Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
  • C07C239/08—Hydroxylamino compounds or their ethers or esters
  • C07C239/20—Hydroxylamino compounds or their ethers or esters having oxygen atoms of hydroxylamino groups etherified
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/30—Only oxygen atoms
  • C07D251/34—Cyanuric or isocyanuric esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
  • C07F9/40—Esters thereof
  • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
  • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl

Definitions

• the present invention relates to polyalkoxyamines obtained from ⁇ -substituted nitroxides, which can be used in particular as initiators of radical polymerizations.
• M representing a polymerizable olefin
• P representing the growing polymer chain
• the control key is linked to the constants k deact , k act and k p (T. Fukuda and A. Goto, Macromolecules 1 999, 32, pages 61 8 to 623). If the ratio k inact / k act is too high, the polymerization is blocked, while when the ratio k p / k inact is too high, or when the ratio k inact / k act is too low, the polymerization is not controlled.
• A represents a polyfunctional core and R L a radical having a molar mass greater than 1 5, A and R L will be more fully defined later, it could synthesize polymers and copolymers with well defined architectures.
• the subject of the invention is therefore polyalkoxyamines of formula
• - A represents a di- or multipurpose structure which can be chosen from the structures given below without implied limitation:
• R 1 and R 2 represent an alkyl radical, linear or branched having a number of carbon atoms ranging from 1 to 10, phenyl or thienyl radicals optionally substituted by a halogen atom such as F, Cl, Br, or alternatively by an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 4, or alternatively by nitro, alkoxy, aryloxy, carbonyl, carboxy radicals; a benzyl radical, a cycloalkyl radical having a number of carbon atoms ranging from 3 to 1 2, a radical comprising one or more unsaturations;
• B represents a linear or branched alkylene radical, having a number of carbon atoms ranging from 1 to 20;
• m is an integer ranging from 1 to 10;
• R 3 and R 4 identical or different, represent aryl, pyridyl, furyl, thienyl radicals optionally substituted by a halogen atom such as F, Cl, Br, or else by an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 4, or alternatively by nitro, alkoxy, aryloxy, carbonyl, carboxy radicals;
• D represents an alkylene radical, linear or branched, having a number of carbon atoms ranging from 1 to 6, a phenylene radical, a cycloalkylene radical; p ranging from 0 to 10;
• R 5 , R 6 and R 7 identical or different, have the same meanings as R 1 and R 2 of the formula (II), q, r and s are whole numbers ranging from 1 to 5;
• R 8 has the same meaning as R 3 and R 4 of formula (III), t is an integer ranging from 1 to 4, u is> 2 and ⁇ 6;
• R 9 has the same meaning as the radical R 8 of the formula (V) and v is> 2 and ⁇ 6;
• R 10 , R 1 1 and R 12 identical or different, represent a phenyl radical, optionally substituted by a halogen atom such as Cl, Br, or else by an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 10,; W represents an oxygen, sulfur, selenium atom, w is zero or 1;
• R has the same meaning as R 1 of formula (II), R 14 has the same meaning as R 3 or R 4 of formula (III);
• R 15 and R 16 which are identical or different, represent a hydrogen atom, an alkyl radical, linear or branched, having a number carbon atoms ranging from 1 to 1 0, an aryl radical, optionally substituted by a halogen atom or a hetero atom,
• R L has a molar mass greater than 1 5;
• the radical R L monovalent is said to be in position ⁇ relative to the nitrogen atom, the remaining valences of the carbon atom and of the nitrogen atom in formula (1) may be linked to radicals various such as a hydrogen atom, a hydrocarbon radical such as an alkyl, aryl or aralkyl radical, comprising from 1 to 10 carbon atoms, the carbon atom and the nitrogen atom in formula (1) can also be linked together via a bivalent radical, so as to form a ring; preferably, however, the remaining valences of the carbon atom and the nitrogen atom of formula (I) are linked to monovalent radicals; preferably, the radical R L has a molar mass greater than 30, the radical R L can for example have a molar mass of between 40 and 450, for example, the radical R L can be a radical comprising a phosphoryl group , said radical R L can be represented by the formula:
• R 17 and R 18 which may be identical or different, can be chosen from the alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxyl, perfluoroalkyl, aralkyl radicals and can comprise from 1 to 20 carbon atoms; R 17 and / or R 18 may also be a halogen atom such as a chlorine or bromine or fluorine or iodine atom; the radical R L may also comprise at least one aromatic ring such as the phenyl radical or the naphthyl radical, the latter possibly being substituted, for example by an alkyl radical comprising from 1 to 10 carbon atoms.
