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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
  • C08G65/4043—(I) or (II) containing oxygen other than as phenol or carbonyl group
  • C08G65/405—(I) or (II) containing oxygen other than as phenol or carbonyl group in ring structure, e.g. phenolphtalein
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/52—Polyethers
  • B01D71/522—Aromatic polyethers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
  • B01D71/68—Polysulfones; Polyethersulfones
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
  • C08G65/4043—(I) or (II) containing oxygen other than as phenol or carbonyl group
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
  • C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
• • 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
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/20—Polysulfones
  • C08G75/23—Polyethersulfones
• • 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
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
  • C08G2650/26—Sugars or saccharides used as initiators
• • 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
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
  • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
  • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
• • 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
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/62—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the nature of monomer used
  • C08G2650/64—Monomer containing functional groups not involved in polymerisation

Definitions

• the invention relates to the field of polymers and relates to a process for the synthesis of semi-aromatic polyethers based on aliphatic diols, semi-aromatic polyethers based on aliphatic diols obtained by said process and the use of said semi-polyethers. aromatics based on aliphatic diols for the manufacture of membranes, manufactured parts and coatings.
• Aromatic polyethers obtained by aromatic nucleophilic substitution such as polyethersulfones, polyetherketones and polyetherbenzonitriles, are recognized as being high performance polymers due to their excellent thermal stability and mechanical properties.
• the main application of these polymers is liquid and gas phase separation membranes.
• the polyethersulfones available on the market are in particular synthesized from aromatic diols such as bisphenol A or 4,4′-dihydroxyphenyl with dichlorodiphenyl sulfone. Industrialists have thus taken an interest in partially or totally substituting aromatic diols such as bisphenol A, known to be an endocrine disruptor, with aliphatic diols.
• Isohexides or 1, 4: 3,6-dianhydrohexitols, are rigid bicyclic chiral diols derived from sugars.
• isosorbide is obtained from the double dehydration reaction of sorbitol, itself resulting from the reaction of hydrogenation of glucose.
• Isohexides constitute the intermediates of choice in the synthesis of numerous compounds which find their applications in various fields such as that of the plastics industry, thus replacing their counterparts resulting from the petrochemical industry.
• Kricheldorf et al. first described the preparation and characterization of polyethersulfones containing isosorbide from silylated isosorbide and difluorodiphenylsulfone (H. Kricheldorf et al., J. Polymer Soi., Part A: Polym. Chem., 1995, 33, 2667-2671).
• Silylated isosorbide having a high cost, Kricheldorf and Chatti modified their polymerization conditions and described the synthesis of polyethersulfones containing isosorbide from unfunctionalized isosorbide and difluorodiphenylsulfone in the presence of potassium carbonate ( S. Chatti et al., High Perform. Polym., 2009, 21, 105-1 18).
• Application WO 2013/023997 A1 describes a process for preparing aromatic polyetherketones based on isosorbide. The process involves the reaction between 4,4'-difluorobenzophenone and isosorbide in the presence of potassium carbonate at a temperature of 210 ° C.
• Application WO 2014/072473 A2 describes a process for preparing aromatic polyethersulfones based on isosorbide. The process involves the reaction between difluorodiphenylsulfone or dichlorodiphenylsulfone, optionally in the presence of a fluorinating agent, and isosorbide in the presence of potassium carbonate at a temperature of 210 ° C.
• Application US 2015/0129487 A1 describes a process for preparing semi-aromatic polyethersulfones based on non-aromatic cyclic diols such as cyclohexanedimethanol, 1, 5-cyclooctanediol or tetramethylcyclobutanediol.
• the process involves the reaction between 4,4'-difluorodiphenylsulfone and a non-aromatic cyclic diol in the presence of potassium carbonate at a minimum temperature of 160 ° C and the reaction between 4,4'-dichlorodiphenylsulfone and a non-cyclic diol.
• -aromatic in the presence of potassium carbonate at a minimum temperature of 210-215 ⁇ C.
• Block copolymerization is also envisaged by aromatic nucleophilic substitution between two blocks (LF Hancock, et al., Biomaterials, vol. 21, no 7, p. 725-733, 2000.) or by transetherification between a polymer and an oligomer of PEG in the presence of the strong base NaH (L. Wang et al., Polymer Chemistry, vol. 5, no. 8, p. 2836-2842, 2014.).
• the processes for preparing polyethersulfones based on diols and on dichlorodiphenyl sulfone of the prior art require either heating at high temperature ( 210-215 ° C) in the presence of a weak base such as K2CO3, ie the use of a strong base such as NaH which makes it possible to moderate the temperatures.
• a weak base such as K2CO3
• strong base such as NaH which makes it possible to moderate the temperatures.
• strong bases are known to induce side reactions of hydrolysis of dihalogenated diphenyl sulfone (RN Johnson and AG Farnham, J. Polym. Soi. A-1 Polym. Chem., Vol. 5, no. 9, p. . 2415-2427, 1967).
• the invention improves the situation in that it makes it possible to obtain semi-aromatic polyethers by aromatic nucleophilic substitution based on aliphatic diols with high average molar masses in number without requiring heating at high temperature for long durations.
