Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
• • 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
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
• • 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
  • C08G65/48—Polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides

Definitions

• the present invention relates to a process for producing a polymer composition
• a process for producing a polymer composition comprising
• the present invention relates to polymer compositions obtainable by the process, to mixtures which comprise these polyarylene ethers and to the use of the polymer compositions according to the invention for the toughening of epoxy resins.
• Polyarylene ethers belong to the group of high-performance thermoplastics and are used in highly stressed applications because of their high heat resistance and chemical resistance. See G. Blinne, M. Knoll, D. Müller, K. Schlichting, Kunststoffe 75, 219 (1985), EM Koch, H .-M. Walter, Kunststoffe 80, 1 146 (1990) and D. Döring, Kunststoffe 80, 1149 (1990).
• a widely used product for this application is Sumikaexcel® 5003 P from Sumitomo.
• the preparation of this product is carried out by condensation of the corresponding monomers in diphenyl sulfone and subsequent purification of the material by extraction with organic solvents.
• This process is expensive and also provides a polymer composition which has a high proportion of phenolate end groups and thus of potassium (> 700 ppm), which is disadvantageous for further processing. If such polymer compositions are isolated by precipitation, finely divided precipitates are formed, which are difficult to handle for industrial processes.
• the preparation of the polyarylene ethers is usually carried out by polycondensation of suitable starting compounds in dipolar aprotic solvents at elevated temperature (RN Johnson et al., J. Polym. Sci. A-15 (1967) 2375, JE McGrath et al. Polymer 25 (1984) 1827). McGrath et al., Polymer 30 (1989), 1552 also discloses that, after the condensation reaction has ended, the proportion of amino end groups can be reduced by the addition of acetic acid during the workup of polyarylene ethers.
• the object of the present invention was to provide reactive, d. H. OH-terminated polyarylene ether. It was the object of the present invention to avoid the disadvantages of the prior art. It was a further object of the present invention to provide a process for the preparation of OH-terminated polyarylene ethers wherein the product is obtained as a readily handleable precipitate.
• the polymer compositions obtainable in this way should have high color stability and temperature stability. In particular, the OH-terminated polyarylene ethers should discolor as little as possible when processed in the melt.
• the process for their preparation should be easy to carry out and provide a high polymer yield.
• the process for the preparation of polyarylene ethers comprises the following steps in the sequence a-b-c:
• t, q independently of one another 0, 1, 2 or 3
• Ar, Ar 1 independently of one another an arylene group having from 6 to 18 carbon atoms,
• phenolate end groups are understood as meaning negatively charged oxygen atoms in the form of an end group which are bonded to an aromatic nucleus. These end groups are derived from the phenolic end groups by removal of a proton.
• a phenolic end group is understood as meaning a hydroxy group which is bonded to an aromatic nucleus.
• the aromatic nuclei mentioned are preferably 1,4-phenylene groups.
• the polyarylene ethers (P) of the present invention may, on the one hand, have phenolate or phenolic OH end groups and, on the other hand, halogen end groups.
• the polymer composition of the present invention preferably consists essentially of polyarylene ethers having predominantly phenolic end groups, i. from OH-terminated polyarylene ethers.
• predominantly phenolate end groups is to be understood as meaning that more than 50% of the end groups present are phenolate end groups. Accordingly, the term “predominantly phenolic end groups” is to be understood as meaning that more than 50% of the end groups present are phenolic in nature ,
• the determination of the proportion of phenolate end groups is preferably carried out by determining the OH end groups by potentiometric titration and determination of the organically bound halogen end groups by means of atomic spectroscopy and subsequent calculation of the respective numerical proportions in%. Corresponding methods are known to the person skilled in the art. Alternatively, the determination of the proportions of the respective end groups can be carried out by means of 13 C nuclear magnetic resonance spectroscopy.
• step (a) the provision of the polyarylene ether or of the polyarylene ethers (P) with predominantly phenolate end groups in step (a) is carried out by reaction at least one starting compound of the structure X-Ar-Y (A1) with at least one starting compound of the structure HO-ArI-OH (A2) in the presence of a solvent (L) and a base (B), wherein
• - Y is a halogen atom
• - X is selected from halogen atoms and OH
• Ar and Ar 1 independently represent an arylene group having 6 to 18 carbon atoms.
