cycloolefin is advantageously chosen from bridged cycloalkenes, unbridged cycloalkenes, their oligomers and their mixtures.
• cycloalkene is meant a cyclic hydrocarbon comprising at least one double bond.
• Bridged cycloalkenes are generally the reaction products of cyclopentadiene with a dienophile, such as dicyclopentadiene, norbomene, norbomadiene, ethylidene norbomene, vinylnorbomene, 5-alkyl-2-norbomene, 5, 6-dialkyl- 2 -norbomene, 5-alkenyl-2 -norbomene, 5-alkoxycarbonyl-2-norbomene, 5-phenyl-2 -norbomene and norbomene dicarboxylic anhydride.
• Unbridged cycloalkenes can in particular be chosen from cycloheptene, cyclooctene, cyclododecene and cyclooctadiene.
• the molar ratio of said olefin or of each of said olefins to said catalyst is advantageously between 15,000: 1 and 50: 1, preferably between 10,000: 1 and 100: 1, more preferably between 3,000: 1 and 500: 1. In any condition As a result, those skilled in the art will be able to adjust the catalytic charge as a function of the type of reaction which is carried out and the reagents involved.
• the reaction mixture may contain, in addition to the solvent optionally present in the catalyst solution when the latter is used in this form, at least one reaction solvent.
• This solvent can be chosen from the organic solvents listed above. It is preferred in this invention to use an oxygenated solvent, more particularly ethyl acetate, or alternatively a hydrocarbon, preferably toluene. However, the presence of a reaction solvent is not essential since one of the olefins can play this role.
• the method according to the invention can be implemented in the presence of one or more additives, in particular organic and / or inorganic fillers; reinforcements ; plasticizers; pigments and / or dyes; antioxidants; surfactants or amphiphilic polymers; flame retardants; UV absorbers; light stabilizers; anti-shock agents; anti-static agents; non-stick agents; lubricants; blowing agents; fungicides; and their mixtures.
• the fillers mentioned above can be in the form of powders, granules, beads, microspheres and particles of any form based on glass, metal oxides, metal carbides, metal nitrides, ceramics, fly ash, or alternatively of thermoplastic or thermosetting polymer or of elastomer.
• the method according to the invention can also be implemented in the presence of other additives such as chain transfer agents and / or crosslinking agents.
• the process according to the invention can be carried out at atmospheric pressure or, more particularly in the case of ethenolysis, under pressure and, in the case in particular of the polymerization of acyclic olefins (ADMET), under partial vacuum.
• ADMET acyclic olefins
• the catalyst, the activator, the retarding agent and the olefin are brought into contact simultaneously or successively.
• the catalyst, the retarding agent and the olefin are brought into contact until the system is homogenized, then the activator is added.
• the contacting of the catalyst, of olefin, of the retarding agent and of the activator is generally carried out with stirring until a homogeneous mixture is obtained which is then heated.
• the contacting of the catalyst, the olefin, the retarding agent and the activator can be carried out in a container such as a mold or a reaction tank, previously heated.
• the reaction can be carried out at a temperature of 20 to 190 ° C, preferably 60 to 110 ° C.
• a reaction solvent it is preferred that the reaction be carried out at reflux of this solvent.
• the duration of the reaction can be between approximately 1 minute and 10 h, preferably between 1 h and 6 h, for example between 2 h and 5 h.
• the contacting of the catalyst, the olefin, the retarding agent and the activator is carried out by the contacting of at least two compositions, in which the catalyst are distributed, the olefin, the retarding agent and the activator. More particularly, the method may include contacting and mixing a first composition containing the olefin, the catalyst and the retarding agent, with a second composition containing the olefin and the activator.
• the first and second compositions are advantageously mixed in a volume ratio of between 50: 1 and 1: 50, preferably in a volume ratio of 5: 1 to 1: 5 and more preferably in a volume ratio of 1: 1.
• the catalyst and the retarding agent may, independently of one another, be in the form of a solid or a liquid, dispersed or dissolved in one or more solvents and / or in olefin.
• the activator may be in the form of a solid or a liquid, dispersed or dissolved in one or more solvents and / or in the olefin.
• fillers possibly used in the process according to the invention may possibly be present in the mold in which the process of the invention is implemented.
• the method according to the invention can be used for the manufacture of parts according to different techniques and in particular by reactive injection molding, rotational molding, pultrusion, or resin infusion.
• the contacting and mixing of the catalyst, the olefin, the retarding agent and the activator can be carried out in the mold, or alternatively, outside the mold and then be introduced into the mold.
• the heated mixture in the mold is at least partially polymerized, so that the part takes shape in the mold and can then be removed from the mold.
• the invention also relates to a kit for implementing the method according to the invention.
• This kit typically contains:
• the kit includes:
• the total amount of olefin is thus shared between two compositions.