• the invention relates to a process for preparing semi-aromatic polyethers based on aliphatic diols comprising the following successive steps:
• the invention also relates to a semi-aromatic polyether based on an aliphatic diol of formula I which can be obtained by said process:
• Ar is from a dihalogenated aromatic or heteroaromatic compound
• R is from an aliphatic diol
• X is halogen
• n is an integer between 2 and 100, n being determined by size exclusion chromatography.
• the invention also relates to the use of a semi-aromatic polyether according to the invention for the manufacture of membranes, manufactured parts and coatings.
• the characteristics exposed in the following paragraphs can, optionally, be implemented. They can be implemented independently of each other or in combination with each other.
• the aliphatic diol used in step a) of the process of the invention is chosen from linear aliphatic diols, branched aliphatic diols and cyclic aliphatic diols.
• the aliphatic diol used in step a) of the process of the invention is a branched aliphatic diol.
• the aliphatic diol used in step a) of the process of the invention is a cyclic aliphatic diol.
• the linear diol used in step a) of the process of the invention is a linear aliphatic diol.
• the aliphatic diol used in step a) of the process of the invention is chosen from 1, 4: 3,6-dianhydrohexitols.
• the 1,4: 3,6-dianhydrohexitol used in step a) of the process of the invention is isosorbide.
• the aromatic or dihalogenated heteroaromatic compound used in step a) of the process of the invention is chosen from dihalogenated aromatic sulfones, dihalogenated aromatic ketones, dihalogenated benzonitriles, dihalogenated diazene, bis (halophenyl) -oxadiazoles, dihalogenated nitrobenzenes, dihalogenated benzoyl-naphthalenes, and dihalogenated pyridines.
• the hindered strong base used in step a) of the process of the invention is chosen from potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium tert-pentoxide, sodium tert-pentoxide, potassium trimethylsilanolate, sodium trimethylsilanolate, lithium trimethylsilanolate, potassium tetramethylpiperidide, lithium tetramethylpiperidide, potassium bis (trimethylsilyl) amide, and lithium bis (trimethylsilyl) amide.
• the hindered strong base / aliphatic diol molar ratio is between 1 and 3.
• the organic solvent used in step a) of the process of the invention is a polar aprotic solvent or a mixture of polar aprotic solvents.
• the aliphatic diol / dihalogenated aromatic compound molar ratio is between 0.5 and 1.5.
• the semi-aromatic polyether based on an aliphatic diol of the invention is characterized in that R originates from an aliphatic diol selected from linear aliphatic diols and branched aliphatic diols.
• the semi-aromatic polyether based on an aliphatic diol of the invention is characterized in that R originates from a 1, 4: 3,6-dianhydrohexitol.
• the semi-aromatic polyether based on an aliphatic diol of the invention is characterized in that its polydispersity index is between 1, 5 and 5.
• the semi-aromatic polyether based on an aliphatic diol of the invention is characterized in that its number-average molar mass is greater than or equal to 5,000 g / mol, said molar mass number average being measured by size exclusion chromatography in dimethylformamide at 70 ° C. with a flow rate of 0.7 mL / min and with a polystyrene calibration.
• the semi-aromatic polyether based on an aliphatic diol of the invention is characterized in that it has a glass transition temperature greater than 100 ° C.
• the semi-aromatic polyether based on an aliphatic diol of formula I is characterized in that X is chlorine. In one embodiment, the semi-aromatic polyether based on an aliphatic diol of formula I is characterized in that it contains a residual fluorine level of less than 100 ppm.
• the semi-aromatic polyether based on an aliphatic diol of formula I is characterized in that it contains a residual silicon content of between 10 and 1000 ppm.
• the semi-aromatic polyether based on an aliphatic diol of formula I is characterized in that it contains a residual chlorine level of between 100 and 10,000 ppm.
• the invention and variants thereof may make it possible, in general, to provide a process for preparing semi-aromatic polyethers based on an aliphatic diol.
• the Applicant has shown that it is possible to synthesize semi-aromatic polyethers from an aliphatic diol, in particular secondary, and from an aromatic or heteroaromatic dihalogen compound in the presence of a strong base encumbered at a temperature less than or equal to 120 ° C for a period of less than or equal to 12 hours.
• Such a solution makes it possible to solve the problems posed by the known solutions and to obtain semi-aromatic polyethers based on an aliphatic diol with high number-average molar masses, that is to say greater than 5,000 g / mol, preferably greater than 6,000 g / mol, more preferably greater than 7,000 g / mol, said number-average molar masses being measured by size exclusion chromatography in dimethylformamide at 70 ° C with a flow rate of 0.7 mL / min and with a polystyrene calibration, without requiring high temperature heating.
• the process described by the Applicant has the advantages of being faster than the usual processes, of using non-toxic solvents, and of making it possible to obtain uncolored polymers.
• the present invention relates to a process for preparing semi-aromatic polyethers based on an aliphatic diol comprising the following successive steps:
• polysemi-aromatic polyether means a polymer of polyether type formed from two monomers, one of which is aromatic or heteroaromatic and the other is non-aromatic.
• the first step of the process according to the invention consists in preparing a mixture comprising an aliphatic diol or a mixture of aliphatic diols, preferably an aliphatic diol, a dihalogenated aromatic compound, a strong base hindered in an organic solvent.