• step (a) of the process according to the invention at least one polyarylene ether (P) is provided in the presence of a solvent (L), wherein the at least one polyarylene ether (P) is built up from building blocks of the general formula I with the meanings as defined above and predominantly phenolate end groups:
• the polyarylene ether (P) preferably has at least 60%, particularly preferably at least 80%, in particular at least 90% of phenolate end groups, based on the total number of end groups.
• the provision of the polyarylene ether (P) is preferably carried out in the form of a solution in the solvent (L).
• Q, T and Y in formula (II) are independently selected from -O- and -SO 2 -, provided that at least one of Q, T and Y is -SO 2 -.
• R a and R b are each independently a hydrogen atom or a C 1 -C 12 alkyl, C 1 -C 12 alkoxy or C 6 -C 18 aryl group.
• C 1 -C 12 -alkyl groups include linear and branched, saturated alkyl groups having from 1 to 12 carbon atoms.
• the following radicals are to C 1 -C 6 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, 2- or 3-methyl-pentyl and longer-chain radicals such as unbranched heptyl, octyl, nonyl , Decyl, undecyl, lauryl and the mono- or poly-branched analogs thereof.
• Suitable alkyl radicals in the abovementioned usable C 1 -C 12 -alkoxy groups are the alkyl groups having from 1 to 12 carbon atoms defined above.
• Preferred cycloalkyl radicals include in particular C 3 -C 12 -CCCl-alkyl radicals, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclpentylethyl, -propyl, -butyl , -pentyl, -hexyl, cyclohexylmethyl, -dimethyl, -trimethyl.
• Ar and Ar 1 independently represent a C 1 -C 6 -arylene group.
• Ar is preferably derived from an electron-rich, readily electrophilically attackable aromatic substance, which is preferably selected from the group consisting of hydroquinone, resorcinol, dihydroxynaphthalene, in particular 2,7-dihydroxynaphthalene, and 4,4 '. -Bisphenol is selected.
• Ar 1 is an unsubstituted C 6 or C 12 arylene group.
• Phenylene groups such as 1, 2, 1, 3 and 1, 4-phenylene, naphthylene groups, such as, for example, 1, 6, 1, 7, and 2,6, are used as C 6 -C 18 -arylene groups Ar and Ar 1 - And 2,7-naphthylene, and derived from anthracene, phenanthrene and naphthacene arylene groups into consideration.
• Ar and Ar 1 in the preferred embodiment according to formula (I) are preferably selected independently from the group consisting of 1, 4-phenylene, 1, 3-phenylene, naphthylene, in particular 2, 7-dihydroxynaphthalene, and 4,4'- biphenylene.
• polyarylene ether (P) preferably present blocks are those which contain at least one of the following recurring structural units Ia to Io:
• those building blocks are also preferred in which one or more 1,4-dihydroxyphenyl units are replaced by resorcinol or dihydroxynaphthalene units.
• Particularly preferred building blocks of the general formula I are the building blocks Ia, Ig and Ik. It is also particularly preferred if the polyarylene ethers of the polyarylene ethers (P) are essentially composed of one kind of building blocks of the general formula I, in particular of one building block selected from Ia, Ig and Ik.
• PESU polyethersulfone
• the polyarylene ethers (P) which are provided in the context of step (a) predominantly comprise phenolate end groups according to the invention.
• the phenolate end groups are converted in the course of the process according to the invention to phenolic end groups.
• the polyarylene ether thus has phenolic end groups.
• polyarylene ethers with predominantly phenolic end groups are referred to below as reactive polyarylene ethers.
• the polyarylene ethers (P) have average molecular weights M n (number average) in the range from 2,000 to 60,000 g / mol, in particular 5,000 to 40,000 g / mol, determined by gel permeation chromatography in the solvent dimethylacetamide against narrow-distribution polymethyl methacrylate as standard.
• the polyarylene ethers (P) preferably have relative viscosities of from 0.20 to 0.95 dl / g, in particular from 0.30 to 0.80. Depending on the solubility of the polyarylene ether sulfones, the relative viscosities are measured either in 1% strength by weight N-methylpyrrolidone solution, in mixtures of phenol and dichlorobenzene or in 96% strength sulfuric acid at 20 ° C. and 25 ° C., respectively.
