Classifications

• • 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
  • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
  • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
  • C08G79/025—Polyphosphazenes
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B21/00—Nitrogen; Compounds thereof
  • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
  • C01B21/097—Compounds containing nitrogen and non-metals and optionally metals containing phosphorus atoms
  • C01B21/098—Phosphonitrilic dihalides; Polymers thereof
  • C01B21/0986—Phosphonitrilic dichlorides; Polymers thereof

Definitions

• the invention relates to a process for the preparation of linear polychlorophosphazenes having a terminal group -PXC1-- X denoting an oxygen or sulfur atom, -by polycondensation of the monomers P 2 NXC1_.
• n can take values ranging from 4 to 1000 for example - or even up to higher values which can reach 5000 or more.
• Formula (II) is assumed to be the structural formula of linear polychlorophosphazenes having the raw formula (I).
• the invention provides an improvement to the aforementioned process for the preparation of linear polychlorophosphazenes with terminal grouping -PXC1 2 , which makes it possible to minimize the crosslinking phenomena during polycondensation and thus to obtain high degrees of polycon ⁇ densation in a perfectly reproducible manner .
• the process according to the invention for the preparation of linear polychlorophosphazenes having a terminal group -PXC1 2 , X denoting an oxygen or sulfur atom is of the type in which a monomer of formula P 2 NXC1 5 is polycondensed under pressure and temperature conditions suitable for releasing PXC1 3 with continuation of said heating after cessation of the release of PXC1-, and it is characterized in that at least the polycondensation phase which follows the release of PXC1- is carried out , operating in solution in a medium dissolving both the monomer and rophosphazène polychlorinated which forms and inert to the consti ⁇ tuants of p reaction 'olycondensation.
• the solvent can also be added to the reaction medium during the mass polycondensation phase with release of PXCl, this addition being able to be carried out at any time during the course of said polycondensation phase.
• the solvent is present from the start to the end of the polycondensation of the monomer.
• the solvent When it is added to the polycondensation reaction medium during the mass polycondensation phase with release of PXCl, or when it is present from the start of the polycondensation of the monomer, the solvent must not form an azeotrope with the compound PXCl - And must have a higher boiling point, advantageously at least 20 ° C, than that of said compound PXC1-.
• the solvent used for carrying out the polycondensation of the monomer in solution r > could consist of a single solvent or of a mixture of solvents.
• Said solvent can in particular consist of one or more compounds chosen from aromatic hydrocarbons and their chlorinated derivatives. Examples of such solvents are in particular benzene, naphthalene, diphenyl, chlorobenzene, dichlorobenzenes, trichlorobenzenes, tetrachlorobenzene, pentachlorobenzene, hexachlorobenzene, chloronaphthalenes and chlorodiphenyls.
• the single polycondensation in solution or each of the phases of the polycondensation can be carried out at temperatures between 125 ° C and 380 ° C and more particularly from 190 ° C to 350 ° C. More specifically, the polycondensation temperatures are chosen from 200 ° C to 320 ° C and preferably from 210 ° C to 300 ° C.
• the pressures used for polycondensation generally range from atmospheric pressure to about 60 bars.
• the polycondensation in solution is carried out in a solvent according to the invention, the boiling point of which at atmospheric pressure is at least equal to the temperature chosen for said polycondensation in solution.
• the solvent used for the polycondensation in solution has a boiling point at the pressure considered which is higher than the temperature chosen for said polycondensation in solution.
• the quantity of solvent to be used for carrying out the polycondensation in solution can vary quite widely.
• the weight quantity of solvent to be used for the polycondensation in solution represents from 0.1 to 5 times and preferably from 0.3 to 2 times the weight quantity of monomer used in the polycondensation reaction.
• Subsequent substitution reactions of the chlorine atoms of polychlorophosphazene resulting from the polycondensation must be taken into account when choosing the solvent to be used for polycondensation in solution. For example, if one wishes to replace the chlorines of polychlorophosphazene by alcoholate residues, it must be taken into account that the chlorine atoms possibly present in the solvent molecule can react with the alcoholates and, to avoid losses of both solvent and alcoholates during the substitution treatment, choose for polycondensation in solution either U n chlorinated solvent capable of being easily removed from the polycondensate by distillation or better a non-chlorinated solvent.
• linear polychlorophosphazenes obtained by the process according to the invention can be used in the applications described with regard to the linear polychlorophosphazenes which are the subject of French patent n ° 79 24037. In particular they can be subjected to various substitution reactions for chlorine atoms that they contain organic or other residues, in particular alkoxy or aryloxy residues, for the production of polyorganophosphazenes.
• An important advantage of the process according to the invention lies in the fact that, at the end of polycondensation, the reaction medium containing the polycondensate is, after cooling to around 60-70 ° C., in the form of a more or less viscous mass. that can easily be diluted with solvents such as benzene to quickly form a suitable solution to be sent to the zone where the substitution reaction takes place.
• the method according to the invention therefore makes it possible to achieve an appreciable time saving for carrying out this dissolution, which significantly reduces the duration of the cycle of operations leading to the polyorganophosphazenes.
• the invention is illustrated by the following examples given without limitation.