• aliphatic diol is meant within the meaning of the present invention a non-aromatic organic compound comprising two hydroxyl functions.
• the aliphatic diol can be linear, branched or cyclic.
• linear aliphatic diols and “branched aliphatic diols” do not include cycles.
• cyclic aliphatic diols comprise one or more rings.
• the aliphatic diol is a branched aliphatic diol or a cyclic aliphatic diol. More preferably, the aliphatic diol is a branched aliphatic diol.
• the aliphatic diol may, in addition to the oxygen atoms of the two hydroxyl groups, contain one or more heteroatoms such as, for example, oxygen, nitrogen and sulfur atoms.
• the aliphatic diol is used in the present invention as a monomer for the formation of the semi-aromatic polyether.
• linear aliphatic diols that may be mentioned include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol and / or 1, 10-decanediol.
• branched aliphatic diols mention may be made of 2-methyl-1, 3-propanediol, 2,2-dimethylpropane-1, 3-diol, 2,2,4-trimethyl-1, 3-pentanediol, 2 -ethyl-2-butyl-1, 3-propanediol and / or propylene glycol.
• cyclic aliphatic diols examples include cyclohexanedimethanols, tetramethylcylcohexanedimethanol, hydrogenated bisphenols, 1, 5-cyclooctanediol, 1, 4: 3,6-dianhydrohexitols, spiroglycols, adamantimetanediodol and / or lehanol.
• 1, 4: 3,6-dianhydrohexitol is meant within the meaning of the present invention a heterocyclic compound obtained by double dehydration of a hexitol such as mannitol, sorbitol and iditol.
• 1,4: 3,6-dianhydrohexitols occur mainly in the form of stereoisomers: isomannide, isosorbide and isoidide.
• 1,4: 3,6-dianhydrohexitol is used in the present invention as a monomer for the formation of the semi-aromatic polyether.
• the 1,4: 3,6-dianhydrohexitol used in step a) of the process of the invention is isosorbide.
• the term “dihalogenated aromatic compound” means a compound comprising at least one aromatic ring, preferably two aromatic rings, two halogen atoms, and a function of electron withdrawing type.
• the halogen atoms are chosen from bromine, iodine, chlorine or fluorine, preferably from chlorine and fluorine, more preferably, the halogen atoms are chlorine atoms.
• the two halogen atoms are identical.
• the compound dihalogenated aromatic is used in the present invention as a monomer for the formation of the semi-aromatic polyether.
• dihalogenated heteroaromatic compound is meant within the meaning of the present invention a compound comprising at least one heteroaromatic ring, and two halogen atoms.
• the halogen atoms are chosen from bromine, iodine, chlorine or fluorine, preferably from chlorine and fluorine, more preferably the halogen atoms are chlorine atoms.
• the two halogen atoms are identical.
• the dihalogenated heteraromatic compound is used in the present invention as a monomer for the formation of the semi-aromatic polyether.
• the dihalogenated aromatic or heteraromatic compound used in step a) of the process of the invention is advantageously chosen from dihalogenated aromatic sulfones, dihalogenated aromatic ketones, dihalogenated benzonitriles, dihalogenated diazenes, bis (halophenyl) - oxadiazoles , dihalogenated nitrobenzenes, dihalogenated benzoyl-naphthalenes and dihalogenated pyridines.
• the dihalogenated aromatic or heteroaromatic compound is chosen from dihalogenodiphenyl sulfones, dihalodiphenyl ketones, dihalogenated benzonitriles and dihalogenated pyridines.
• the dihalogenated aromatic or heteroaromatic compound is chosen from dichlorodiphenyl sulfones, dichlorodiphenyl ketones, dichlorobenzonitriles and dichloropyridines. More preferably, the dihalogenated aromatic or heteroaromatic compound is chosen from 4,4′-dichlorodiphenyl sulfone, 4,4′-dichlorobenzophenone, 2,6-dichlorobenzonitrile and 2,6-dichloropyridine. Even more preferably, the dihalogenated aromatic or heteroaromatic compound is chosen from 4,4′-dichlorodiphenyl sulfone, 2,6-dichlorobenzonitrile and 2,6-dichloropyridine.
• hindered strong base is meant within the meaning of the present invention a base comprising a group of atoms occupying a large volume, such as for example a branched aliphatic group.
• the hindered strong base is chosen from potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium tert-pentylate, tert-pentylate sodium, potassium trimethylsilanolate, sodium trimethylsilanolate, lithium trimethylsilanolate, potassium tetramethylpiperidide, lithium tetramethylpiperidide, potassium bis (trimethylsilyl) amide, and lithium bis (trimethylsilyl) amide. More preferably, the hindered strong base used in step a) of the process of the invention is potassium trimethylsilanolate.
• a hindered strong base at a temperature less than or equal to 120 ° C makes it possible to limit the side reactions that may be generated when using an unhindered strong base, and thus makes it possible to obtain polymers with high number average molar masses, that is to say number average molar masses greater than 5,000 g / mol , preferably greater than 6,000 g / mol, more preferably greater than 7,000 g / mol, said number-average molar masses being measured by size exclusion chromatography in dimethylformamide at 70 ° C with a flow rate of 0.7 mL / min and with a polystyrene calibration.