• the kit comprises:
• the kit comprises:
• the additives mentioned above can be present, independently of each other, in one and / or the other of the compositions of the kit.
• the invention further relates to a method for delaying the metathesis of olefins in the presence of a catalyst consisting of at least one ruthenium alkylidene complex comprising two identical or different N-heterocyclic diaminocarbene ligands, of which at least one l-aryl ligand -3- cycloalkyl-imidazoline-2-ylidene, comprising bringing said catalyst into contact with a retarding agent consisting of at least one phosphite, followed by activation of the catalyst using an activator chosen from Lewis acids, peroxides and their mixtures.
• a catalyst consisting of at least one ruthenium alkylidene complex comprising two identical or different N-heterocyclic diaminocarbene ligands, of which at least one l-aryl ligand -3- cycloalkyl-imidazoline-2-ylidene, comprising bringing said catalyst into contact with a retarding agent consisting of at least one
• an activator chosen from Lewis acids, peroxides and their mixtures can therefore be used for the activation of a catalyst consisting of at least one ruthenium alkylidene complex comprising two diaminocarbene N ligands -heterocyclic identical or different, including at least one ligand l-aryl-3-cycloalkyl-imidazoline-2-ylidene, said catalyst having been brought into contact with a delaying agent consisting of at least one phosphite, in a metathesis process d 'olefins.
• Figure 1 shows the evolution of the conversion of a cyclizing metathesis reaction
• Figure 2 shows the evolution of the conversion of a cyclizing metathesis reaction
• Figure 3 represents the evolution of the conversion of a cyclizing metathesis reaction
• 1,7-octadiene catalyzed by BisIMcsCV, in the presence of P (OEt) 3 and different amounts of SiCl 4 .
• Cyclohexylamine (1.13 mL, 10 mmol) is introduced into a flask and is cooled using an ice bath. Tetrafluoroboric acid (1.57 mL, 12 mmol) is added slowly with stirring and the ice bath is removed. 2,4,6-trimethylaniline (1.41 mL, 10 mmol), formaldehyde (0.74 mL, 10 mmol) and glyoxal (1.14 mL) are successively added with stirring then the mixture is brought to 90 ° C for 15 min.
• the mixture is cooled to ambient temperature and the selectivity measured by 1 H NMR in CDCb (selectivity of 84% in IMesC6.HBF4, 6% in BisC6.HBF4 and 10% in BisMes.HBF4).
• the aqueous phase is removed by decantation and the crude product is dried under vacuum.
• Ethyl acetate is added (20 mL) and the mixture is triturated until a precipitate is formed.
• the solid is filtered, washed with ethyl acetate (2 x 10 mL) and then dried under vacuum.
• IMesC6.HBF4 salt is obtained in the form of a pale white solid (962 mg, 27%).
• Rimidazolium (3 mmol, 3 eq.) was introduced into a Schlenk tube in a glove box, then 1 ml of toluene was added, followed by 6 ml of potassium hexamethyldisilazane (0.5M, 3 mmol, 3 eq. ). The mixture was then left under stirring for 30 minutes and then 0.92 g of precursor ruthenium complex (PI, P2 or P3 illustrated below; 1.0 mmol, 1 eq.) Was added all at once. The Schlenk tube was then closed and placed at 40 ° C outside the glove box. After 2 hours of reaction, the reaction medium was concentrated under vacuum and then purified by chromatography on silica gel.
• precursor ruthenium complex PI, P2 or P3 illustrated below; 1.0 mmol, 1 eq.
• the RV1 mobile is preferably used because it allows the lowest viscosities to be measured.
• 1,7-octadiene (29.6 pL; 0.2 mmol; 1 equiv.), Mesitylene (18.64 pL; 0.1334 mmol; 2/3 equiv.), CuCl were introduced into a schlenk. (1 mg; 0.01 mmol; 0.05 equiv.) And toluene (2 mL; 0.1 M).
• a portion of the P (OEt) 3 solution 200 pL; 0.01 mmol; 0.05 equiv.
• As well as a portion of the BisIMesCe catalyst solution (360 pL; 0.002 mmol; 0.01 equiv.) have been added.
• 1 H NMR spectrum was recorded at tO. Then, the mixture was stirred at 80 ° C.
• the reaction carried out in the absence of activator and retarder reaches a conversion of 100% after 30 minutes.
• the presence of 5 mol% of CuCl only strongly accelerates the reaction since a complete conversion is obtained after only 2 minutes, while the presence of 5 mol% of P (OEt) 3 only strongly slows down the reaction (no conversion after 6 h ).
• the reaction time can be adjusted to 1 hour using an equimolar mixture of CuCl and P (OEt) 3 (5 mol% of each).

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• 2018
  • 2018-11-16 FR FR1860602A patent/FR3088641B1/fr active Active
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