• the operation was carried in a polycondensation reactor consisting of a flask of 500 ml three-necked equipped with a decision "internal temperature, an inlet for the reactants and a reflux condenser surmounted in turn a distillation head , a horizontal condenser and a graduated recipe, the whole being kept under an inert atmosphere
• the flask was immersed in a bath of silicone oil heated by a magnetic heating stirrer, which is also used for stirring the contents of the reactor.
• the reactor was loaded with 372.34 g of P 2 NOCl t -, prepared as described in Example I of French Patent No. 79 24037, and 184.5 g of trichloro - 1,2,4 benzene of point boiling at 210 ° C at atmospheric pressure, the latter acting as a solvent.
• the trifluoroethoxylated polymer. obtained had a weight average molecular mass (Mw), determined by light scattering, equal to 371000, an intrinsic viscosity (V)), determined at 30 ° C. in tetrahydrofuran (abbreviated THF), of 45 ml / g and an average degree of polycondensation by weight DP of 1530.
• Mw weight average molecular mass
• V intrinsic viscosity
• THF tetrahydrofuran
• DP represents the quotient of Mw by the molecular mass of a unitary unit, that is to say of the unit -N (CF, CH 2 O) 2 -, of the trifluoroethoxylated polymer.
• the benzene solution of the polychlorophosphazene obtained was free from gels.
• the polytrifluoroethoxyphosphazene obtained by substitution of the chlorines of the polychlorophosphazene, as indicated in Example 1, had the following characteristics: Mw 318,000
• Example 2 The procedure was similar to that of Example 1, replacing the 1,2,4,4-trichloro benzene by the same weight amount of naphthalene and working at the reflux temperature of naphthalene, that is to say at 218 ° C, at atmospheric pressure.
• the release of POCl lasted 101 hours and the heating phase of the reaction medium after cessation of the release of POCl- was continued for an additional 240 hours at reflux of naphthalene.
• reaction medium was cooled to around 70 ° C. and diluted with benzene.
• the benzene solution of the polychlorophosphazene obtained was free from gels.
• reaction medium was cooled to around 70 ° C. and then diluted with benzene.
• the benzene solution of the polychlorophosphazene obtained was free from gels.
• the polychlorophosphazene was transformed into polytrifluoroethoxyphosphazene by operating as indicated in Example 1 but with an excess of CF, CH 2 ONa which took into account the chlorides of tetrachlorodiphenyl left in the medium.
• the operation was carried out in a jacketed reactor with a capacity of 2 liters made of enamelled steel and equipped with an internal temperature measurement, an inlet for the reactants and a reflux condenser successively surmounted by a head. distillation, a horizontal condenser and a recipe consisting of a glass tube designed to resist pressure, the whole being kept under an inert atmosphere.
• the reactor was heated by circulation of oil in the jacket and included an anchor agitation system.
• the reactor was loaded with 992 g of P 2 NOCl g and 1000 g of 1,4-dichloro-benzene. The whole was maintained under a nitrogen pressure equal to 9 bars, which made it possible to operate at reflux of 1,4-dichloro-benzene at 280 ° C.
• the 1,4-dichloro-benzene was then distilled under vacuum at 130 ° C. and the remaining product was diluted with benzene.
• the benzene solution thus formed which contained the polychlorophosphazene resulting from the polycondensation of P-NOCl-, was free from gels.
• Example 2 The operation was carried out by following a procedure similar to that used in Example 1 with, however, replacement of the 1,2,4-trichloro benzene with 740 g of trichlorodiphenyl and use of all of the polycondensation at a temperature of 240 ° C under atmospheric pressure. .After 19 hours of maintaining the reaction medium at 240 ° C. the release of P0Cl 3 ceased and after cessation of said release the heating of the reaction medium was further continued at said temperature for 36 hours.
• reaction medium was cooled to around 70 ° C. and then diluted with benzene.
• the benzene solution containing the polychlorophosphazene was free from gels.
• the polychlorophosphazene was transformed into polytrifluoroethoxyphosphazene by operating as indicated in Example 1 but with an excess of CF, CH 2 ONa which takes into account the chlorides of trichlorodiphenyl left in the medium.
• the polycondensation of the monomer P 2 NSC1, - was carried out.
• This monomer was synthesized by first preparing P, NC1., 2 by reaction of PC1 5 on NH.C1 in POC1, as indicated by SEGLIN et al (US Patent No. 3,231,327), then reacting the compound P, NC1, 2 obtained with P -. S .. under the operating conditions described by KHODAK and GILYAROV (Izv. Akad. Nauk SSSR, Ser. Khim., 1979 (4), p. 924).
• the polycondensation was carried out by following a procedure analogous to that of Example 1 with, however, the use of 350 g of P-NSC1- and 116 g of trichloro - 1,2,4 benzene.
• the reaction medium was heated to its reflux temperature and all of the PSCl was collected after 65 hours. After cessation of the release of the compound PSCl.- the heating of the reaction medium was further continued for 89 hours. At the end of this time, almost all of the 1,2,4-trifluoro-benzene was removed by vacuum distillation and the polycondensate obtained was dissolved in benzene.
• the benzene solution obtained did not contain gels.
• the polychlorophosphazene resulting from the poly ⁇ condensation of P-NSCl ,. was transformed into polytrifluoroethoxyphosphazene by operating as indicated in example 1.
• the polytrifluoroethoxyphosphazene obtained had the following characteristics:

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• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

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Citations (4)

• 1984
  • 1984-10-17 FR FR8415892A patent/FR2571710B1/fr not_active Expired
• 1985
  • 1985-10-15 DE DE8585402001T patent/DE3562761D1/de not_active Expired
  • 1985-10-15 WO PCT/FR1985/000294 patent/WO1986002344A1/fr not_active Ceased
  • 1985-10-15 EP EP85402001A patent/EP0178997B1/fr not_active Expired
  • 1985-10-15 JP JP60504580A patent/JPS62501144A/ja active Granted
  • 1985-10-15 US US06/882,958 patent/US4693876A/en not_active Expired - Fee Related
  • 1985-10-16 BE BE0/215733A patent/BE903456A/fr not_active IP Right Cessation
  • 1985-10-16 CA CA000493085A patent/CA1248323A/fr not_active Expired
  • 1985-10-17 IT IT22530/85A patent/IT1201482B/it active

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