• the monovalent radicals linked to the carbon atom carrying the radical R L may be a hydrogen atom, an alkyl radical, linear or branched having a number of carbon atoms ranging from 1 to 1 2, a phenyl radical, an aralkyl radical comprising for example from 1 to 1 0 carbon atoms.
• a hydrogen atom an alkyl radical, linear or branched having a number of carbon atoms ranging from 1 to 1 2
• a phenyl radical an aralkyl radical comprising for example from 1 to 1 0 carbon atoms.
• the two remaining valences of the carbon atom can also be linked to a divalent radical so as to form a ring including the carbon atom carrying the radical R L , said cycle possibly having a carbon number ranging from 3 to 10 and which may contain a heteroatom such as N, O, S.
• This method consists in transferring an atom or a group of atoms onto another molecule in the presence of an organometallic CuX / ligand system in solvent medium according to the scheme:
• a generally used procedure consists in dissolving the organometallic system such as CuBr / Iigand in an organic solvent preferably aromatic such as benzene or toluene, then in introducing into the solution the compound A (X) n and the nitroxide ⁇ -substituted
• ligands used include bipyridine, 4- 4'-di (5nonyl) 2,2'-bipyridine, tris (2-pyridylmethyl) amine (TPA).
• TPA 2,2'-bipyridine
• the reaction mixture is then stirred at a temperature between 20 ° C and 90 ° C for a period which can reach 48 hours, or even more.
• the precipitate is filtered, rinsed with a solvent such as ether then the filtrate is washed with an aqueous solution at 5% by weight of CuSO 4 then finally with water. It is dried over magnesium sulfate, then the solvents are evaporated under reduced pressure.
• a metal salt MX such as CuX, a ligand, the compound A (X) n and the ⁇ -substituted nitroxide are mixed with stirring in an organic solvent:
• the reaction medium is kept under stirring at a temperature between 20 ° C and 90 ° C until disappearance of the ⁇ -nitroxide substituted, the organic phase is recovered which is washed with water and then the polyalkoxyamine (I) is isolated by evaporation of the organic solvent under reduced pressure.
• ligands used according to this procedure include:
• HMTETA 10-hexamethyltriethylenetetramine
• cyclic polyamines such as:
• PMDETA should preferably be used.
• the degree of oxidation of the active species of the metal M of the metal salt is equal to 1 (M 1 ).
• This active species can be added as such to the reaction medium, preferably in the form of a metal halide such as
• the active species can also be generated in situ according to the REDOX reaction:
• the ligand is used according to a ligand / M 'molar ratio ranging from 1 to 5 and, preferably, ranging from 1 to 2.
• the molar ratio ⁇ -substituted nitroxide / A (X) n ranges from n to 1.4n and preferably is close to 1.
• R 5 , R 6 and R 7 identical or different, represent an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 10, a phenyl radical, a benzyl radical, a radical cycloalkyl having a number of carbon atoms ranging from 3 to 1 2, q, r and s are whole numbers ranging from 1 to 5.
• the compounds obtained are identified by mass spectrometry and by 1 H and 13 C NMR.
• the polyalkoxyamines of formula (I) according to the present invention can be used for the polymerization and the copolymerization of any monomer having a carbon-carbon double bond capable of polymerizing by radical route.
• the polymerization or copolymerization is carried out under the usual conditions known to those skilled in the art, taking into account the monomer (s) considered.
• the polymerization or copolymerization can be carried out in bulk, in solution, in emulsion, in suspension, at temperatures ranging from 50 ° C to 250 ° C and, preferably, ranging from 70 ° C to 150 ° C.
• vinyl aromatic monomers such as styrene, substituted styrenes, dienes, acrylic monomers such as alkyl or aryl acrylates and methacrylates, optionally fluorinated such as methyl acrylate, butyl acrylate, methyl methacrylate, acrylamides such as N, N-dimethylacrylamide.
• the monomer can also be vinyl chloride, vinylidene difluoride or acrylonitrile.
• a nitroxide can be added to the polymerization medium - optionally corresponding to the polyalkoxyamine (I) used - in a nitroxide / polyalkoxyamine (I) molar ratio ranging from
• n% 0.01 n% to 20n% and preferably ranging from n% to 10n%.