• the proportion of congested strong base in the mixture is between 1 and 3 mole equivalents relative to the amount of aliphatic diol.
• the strong hindered base / aliphatic diol molar ratio is between 1 and 3.
• the strong hindered base / aliphatic diol molar ratio is approximately 2.
• the organic solvent used in step a) of the process of the invention is advantageously chosen from aprotic polar solvents.
• aprotic polar solvent means a solvent having a dipole moment without an acidic hydrogen atom, that is to say linked to a heteroatom.
• the solvent is chosen from aprotic polar solvents containing at least one sulfur atom or at least one nitrogen atom. More preferably, the solvent is chosen from dimethylsulfoxide, diethylsulfoxide, sulfolane, dimethylsulfone, diethylsulfone, diisopropylsulfone, diphenylsulfone, tetrahydrothiophene-1 -monoxide, dimethylacetamide, N, N-dimethylformamide, fluorine or methyl-5- (dimethylamino) -2-methyl-5-oxopentanoate, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, alone or in mixed. More preferably, the solvent is dimethylsulfoxide.
• the aliphatic diol used in step a) of the process of the invention is advantageously chosen from linear aliphatic diols, branched aliphatic diols and cyclic aliphatic diols.
• the aliphatic diol used in step a) of the process of the invention is chosen from branched aliphatic diols and cyclic aliphatic diols. More preferably, the aliphatic diol used in step a) of the process of the invention is chosen from branched aliphatic diols.
• the aliphatic diol used in step a) of the process of the invention is a linear aliphatic diol.
• the linear aliphatic diol used in step a) of the process of the invention is chosen from ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol and 1, 10-decanediol, alone or as a mixture.
• the aliphatic diol used in step a) of the process of the invention is a branched aliphatic diol.
• the branched aliphatic diol used in step a) of the process of the invention is chosen from 2-methyl-1, 3-propanediol, 2,2-dimethylpropane-1, 3-diol, 2, 2,4-trimethyl-1, 3-pentanediol, 2-ethyl-2-butyl-1, 3-propanediol and propylene glycol, alone or as a mixture.
• the branched aliphatic diol used in step a) of the process of the invention is 2,2-dimethylpropane-1, 3-diol.
• the aliphatic diol used in step a) of the process of the invention is a cyclic aliphatic diol.
• the cyclic aliphatic diol used in step a) of the process of the invention is chosen from cyclohexanedimethanols, tetramethylcylcohexanedimethanol, hydrogenated bisphenols, 1, 5-cyclooctanediol, 1, 4: 3,6-dianhydrohexitols , spiroglycols, adamantanediols and tricyclododecanedimethanol, alone or as a mixture.
• the cyclic aliphatic diol used in step a) of the process of the invention is chosen from 1, 4: 3,6-dianhydrohexitols. More preferably, the cyclic aliphatic diol used in step a) of the process of the invention is isosorbide.
• the isosorbide used may be in solid form, in particular in powder, granule or scale form, or else in liquid form, in particular in molten form.
• the isosorbide is in solid form.
• the aromatic or dihalogenated heteroaromatic compound used in step a) of the process of the invention is a dichlorinated aromatic compound.
• the dihalogenated aromatic or heteroaromatic compound used in step a) of the process of the invention is chosen from dichlorinated aromatic sulfones, dichlorinated aromatic ketones, dichlorinated benzonitriles and dichlorinated pyridines. More preferably, the dihalogenated aromatic or heteroaromatic compound used in step a) of the process of the invention is chosen from dichlorodiphenyl sulfones, dichlorodiphenyl ketones, dichlorobenzonitriles and dichloropyridines.
• the dihalogenated aromatic or heteroaromatic compound used in step a) of the process of the invention is chosen from 4,4'-dichlorodiphenyl sulfone, 4,4'-dichlorobenzophenone, 2,6-dichlorobenzonitrile and 2,6-dichloropyridine. Even more preferably, the dihalogenated aromatic or heteroaromatic compound used in step a) of the process of the invention is chosen from 4,4′-dichlorodiphenyl sulfone, 2,6-dichlorobenzonitrile and 2,6-dichloropyridine.
• dichlorinated aromatic derivatives in the process of the invention makes it possible to obtain semi-aromatic polyethers having high number average molar masses comparable to those obtained in the case of semi-aromatic polyethers prepared from difluorinated aromatic derivatives.
• the use of dichlorinated aromatic derivatives thus has an economic advantage, in fact, they are often less expensive than the corresponding difluorinated aromatic derivatives.
• the method of the invention unexpectedly makes it possible to improve the substitution kinetics when an aromatic compound or dichlorinated heteroaromatic is used in step a).
• the processes of the prior art usually use difluorinated monomers to overcome the low reactivity of aliphatic diols.
• halogenated derivative used can be identified by analysis of the polymer by combustion / ion chromatography coupling (Combustion Ion Chromatography in English).
• the molar ratio of aromatic or heteroaromatic dihalogenated compound / aliphatic diol in the mixture is between 0.5 and 1.5, preferably between 0.7 and 1.3, more preferably between 0.9 and 1 , 1. More preferably, the aromatic or heteroaromatic dihalogenated compound / aliphatic diol molar ratio in the mixture is approximately 1.
