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
  • 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

Definitions

• the invention relates to a process for the production of polyethers, in particular polyethers containing sulfone groups.
• polysulfone ethers are preferably prepared by reacting aromatic alkali phenolates with aromatic halogen compounds. Aqueous solutions of the alkali metal hydroxide are added in the preparation of the alkali metal salt. Exactly stoichiometric amounts must be adhered to here, since an excess or deficit of the base leads to unsatisfactory molecular weights. In addition, large phenolate agglomerates often form due to the water present, which can lead to considerable disturbances in the polycondensation.
• Suitable bisphenols are compounds which differ from the general formula can be derived in which Ar is an aromatic radical with 6 carbon atoms, A is a divalent radical from the group -S0 2 -, -CO- and n and m is 0 or 1.
• Such bisphenols are, for example, hydroquinone, resorcinol, 4,4f-bisphenol, bis (4-oxyphenyl) sulfone and bis (4-oxyphenyl) ketone.
• the bisphenols mentioned can be used individually or in the form of mixtures.
• Bis (4-oxyphenyl) sulfone is preferably used.
• Derivatives of the general formulas are suitable as dichlorobenzene compounds in which B represents the radical -CO- or -S0 2 -, D represents -0-or -S- and x is 0 or 1.
• dichlorobenzene compounds examples include: bis (4-chlorophenyl) sulfone, bis (4-chlorophenyl) ketone, 1,4-bis (4-chlorobenzoyl) benzene, 1,4-bis (4- chlorobenzenesulfonyl) benzene, 4,4'-bis (4-chlorobenzoyl) diphenyl ether, 4,4'-bis (4-chlorobenzyl) diphenyl sulfide, 4,4'-bis (4-chlorobenzoyl) diphenyl, 4,4'-bis (4-chlorobenzenesulfonyl) diphenyl ether, 4,4'-bis (4-chlorobenzenesulfonyl) diphenyl sulfide or 4,4'-bis (4-chlorobenzenesulfonyl) diphenyl.
• the dichlorobenzene compounds can also be used individually or as a mixture.
• N-substituted acid amides the sulfoxides or sulfones
• N-substituted acid amides for example N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone (sulfolane) or, are used as polar, aprotic solvents Diphenyl sulfone.
• N-methylpyrrolidone is preferably used.
• the polar, aprotic solvents are used in amounts of 5 to 100, preferably 10 to 20, moles, based on one mole of bisphenol or dichlorobenzene compound. This means that the reaction solutions in the absence of alkali carbonate and azeotroping agent have a solids content of 5 to 50% by weight, preferably 20 to 35% by weight, based on the total weight.
• anhydrous alkali carbonates are sodium and preferably potassium carbonate.
• 1 to 2 preferably 1.0 to 1.2, mol of anhydrous alkali metal carbonate are used per mole of bisphenol and dichlorobenzene compound.
• Suitable water azeotroping agents are all substances which boil in the range of the reaction temperature at normal pressure can be mixed homogeneously with the reaction mixture without undergoing chemical reactions.
• azeotroping agents of the type mentioned are: chlorobenzene, toluene and xylene.
• Chlorobenzene is preferred.
• the azeotroping agents are used in amounts such that the quantitative separation of the water formed during the neutralization of hydrogen chloride and alkali carbonate is ensured.
• the amount of azeotroping agent required also depends on the type and size of the device. However, the required amount can easily be determined experimentally.
• azeotrope is not circulated, it has proven to be advantageous to use about 2 to 10 moles of azeotrope per mole of alkali metal carbonate in the first reaction stage.
• the process according to the invention is preferably used for the polycondensation of about 1 mol of bis (4-oxyphenyl) sulfone with about 1 mol of bis (4-chlorophenyl) sulfone in N-methylpyrrolidone as an aprotic solvent in the presence of 1.0 to 1.2 Mol of anhydrous potassium carbonate and chlorobenzene used as water azeotrope to polyethers.
• the reaction mixture in the first reaction stage is separated off at least 90% by weight, preferably 90 to 96% by weight, based on the total weight, of what is theoretically possible amount of water advantageously heated for 0.5 to 4 hours, preferably 1 to 2 hours.
• the reaction mixture is polycondensed until completely water-free and for this purpose, the reaction mixture is continuously mixed with further azeotrope and the azeotrope mixture formed is distilled off simultaneously.
• the reaction time is approximately 1.5 to 4 hours, preferably 1 to 2 hours.
• the polycondensation is then stopped by introducing methyl chloride.
• the reaction time for this is approximately 0.1 to 2, preferably 0.2 to 0.5 hours.
• the isolation of the polyether in the fourth stage can be carried out in various ways.
• the solid polymer can be separated by mixing the reaction solution with a precipitant, e.g. Water and / or methanol, by vigorous stirring, splashing or atomizing.
• a precipitant e.g. Water and / or methanol
• the solvent can also be evaporated.
• the inorganic constituents can be removed from the polyether by suitable methods such as dissolving, filtering or sieving.
• the polyethers produced using the process according to the invention have reduced viscosities (measured at 24 ° C. in a 1% strength sulfuric acid solution) from 0.4 to 1.5. This corresponds to molecular weights of 15,000 to 120,000.
• the polyethers produced are particularly suitable for the production of moldings, fibers, films, adhesives and coating materials.
• the invention is illustrated by the following examples and comparative examples.
• the parts mentioned are parts by weight.
• the reduced viscosities ( ⁇ red ) were measured at 24 ° C in 1% sulfuric acid solution and according to the formula certainly.
• the color evaluation of the polyethers was carried out by UV measurement on 1% sulfuric acid solutions.
• the light transmittance of the solution was measured in the range from 400 to 800 m ⁇ at intervals of 50 m / u and the average transmittance was calculated from this.
• Example 3 Analogously to Example 3, 66.1 parts of resorcinol are used for the reaction.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyethers (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1977
  • 1977-07-14 DE DE19772731816 patent/DE2731816A1/de not_active Withdrawn
• 1978
  • 1978-06-05 US US05/912,176 patent/US4200728A/en not_active Expired - Lifetime
  • 1978-06-30 EP EP78100283A patent/EP0000361B1/fr not_active Expired
  • 1978-06-30 DE DE7878100283T patent/DE2862403D1/de not_active Expired

Patent Citations (2)

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