• polyarylene ethers (P) can in principle be carried out in various ways.
• a corresponding polyarylene ether (P) may be contacted directly with a suitable solvent and directly, i. H. without further implementation, be used in the process according to the invention.
• prepolymers of polyarylene ethers can be used and brought to reaction in the presence of a solvent, wherein the described polyarylene (P) arise in the presence of the solvent.
• the polyarylene ethers (P) are prepared starting from suitable starting compounds, in particular starting from monomers in the presence of a solvent (L) and a base (B). Such production methods are known per se to the person skilled in the art.
• step (a) of this preferred embodiment the reaction of at least one starting compound of the structure X-Ar-Y (A1) with at least one starting compound of the structure HO-Ar 1 -OH (A2) takes place in the presence of a Solvent (L) and a base (B), wherein
• Y is a halogen atom
• - X is selected from halogen atoms and OH, preferably from halogen atoms, in particular F, Cl, or Br and
• Ar and Ar 1 independently represent an arylene group having 6 to 18 carbon atoms.
• the ratio of (A1) and (A2) is chosen so that the number of phenolic or phenolate end groups exceeds the number of halogen end groups.
• a polyarylene ether is thus prepared which is in contact with a solvent (L) and is preferably dissolved therein.
• Suitable starting compounds are known to the person skilled in the art and are not subject to any fundamental restriction, provided that the abovementioned substituents are sufficiently reactive in the context of a nucleophilic aromatic substitution.
• the reaction in step (a) is simultaneously a polycondensation with arithmetic elimination of hydrogen halide.
• Preferred starting compounds are difunctional in the context of AF-vz.
• Difunctional means that the number of reactive groups in the nucleophilic aromatic substitution is two per starting compound.
• Another criterion for a suitable difunctional starting compound is sufficient solubility in the solvent, as explained in more detail below.
• preferred compounds (A2) are those having two phenolic hydroxyl groups.
• reaction of the phenolic OH groups preferably takes place in the presence of a base in order to increase the reactivity with respect to the halogeno substituents of the starting compound (A1).
• Step (a) is preferably carried out starting from monomers and not starting from prepolymers.
• the starting compound (A1) used is a dihalodiphenylsulfone.
• the starting compound (A2) used is preferably dihydroxydiphenylsulfone.
• Suitable starting compounds (A1) are, in particular, dihalodiphenylsulfones, such as 4,4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, 4,4'-dibromodiphenylsulfone, bis (2-chlorophenyl) sulfones, 2,2'-dichlorodiphenylsulfone and 2,2'-dichloromethane.
• Difluordiphenylsulfon, with 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl are particularly preferred.
• Preferred starting compounds (A2) having two phenolic hydroxyl groups are selected from the following compounds:
• Dihydroxynaphthalenes in particular 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene;
• Dihydroxybiphenyls especially 4,4'-biphenol and 2,2'-biphenol;
• Bisphenyl ethers especially bis (4-hydroxyphenyl) ether and bis (2-hydroxyphenyl) ether;
• Bis-phenylpropanes especially 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane;
• Bisphenylmethanes especially bis (4-hydroxyphenyl) methane
• Bisphenylsulfones especially bis (4-hydroxyphenyl) sulfone
• Bisphenyl sulfides especially bis (4-hydroxyphenyl) sulfide
• - Bisphenylketone in particular bis (4-hydroxyphenyl) ketone
• Bis-phenylhexafluoropropanes especially 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) hexafluoropropane
• Bisphenylfluorenes especially 9,9-bis (4-hydroxyphenyl) fluorene.
• aromatic dihydroxy compounds (A2) it is preferable, starting from the abovementioned aromatic dihydroxy compounds (A2), to prepare their dipotassium or disodium salts by addition of a base (B) and to react with the starting compound (A1).
• the aforementioned compounds can also be used individually or as a combination of two or more of the aforementioned compounds.
• Hydroquinone, resorcinol, dihydroxynaphthalene, especially 2,7-dihydroxynaphthalene, and 4,4'-bisphenol are particularly preferred as the starting compound (A2).