• the semi-aromatic polyether is formed by reaction between the aliphatic diol and the aromatic or heteroaromatic dihalogenated compound as monomers.
• the total proportion of monomers that is to say the sum of the quantity of aliphatic diol and of the quantity of aromatic or heteroaromatic dihalogen compound, is between 10% and 50%, preferably between 20% and 40%. % by mass relative to the sum of the mass of the solvent and the mass of the monomers. More preferably, the proportion of monomers is about 30% by mass based on the sum of the mass of the solvent and the mass of the monomers.
• the second step of the process of the invention consists in heating the mixture prepared in step a) at a temperature between 30 ° C and 120 ° C for a period of less than or equal to 12 hours. This heating step makes it possible to start the reaction between the aliphatic diol and the dihalogenated aromatic or heteroaromatic compound in order to form the semi-aromatic polyether.
• the heating step is carried out at a temperature between 35 ° C and 110 ° C, more preferably between 40 ° C and 100 ° C, for a period of less than or equal to 1 1 hours , more preferably less than or equal to 10 hours.
• the process of the invention is particularly advantageous in terms of productivity since it makes it possible to obtain semi-aromatic polyethers on a duration less than or equal to 12 hours, but also in terms of energy saving since it does not require heating to a temperature above 120 ° C.
• the heating step is started at a temperature between 30 ° C and 50 ° C, preferably between 35 ° C and 45 ° C, more preferably at a temperature of approximately 40 ° C, then the temperature is gradually increased to a temperature between 80 ° C and 120 ° C, preferably between 90 ° C and 110 ° C, more preferably at a temperature of about 100 ° C.
• the semi-aromatic polyether obtained can be recovered by techniques known to those skilled in the art, such as for example the precipitation of the semi-aromatic polyether.
• a preferred technique for precipitating the semi-aromatic polyether consists in adding the reaction medium to a large volume of water, approximately 10 times the volume of the reaction medium.
• the semi-aromatic polyether can then be dried according to techniques known to those skilled in the art, for example in a vacuum oven.
• the process of the invention thus makes it possible to obtain semi-aromatic polyethers based on an aliphatic diol exhibiting physical properties which are particularly suitable for the production of films.
• Another object of the invention relates to a semi-aromatic polyether based on an aliphatic diol obtainable by the process according to invention.
• This semi-aromatic polyether is characterized in that it corresponds to formula I:
• Ar is from a dihalogenated aromatic or heteroaromatic compound
• R is from an aliphatic diol
• X is halogen
• n is an integer between 2 and 100, n being determined by size exclusion chromatography.
• the polydispersity index of the semi-aromatic polyether based on an aliphatic diol of the invention can be determined by techniques known to those skilled in the art, in particular by size exclusion chromatography, for example in dimethylformamide at 70 ° C with a flow rate of 0.7 mL / min and with a polystyrene calibration.
• the semi-aromatic polyether based on an aliphatic diol according to the invention has a polydispersity index of between 1.5 and 5, preferably between 2 and 4.5.
• the number-average molar mass of the semi-aromatic polyether based on an aliphatic diol of the invention can be determined by techniques known to those skilled in the art, in particular by size exclusion chromatography, for example in dimethylformamide at 70 ° C with a flow rate of 0.7 mL / min and with a polystyrene calibration.
• the semi-aromatic polyether based on an aliphatic diol of the invention has a number-average molar mass greater than or equal to 5,000 g / mol, preferably greater than or equal to 6,000 g / mol, of more preferably greater than or equal to 7000 g / mol.
• the semi-aromatic polyether based on an aliphatic diol of the invention has a number-average molar mass of between 6000 and 9000 g / mol, preferably between 6500 and 9000 g / mol, more preferably between 7000 and 9000 g / mol, said number-average molar mass being measured by size exclusion chromatography in dimethylformamide at 70 ° C with a flow rate of 0.7 mL / min and with a polystyrene calibration.
• the glass transition temperature of the semi-aromatic polyether based on an aliphatic diol of the invention can be determined by techniques known to those skilled in the art, in particular by differential scanning calorimetry (DSC) with a flow rate 80 mL / min with nitrogen at 10 ° C / min or 20 ° C / min, preferably 10 ° C / min, from 20 ° C to 300 ° C and in a drilled aluminum crucible.
• the semi-aromatic polyether of the invention has a glass transition temperature greater than 100 ° C, preferably greater than 120 ° C, more preferably greater than 140 ° C.
• the glass transition temperature of the semi-aromatic polyether based on an aliphatic diol of the invention is greater than 140 ° C, preferably between 140 ° C and 260 ° C, more preferably between 150 ° C and 250 ° C.
• the semi-aromatic polyether based on an aliphatic diol of the invention may be semi-crystalline.
• semi-crystalline polymer is meant a polymer having crystalline zones and amorphous zones.
• the contact angle of the semi-aromatic polyether of the invention can be determined by techniques known to those skilled in the art, in particular by measuring the angle with a goniometer.
• the semi-aromatic polyether to be obtained by the process according to the invention has a contact angle with water of between 50 ° and 70 °, preferably of about 63 °.