• the polyalkoxyamines (I) according to the present invention can also be used for the synthesis of so-called block block copolymers according to an operating protocol which consists in carrying out in a first step the polymerization in mass, in solution, in suspension or in emulsion of a monomer M 1 or a mixture of monomers having a carbon-carbon double bond capable of polymerizing by the radical route in the presence of a polyalkoxyamine (I) at a temperature ranging from 50 ° C to 250 ° C and, preferably, ranging from
• block block copolymers such as polystyrene - polybutylacrylate - polystyrene (PS-ABU-PS) can be prepared in this way.
• PS-ABU-PS polystyrene - polybutylacrylate - polystyrene
• H was obtained by oxidation of diethyl 2,2-dimethyl-1 - (1, 1 - dimethylethylamino) propylphosphonate using acid metachloroperbenzoic agent according to a protocol described in international application WO 96/24620.
• the polyazotated ligands used are:
• A- (X) n denotes a polyfunctional core comprising n halogenated functions.
• Example 8 where we used the paradi (bromo1 -ethyl) benzene obtained according to a conventional method by reaction of diethylbenzene with two equivalents of N-bromosuccinimide.
• the triestertribrominated used in Example 5 is obtained by reaction of 1,3,5-tris (2-hydroxyethyl) cyanuric acid with 2-bromopropionyl bromide and is described in Example 5.
• alkoxyamines A1, A2 are those having acrylate-DEPN type sequences. Those designated by a type name S1, S2, S3, S4 have phenylethyl-DEPN type sequences. EXAMPLE 1
• the product is purified by chromatography on a silica column using an eluent ether / heptane 4/1, then ether / methanol 1/1. Out of 0.96 g used, 0.73 g of colorless oil is recovered.
• the overall yield of isolated product is 75%.
• 1 H, 13 C and 31 P NMR the product has four asymmetric carbon atoms and a center of symmetry.
• the NMR signals are complex and reveal two families of distinct isomers in relative proportions 50/50.
• the different atoms are identified by an index indicated on the formula A1 developed above. When the signals are distinct, the two families of isomers are separated by a ";".
• the procedure is the same as in Example 1.
• the PMDETA ligand makes it possible to reduce the reaction time to 3 h.
• the product is purified by chromatography on a silica column using an el . uant ether / ethanol to 1% ethanol. On 1 g committed, 0.86 g of colorless honey is recovered.
• the product was characterized by mass spectrometry and by 1 H, 13 C and 31 P NMR.
• the NMR spectra show that there are two distinct families of isomers in a relative 50/50 proportion.
• the different atoms are identified by an index on the formula developed below. When the signals are distinct, the two families of isomers are separated by a ";"
• DEPN / triester-tribromé 3
• CuBr / triester-tribromé 3
• PMDETA / CuBr 2
• Cu (0) / CuBr 1
• solvent toluene
• T 20 ° C
• t 7 h .
• the product is purified by washing with water (5x500 ml)
• the material balance is given in table 5.
• the percentages of trialkoxyamine and of mono- and di-alkoxyamines were determined by 1 H and 31 P NMR.
• the content of residual DEPN was determined by HPLC.
• the residual solvent content was determined by 1 H NMR
• the reaction is carried out in a Schlenk tube under an argon atmosphere.
• Para di (bromo 1 -ethyl) benzene and DEPN are degassed beforehand.
• Toluene is distilled under argon on sodium-benzophenone.
• 1.02 g of CuBr are introduced into the 1000 ml Schlenk tube.
• the 31 P NMR shows two families of peaks corresponding to two types of diastereoisomers.
• the reaction is carried out in a Schlenk tube under an atmosphere
• the styrene or butyl acrylate are distilled and stored under an inert atmosphere at 5 ° C.
• the polydispersity index Ip at the end of polymerization is equal to: 1, 4.
• the curve Mn as a function of the conversion - FIG. 2 - clearly indicates that the polymerization with trialkoxyamine A2 is well controlled. In this figure 2:
• the polydispersity index at the end of polymerization is equal to: 1.27.
• the curve Mn as a function of the conversion -figure 3 - clearly indicates that the polymerization with trialkoxyamine S4 is well controlled. In this figure 3:
• the polydispersity index Ip at the end of polymerization is equal to: 1, 4.
• the curve Mn as a function of the conversion - FIG. 4 - clearly indicates that the polymerization with alkoxyamine A1 is well controlled.
• - -O- - represents MnTh
• the polydispersity index Ip at the end of polymerization is equal to: 1, 4.
• the curve Mn as a function of the conversion - FIG. 5 - clearly indicates that the polymerization with trialkoxyamine A2 is well controlled. In this figure 5:
• the polymer obtained is diluted in styrene (260 g).
• the temperature of the reactor is raised to 123 °.

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