• trifunctional compounds In this case, branched structures arise. If a trifunctional starting compound (A2) is used, 1,1,1-tris (4-hydroxyphenylethane) is preferred.
• the proportions to be used arise, in principle, from the stoichiometry of the polycondensation reaction proceeding with the computational elimination of hydrogen chloride and are set by a person skilled in the art in a known manner. However, to increase the number of phenolic OH end groups, an excess of OH end groups is preferable.
• polyaryl ethers with simultaneous control of the end groups is known per se to the person skilled in the art and will be described in more detail below.
• the known polyarylene ethers usually have phenolic halogen, especially -F or -Cl, or phenolic OH or O ⁇ end groups, the latter usually being further reacted in the prior art, in particular to CHsO groups.
• the molar ratio (A2) / (A1) is particularly preferably from 1.005 to 1.2, in particular 1.01 to 1.15, very particularly preferably 1.02 to 1.1.
• an excess of hydroxy groups is set by addition of the starting compound (A2).
• the ratio of the phenolic end groups used to halogen is preferably from 1.01 to 1.2, in particular 1. 03 to 1.15, very particularly preferably 1.05 to 1.1.
• the conversion in the polycondensation in the context of AF-vz according to step (a) in the preferred embodiment is at least 0.9, whereby a sufficiently high molecular weight is ensured.
• the degree of polymerization refers to the number of actual monomers.
• Preferred solvents (L) for the purposes of the present invention are aprotic polar solvents. Suitable solvents also have a boiling point in the range of 80 to 320 ° C, especially 100 to 280 ° C, preferably 150 to 250 ° C. Suitable aprotic polar solvents are, for example, high-boiling ethers, esters, ketones, asymmetrically halogenated hydrocarbons, anisole, dimethylformamide, dimethyl sulfoxide, sulfolane and N-methyl-2-pyrrolidone.
• a preferred solvent is in particular N-methyl-2-pyrrolidone.
• reaction of the starting compounds (A1) and (a2) in said aprotic polar solvents (L), in particular N-methyl-2-pyrrolidone is particularly preferable.
• reaction of the starting compounds (A1) and (A2) takes place in the presence of a base (B).
• the bases are anhydrous.
• Suitable bases are, in particular, anhydrous alkali metal carbonate, preferably sodium, potassium, calcium carbonate or mixtures thereof, with potassium carbonate being particularly preferred, especially potassium carbonate having a volume-weighted mean particle size of less than 100 micrometers, determined by means of a particle size measuring device in a suspension in N. methyl-2-pyrrolidone.
• a particularly preferred combination is N-methyl-2-pyrrolidone as solvent (L) and potassium carbonate as base (B).
• the reaction of the appropriate starting compounds (A1) and (A2) is carried out at a temperature of 80 to 250 ° C, preferably 100 to 220 ° C, the upper limit of the temperature being determined by the boiling point of the solvent.
• the reaction is preferably carried out in a time interval of 2 to 12 h, in particular from 3 to 8 h.
• step (a) the amount of the polyarylene ether (P) based on the total weight of the mixture of polyarylene ether (P) and solvent (L) of 10 to 70 wt .-%, preferably from 15 to 50% by weight.
• step (b) of the process according to the invention at least one polyfunctional carboxylic acid is added to the polyarylene ether (P) from step (a), preferably to dissolve the polyarylene ether (P) in the solvent (L).
• polyfunctional is meant a functionality of at least 2. The functionality is the (optionally average) number of COOH groups per molecule. "" More functionality is understood to mean a functionality of two or higher. "” Carboxylic acids preferred in the context of the present invention are " and trifunctional carboxylic acids.
• polyfunctional carboxylic acid can be carried out in various ways, in particular in solid or liquid form or in the form of a solution, preferably in a solvent which is miscible with the solvent (L).
• the polyfunctional carboxylic acid has a number average molecular weight of at most 1500 g / mol, in particular at most 1200 g / mol.
• the polyfunctional carboxylic acid preferably has a number-average molecular weight of at least 90 g / mol.
• Suitable polyfunctional carboxylic acids are in particular those according to general structure II:
• R represents a hydrocarbon radical having from 2 to 20 carbon atoms, which optionally contains further functional groups, preferably selected from OH and COOH.