• Preferred semi-aromatic polyethers based on an aliphatic diol of formula I are those in which Ar, R, X and n are defined as follows:
• Ar is from a dihalogenated aromatic sulfone, a dihalogenated aromatic ketone, a dihalogenated benzonitrile or a dihalogenated pyridine; preferably Ar is from a dihalogenated diphenyl sulfone, a dihalogenated diphenyl ketone, a dihalogenated benzonitrile or a dihalogenated pyridine; more preferably Ar comes from a dichlorodiphenyl sulfone, from a dichlorodiphenyl ketone, a dichlorobenzonitrile or a dichloropyridine; more preferably, Ar is chosen from:
• Ar is chosen from:
• R is from an aliphatic diol; preferably, R originates from an aliphatic diol selected from linear aliphatic diols, branched aliphatic diols and cyclic aliphatic diols; more preferably, R originates from an aliphatic diol chosen from linear aliphatic diols and branched aliphatic diols;
• X is halogen, preferably X is selected from F and Cl, more preferably X is Cl;
• n is an integer between 2 and 100, preferably n is an integer between 10 and 100, n being determined by size exclusion chromatography, preferably by size exclusion chromatography in dimethylformamide at 70 ° C with a flow rate of 0.7 mL / min and with a polystyrene calibration.
• the semi-aromatic polyether based on an aliphatic diol is as defined by formula I, with the proviso that R does not come from isosorbide, cyclohexanedimethanol, tetramethylcyclobutanediol or cis-1, 5-cyclooctanediol when Ar originates from a 4,4'-halo-diphenyl sulfone, and R does not originate from isosorbide when Ar originates from 4,4'-dihalobenzophenone.
• the aliphatic diol used in step a) of the process of the invention is a linear aliphatic diol.
• R comes from a linear aliphatic diol and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula la:
• L is from a linear aliphatic diol; preferably, L comes from a linear aliphatic diol chosen from ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8 -octanediol and 1, 10- decanediol.
• the aliphatic diol used in step a) of the process of the invention is a branched aliphatic diol.
• R comes from a branched aliphatic diol and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula Ib:
• B is from a branched aliphatic diol; preferably, B comes from a branched aliphatic diol chosen from 2-methyl-1, 3-propanediol, 2,2-dimethylpropane-1, 3-diol, 2,2,4-trimethyl-1, 3- pentanediol, 2-ethyl-2-butyl-1, 3-propanediol and propylene glycol; more preferably, B is from 2,2-dimethylpropane-1, 3-diol.
• the aliphatic diol used in step a) of the process of the invention is 2,2-dimethylpropane-1, 3-diol.
• B comes from 2,2-dimethylpropane-1, 3-diol and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula Ib-i:
• the aliphatic diol used in step a) of the process of the invention is a cyclic aliphatic diol.
• R originates from a cyclic aliphatic diol and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula le:
• Cy is from a cyclic aliphatic diol; preferably, Cy originates from a cyclic aliphatic diol chosen from cyclohexanedimethanols, tetramethylcylcohexanedimethanol, hydrogenated bisphenols, 1, 5-cyclooctanediol, 1, 4: 3,6-dianhydrohexitols, spiroglycols, adametanimetanodediols and adamantanodediols; more preferably, Cy is obtained from a cyclic aliphatic diol selected from 1, 4: 3,6-dianhydrohexitols; even more preferably, Cy is from isosorbide.
• the cyclic aliphatic diol used in step a) of the process of the invention is a 1,4: 3,6-dianhydrohexitol.
• Cy comes from a 1, 4: 3,6-dianhydrohexitol and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula Ic-i:
• the cyclic aliphatic diol used in step a) of the process of the invention is isosorbide.
• Cy comes from isosorbide and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula Ic-ii:
• the dihalogenated aromatic or heteroaromatic compound used in step a) of the process of the invention is 4,4′-dichlorodiphenyl sulfone.
• Ar originates from 4,4′-dichlorodiphenyl sulfone and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula II:
• n and R are as defined in formula I.
• the aliphatic diol used in step a) of the process of the invention is a linear aliphatic diol.
• R comes from a linear aliphatic diol and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula IIa: [0109] [Chem. 13]
• n and L are as defined in formula la.
• the aliphatic diol used in step a) of the process of the invention is a branched aliphatic diol.
• R comes from a branched aliphatic diol and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of the formula Mb:
• n and B are as defined in formula Ib.
• the branched aliphatic diol used in step a) of the process of the invention is 2,2-dimethylpropane-1, 3-diol.
• B comes from 2,2-dimethylpropane-1, 3-diol and the semi-aromatic polyether based on an aliphatic diol according to the invention is that of formula IIb-i:
• the aliphatic diol used in step a) of the process of the invention is a cyclic aliphatic diol.
• R comes from a cyclic aliphatic diol and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of the formula
• n and Cy are as defined in formula le.
• the cyclic aliphatic diol used in step a) of the process of the invention is a 1,4: 3,6-dianhydrohexitol.
• Cy comes from a 1, 4: 3,6-dianhydrohexitol and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of the formula llc-i:
• the cyclic aliphatic diol used in step a) of the process of the invention is isosorbide.