• Preferred polyfunctional carboxylic acids are C 4 to C 10 dicarboxylic acids, in particular succinic acid, glutaric acid, adipic acid, and tricarboxylic acids, in particular citric acid.
• Particularly preferred polyfunctional carboxylic acids are succinic acid and citric acid.
• step (b) of the process according to the invention preference is given to a polyfunctional carboxylic acid in an amount of from 25 to 200 mol% of carboxyl groups, preferably from 50 to 150 mol% of carboxyl groups, particularly preferably from 75 to 125 mol% of carboxyl groups , determined to add based on the amount of phenolate or phenolic end groups determined.
• step (c) of the process according to the invention the recovery of the polymer composition takes place as a solid.
• the preferred precipitation can be carried out in particular by mixing the solvent (L) with a poor solvent (L ').
• a poor solvent is a solvent in which the polymer composition does not dissolve. Such a poor solvent is preferably a mixture of a non-solvent and a solvent.
• a preferred non-solvent is water.
• a preferred solvent (L ') mixture with a non-solvent is preferably a mixture of the solvent (L), especially N-methyl-4-pyrrolidone, and water. It is preferable to add the polymer solution from step (b) to the poor solvent (L '), resulting in the precipitation of the polymer composition. In this case, an excess of the poor solvent is preferably used.
• the addition of the polymer solution from step (a) takes place in finely divided form, in particular in drop form.
• a poor solvent (L ') a mixture of water and N-methyl-2-pyrrolidone (NMP) in combination with N-methyl-2-pyrrolidone as the solvent (L) is preferred.
• NMP N-methyl-2-pyrrolidone
• Particularly preferred as a poor solvent (L ') is a mixture NMP / water of 1: 3 to 1:50, in particular 1: 4 to 1: 30.
• the precipitation is particularly efficient if the content of the polymer composition in the solvent (L) is from 10 to 50% by weight, preferably from 15 to 35% by weight, based on the total weight of the mixture of polymer composition and solvent (L) ,
• the purification of the polyarylene ether copolymers is carried out by methods known to the person skilled in the art, for example washing with suitable solvents in which the polyarylene ether copolymers according to the invention are preferably largely insoluble.
• the polymer composition according to the invention essentially consists of the building blocks of the polyarylene ether or of the polyarylene ether (P), of which predominantly phenolate end groups are present as phenolic end groups, ie OH-terminated.
• the proportion of the phenolic end groups of the polymer composition of the present inventive method is at least 0.1 wt .-% OH calculated as the amount by weight OH based on the total amount of the polymer composition, in particular at least 0.12 wt .-%, particularly preferably at least O, 15% by weight.
• the determination of the phenolic end groups as the amount by weight of OH in relation to the total amount of the polyarylene ether is carried out by means of potentiometric titration.
• the polymer is dissolved in dimethylformamide and titrated with a solution of tetrabutylammonium hydroxide in toluene / methanol. Endpoint detection is potentiometric.
• the polymer composition according to the present invention preferably has a potassium content of at most 600 ppm.
• the potassium content is determined in the context of the present invention by means of atomic spectrometry.
• Another object of the present invention are mixtures, preferably reactive resins, in particular epoxy resins containing the polymer compositions of the invention.
• Such reactive resins are known to those skilled in the art and consist of reactive polymers which, depending on the reaction conditions, with the addition of suitable hardeners, give a thermosetting plastic of high strength and chemical resistance.
• polymer compositions according to the invention for the toughening of reactive resins, in particular epoxy resins, is preferred.
• the viscosity number of the polyarylene ethers (P) was determined in 1% solution in N-methyl-2-pyrrolidone at 25 ° C according to ISO 1628.
• the proportion of OH groups was determined by potentiometric titration.
• the potassium content was determined by atomic spectroscopy.
• the precipitation is assessed according to the following criteria:
• the precipitation was carried out by adding dropwise a polymer solution having a polymer content between 20 and 22 wt .-% in a mixture of water / NMP in the ratio 80/20 at room temperature.