• Cy comes from isosorbide and the semi-aromatic polyether based on an aliphatic diol according to the invention is that of formula IIc-ii: [0119] [Chem. 18]
• the dihalogenated aromatic or heteroaromatic compound used in step a) of the process of the invention is 2,6-dichlorobenzonitrile.
• Ar comes from 2,6-dichlorobenzonitrile and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula III:
• n and R are as defined in formula I.
• the aliphatic diol used in step a) of the process of the invention is a cyclic aliphatic diol.
• R comes from a cyclic aliphatic diol and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula Ilia: [0123] [Chem. 20]
• n and Cy are as defined in formula le.
• the cyclic aliphatic diol used in step a) of the process of the invention is a 1, 4: 3,6-dianhydrohexitol.
• Cy comes from a 1, 4: 3,6-dianhydrohexitol and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula IIIa-i:
• n is as defined in formula le.
• the cyclic aliphatic diol used in step a) of the process of the invention is isosorbide.
• Cy comes from isosorbide and the semi-aromatic polyether based on an aliphatic diol according to the invention is that of formula IIIa-ii: [0127] [Chem. 22]
• n is as defined in formula le.
• the dihalogenated aromatic or heteroaromatic compound used in step a) of the process of the invention is 2,6-dichloropyridine.
• Ar comes from 2,6-dichloropyridine and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula IV:
• n and R are as defined in formula I.
• the aliphatic diol used in step a) of the process of the invention is a cyclic aliphatic diol.
• R comes from a cyclic aliphatic diol and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of the formula
• n and Cy are as defined in formula le.
• the cyclic aliphatic diol used in step a) of the process of the invention is a 1, 4: 3,6-dianhydrohexitol.
• Cy comes from a 1, 4: 3,6-dianhydrohexitol and the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula IVa-i:
• n is as defined in formula le.
• the cyclic aliphatic diol used in step a) of the process of the invention is isosorbide.
• Cy comes from isosorbide and the semi-aromatic polyether based on an aliphatic diol according to the invention is that of formula IVa-ii: [0135] [Chem. 26]
• n is as defined in formula le.
• the aromatic or dihalogenated heteroaromatic compound used in step a) of the process of the invention is a dichlorinated aromatic compound.
• the semi-aromatic polyethers based on an aliphatic diol according to the invention are those of formula I in which X is chlorine.
• the semi-aromatic polyether based on an aliphatic diol according to the invention contains a residual fluorine level of less than 100 ppm, said residual fluorine level being determined by combustion / ion chromatography coupling.
• the semi-aromatic polyether based on an aliphatic diol according to the invention also contains a residual silicon level of between 10 and 1000 ppm, said residual silicon level being determined by combustion / combustion coupling. ion chromatography.
• the semi-aromatic polyether based on an aliphatic diol according to the invention contains a residual chlorine level of between 100 and 10,000 ppm, said residual chlorine level being determined by combustion / combustion coupling. ion chromatography.
• the semi-aromatic polyether based on an aliphatic diol according to the invention exhibits solubility parameters allowing it to be soluble in a suitable solvent for the production of films.
• the semi-aromatic polyether based on an aliphatic diol according to the invention preferably the semi-aromatic polyether based on an aliphatic diol of formula llc-ii, exhibits good solubility at a concentration of 10 mg / mL at room temperature (20-25 ° C) in solvents selected from formic acid, acetonitrile, acetic acid, dimethyl sulfoxide, acrylonitrile, epichlorohydrin, acetone, methyl acetate, N, N-dimethylformamide, 2-methoxyethanol, propylene carbonate, butan-2-one, 2-ethoxyethanol, dimethylethanolamine, pyridine , furfurilic alcohol, N-methyl-2-pyrrolidine, benzaldehyde
• Another object of the present invention relates to the use of the semi-aromatic polyether based on an aliphatic diol according to the invention for the manufacture of membranes, manufactured parts and coatings.
• the membranes can be made from the semi-aromatic polyether based on an aliphatic diol of the invention according to techniques known to those skilled in the art.
• the membranes obtained with the semi-aromatic polyether based on an aliphatic diol according to the invention exhibit interesting hydrophilicity and gas permeability properties.
• the membranes can be in the form of porous or non-porous films.
• the membranes can be manufactured as a monofilament or as hollow fibers.
• the semi-aromatic polyether based on an aliphatic diol according to the invention can be used in aqueous media, including body fluids.
• the semi-aromatic polyether based on an aliphatic diol according to the invention is biocompatible and can therefore be used in the form of a membrane in the medical environment such as for hemodialysis or in the consumption environment (food and beverages), in the wastewater treatment environment.
• porous membranes in the form of tubes or of hollow fibers can have different sizes of pores known to those skilled in the art depending on their application (microfiltration, ultrafiltration, nanofiltration, reverse osmosis).
• the performance of aqueous membranes obtained with polyether semi-aromatic according to the invention can be improved by techniques known to those skilled in the art, in particular the use of sulfonated monomers or the post-treatment of the membranes by sulfonation or by surface treatment to prevent fouling.
• the membranes in the gas phase can be used for the production of nitrogen from the separation of the mixture of nitrogen and oxygen from the air, the production of methane from the separation of methane and C0 2 .
• the performance of the gas membranes obtained with the semi-aromatic polyether according to the invention can be improved by techniques known to those skilled in the art, in particular, the use of hindered monomers or the addition of additives such as substituted bisphenols. , naphthalenes or fluorenes or the use of thermally labile compounds to form pores.
• the membranes in the form of films or plates can be used for optics or for packaging.
• Molded parts can be made from the semi-aromatic polyether based on an aliphatic diol of the invention according to techniques known to those skilled in the art.
• the injection molding of the semi-aromatic polyether based on an aliphatic diol according to the invention can lead to the production of parts used in the health sector, with dental applications to replace metals, glass and others. disposable or reusable utensils, but also in the aeronautics, electronics and automotive sectors.
• Another object of the invention relates to the use of the semi-aromatic polyether based on an aliphatic diol according to the invention as a coating resin for metals to prevent corrosion.
• the coating obtained from the semi-aromatic polyether based on an aliphatic diol according to the invention can be applied to steel, aluminum, copper, metals used in the consumer sector (food and drink), the marine sector with the hulls of the boats, the aerospace, automotive, electrical sectors with cables and electronics with circuits.
• the semi-aromatic polyether resin based on an aliphatic diol according to the invention can also be applied to other substrates such as glass or glass. carbon fiber to form a composite after evaporation of the solvent from the resin.
• the composites formed from the resin of the semi-aromatic polyether based on an aliphatic diol according to the invention can be used in the aerospace and automotive fields to replace metal parts.
• DCDPS 4,4'-dichlorodiphenyl sulfone
• NMP N-methyl-2-pyrrolidone
• PS polystyrene
• Isosorbide (purity> 99.5%): Polysorb® P from Roquette Frées,
• DCDPS purity> 99%: Alfa Aesar, SiOMeaK / THF (2M): Acros Organics,
• DCBN Fluka purified by sublimation.
• Example 1 Preparation of a semi-aromatic polyether sulfone according to the invention based on isosorbide
• the temperature is gradually increased over several hours to 100 ° C and then the medium is left to stir for 2 hours at 100 ° C.
• the medium then takes in viscosity.
• the medium is then precipitated in 300 mL of distilled water and the product obtained is rinsed once with water and then once with an 80:20 (v / v) water / methanol mixture.
• the product is recovered by Büchner filtration and dried in a vacuum oven.
• Example 2 Preparation of a semi-aromatic polyether sulfone according to the invention based on 1, 3-dimethylpropane-diol
• the medium then takes in viscosity.
• the medium is then precipitated in 300 mL of water distilled and the product obtained in the form of a white powder is recovered by Büchner filtration and dried in a vacuum oven.
• the polymer has a melting point Tm of 290 ° C.
• Example 3 Preparation of a semi-aromatic polyetheritrile according to the invention from isosorbide and dichlorobenzonitrile
• Example 4 Preparation of a semi-aromatic polyetheritrile according to the invention from isosorbide and dichloropyridine
• reaction medium is diluted in NMP and then precipitated in the form of a beige powder in a mixture of 300 ml of water / methanol 50:50 (v / v), is filtered on a Büchner funnel, then dried in a vacuum oven.
• the number-average molar masses (Mn) and the polydispersity indices (Ip) of the polyethers obtained are determined by size exclusion chromatography (SEC).
• the glass transition temperatures (Tg) and the melting temperatures (Tm) of the polyethers obtained are determined by differential scanning calorimetry (DSC). The characterizations applied to the examples are described below:
• DSC Differential Scanning Calorimetry
• SEC Steric Exclusion Chromatography
• Elemental analysis estimate of the quantity of an atom in mg / kg (ppm) on a 20 g sample by Combustion / ion chromatography coupling.
• Table 2 shows that with the SiOMeaK base, glass transitions are obtained for short reactions and at low temperature for samples obtained from higher chlorinated monomers compared to reactions employing K 2 C0 3 .
• Example 1 has a residual fluorine level of less than 100 ppm and a silicon level of 80 ppm due to the use of the 3 K SiOMe base.
• a membrane can be prepared from a solution of the 20% by weight polymer in DMSO poured onto a glass plate. The solvent is then evaporated using the following thermal cycle: 80 ° C for 1 hour, 100 ° C for 1 hour, 120 ° C for 1 hour and 150 ° C for 1 hour and 180 ° C for 2 hours. After firing, a transparent and slightly colored membrane is obtained for Example 1.
• Membranes are also obtained with counter-examples 1 and 3 using NMP as solvent.
• Counter-Example 2 is not film-forming.
• ysl is the surface tension of the solid / liquid interfaces
• s1 is the surface tension of the liquid / gas interfaces
• the contact angle of the film obtained from the semi-aromatic polyether of Example 1 obtained by the process according to the invention shows that the polymer is more hydrophilic than the reference polysulfone based on bisphenol (Table 5 ).
• the hydrophilicity of the semi-aromatic polyether is an advantage for the water phase separation properties.
• - nplcit8 L. Wang et al., Polymer Chemistry, vol. 5, no.8, p. 2836-2842, 2014; and - nplcit9: R. N. Johnson and A. G. Farnham, J. Polym. Self. A-1 Polym. Chem., Vol. 5, n ° 9, p. 2415-2427, 1967.

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