• the polyarylene ether (P-1) was obtained by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 509.72 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept under nitrogen atmosphere at 190 ° C for 6 hours. Thereafter, the reaction was diluted by adding 1000 ml of NMP, the solid was separated by filtration and the polymer was isolated by precipitation in NMP / water 1/4. After careful washing with water, the product was dried in vacuo at 120 ° C for 12 hours. The viscosity number of the product was 55.2 ml / g.
• the polyarylene ether (P-2) was obtained by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenyl sulfone, 509.72 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept under nitrogen atmosphere at 190 ° C for 6 hours. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Subsequently, at 80 ° C, 5.54 g of succinic acid was added and stirred for 30 minutes. The polymer was then isolated by precipitation in NMP / water 1/4. After thorough washing with water, the product was dried in vacuo at 120 ° C for 12 hours. The viscosity number of the product was 54.9 ml / g.
• the polyarylene ether (P-3) was prepared by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 512.09 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept at 190 ° C for 6 hours. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Subsequently, the polymer was isolated by precipitation in NMP / water 1/4. After thorough washing with water, the product was dried in vacuo at 120 ° C for 12 h. The viscosity number of the product was 52.5 ml / g.
• the polyarylene ether (P-4) was prepared by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 512.09 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept at 190 ° C. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Then, at 80 ° C, 6.2 g of succinic acid was added and stirred for 30 minutes. Thereafter, the polymer was isolated by precipitation in NMP / water 1/4. After careful washing with water, the product was dried in vacuo at 120 ° C for 12 h. The viscosity number of the product was 52.6 ml / g.
• the polyarylene ether (P-5) was obtained by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 512.09 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept at 190 ° C for 6 hours. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Subsequently, at 80 ° C, 8.13 ml of phosphoric acid (85%) was added and stirred for 30 minutes. Thereafter, the polymer was isolated by precipitation in NMP / water 1/4. After thorough washing with water, the product was dried in vacuo at 120 ° C for 12 hours. The viscosity number of the product was 52.4 ml / g.
• the polyarylene ether (P-6) was prepared by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 512.09 g of dihydroxydiphenylsulfone, under the influence of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept at 190 ° C for 6 hours. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Then, at 80 ° C, 10.1 g of citric acid was added and stirred for 30 minutes. Thereafter, the polymer was isolated by precipitation in NMP / water 1/4. After thorough washing with water, the product was dried in vacuo at 120 ° C for 12 hours. The viscosity number of the product was 52.6 ml / g.
• the polyarylene ether (P-7) was obtained by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 516.07 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept at 190 ° C for 6 hours. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Subsequently, the polymer was isolated by precipitation in NMP / water 1/4. After thorough washing with water, the product was dried in vacuo at 120 ° C for 12 h. The viscosity number of the product was 38.3 ml / g.
• the polyarylene ether (P-8) was prepared by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 512.09 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept at 190 ° C for 6 hours. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Subsequently, at 80 ° C, 13.1 g of citric acid was added and stirred for 30 minutes. Thereafter, the polymer was isolated by precipitation in NMP / water 1/4. After thorough washing with water, the product was dried in vacuo at 120 ° C for 12 h. The viscosity number of the product was 39.4 ml / g.
• the polymer compositions of the present invention have high temperature and color stability.
• the discoloration and turbidity is significantly reduced compared to the use of acetic acid or mineral acids.
• the polymer compositions also have a significantly reduced potassium content.

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• 2009
  • 2009-11-12 KR KR1020117013933A patent/KR101694276B1/ko active IP Right Grant
  • 2009-11-12 MY MYPI20112157 patent/MY150816A/en unknown
  • 2009-11-12 ES ES09755880T patent/ES2399961T3/es active Active
  • 2009-11-12 WO PCT/EP2009/065035 patent/WO2010057822A1/de active Application Filing
  • 2009-11-12 JP JP2011536829A patent/JP5645838B2/ja active Active
  • 2009-11-12 BR BRPI0920955A patent/BRPI0920955A2/pt not_active IP Right Cessation
  • 2009-11-12 US US13/130,139 patent/US20110224386A1/en not_active Abandoned
  • 2009-11-12 EP EP09755880A patent/EP2358787B1/de active Active
  • 2009-11-12 CN CN200980146551.6A patent/CN102224185B/zh active Active

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