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
  • C08G65/48—Polymers modified by chemical after-treatment
• • 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
• • 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
  • 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

Definitions

• This invention is directed to novel crystalline chain extended polymers containing segments of crystalline poly(aryl ether ketones).
• novel materials are easy to prepare and display excellent toughness, fabricability, and very good high temperature and solvent resistance.
• PAE polyCaryl ethers
• PAEK is the acronym of poly(aryl ether ketone)
• PEEK is the acronym of poly(ether ether ketone) in which the 1,4-phenylene units in the structure are assumed.
• PAEKs are well known; they can be synthesized from a variety of starting materials; and they can be made with different melting temperatures and molecular weights.
• the PAEKs are crystalline, and as shown by the Dahl and Dahl et al. patents, supra, at sufficiently high molecular weights they can be tough, i.e., they exhibit high values (>50 ft-lbs/in 2 ) in the tensile impact test
• PAEK's may be produced by the Friedel-Crafts catalyzed reaction of aromatic diacylhalldes with unsubstituted aromatic compounds such as diphenyl ether as described in, for example, U.S. Patent No. 3, 065, 205. These processes are generally inexpensive processes; however, the polymers produced by these processes have been stated by Dahl et al., supra, to be brittle and thermally unstable. The Dahl patents, supra, allegedly depict more expensive processes for making superior PAEK's by Friedel-Crafts catalysis. In contrast, PAEK's such as PEEK made by nucleophllic aromatic substitution reactions generally display good toughness and acceptable mechanical properties.
• the present invention describes chain extended poly(aryl ether ketone) polymers. Both the preparation of the starting poly(aryl ether ketone) segments and their subsequent coupling with a diphenol are performed via the nucleophllic route, i.e. using a base and an aprotlc solvent. Products having superior toughness, good fabricability, and excellent solvent and temperature resistance are obtained.
• the intermediate (3) can be prepared at any desired molecular weight. The higher the excess of the hydroquinone reactant, the lower the molecular weight of the resulting precursor.
• the dihydroxyl terminated precursor (3) is extended to the desired high molecular weight poly(aryl ether ketone) (5) by condensation with a different activated dihaloaromatic compound, i.e.
• X denotes a halogen such as chlorine, fluorine, bromine, or nitro
• Ar is a divalent aromatic residue containing electron-withdrawing groups in positions ortho and/or para to the halogen or nitro functions, with the proviso that Ar cannot be the residue of 1,4-bis(p-fluorobenzoyl)benzene.
• the dihalobenzenoid or dinitrobenzenoid compound can be either mononuclear where the halogens or nitro groups are attached to the same benzenoid ring or polynuclear where they are attached to different benzenoid rings, as long as there is an activating electron withdrawing group in the ortho or para position of that benzenoid nucleus.
• Fluorine and chlorine substituted benzenoid reactants are preferred; the fluorine compounds for fast reactivity and the chlorine compounds for their inexpensiveness.
• Fluorine substituted benzenoid compounds are most preferred, particularly when there is a trace of water present in the polymerization reaction system. However, this water content should be maintained below about IX and preferably below 0.5% for best results.
• An electron withdrawing group is employed as the activator group in these compounds. It should be, of course, inert under the reaction conditions, but otherwise its structure is not critical. Preferred are the strong activating
• the ring contain no electron supplying groups on the same benzenoid nucleus as the halogen or nitro group; however, the presence of other groups on the nucleus or in the residuum of the compound can be tolerated.
• all of the substituents on the benzenoid nucleus are either hydrogen (zero electron withdrawing), or other groups having a positive sigma value, as set forth in J.F. Bunnett in Chem. Rev. 42, 273 (1951) and Quart. Rev., 12, 1 (1958). See also Taft, Steric Effects in Organic Chemistry. John Wiley & Sons (1956), chapter 13; Chem. Rev., 52, 222; JACS, 74, 3120; and JACS, 75, 4231.
• the activating group can be basically either of two types:
• R 2 is a hydrocarbon group, and the ethylidene group X 1 - -X 1 where X 1 can be
• the preferred coupling agents are represented by the formulae (6), (7) and (8).
• the most preferred coupling agents are selected from the group of the difluoro-compounds (6) and (7).
• the molecular weight of (9) can be controlled in a manner similar to that utilized for the control of the molecular weight of (3).
• Precursor (9) is condensed either afteroisolation and purification or directly as prepared, with a diphenol or a mixture of diphenols to give the final copolymer-equation ( IV) .
• the diphenol can be, for example, a dihydroxydiphenyl alkane or the nuclear halogenated derivatives thereof, such as, for example, the
• Other materials also termed appropriately “bisphenols” are also highly valuable and preferred. These materials are the bisphenols of a symmetrical or unsymmetrical joining group, the latter, for example, being an either oxygen (-O-), carbonyl (-C-), sulfone (-S-), or hydrocarbon residue in which the two phenolic nuclei are joined to the same or different carbon atoms of the residue.
• Such din ⁇ clear phenols can be characterized as having the structure:
• Ar is an aromatic group and preferably is a phenylene group
• a 1 and A 2 can be the same or different inert substituent groups such as alkyl groups having from 1 to 4 carbon atoms, halogen atoms, i.e., fluorine, chlorine, bromine or iodine, or alkoxy radicals having from 1 to 4 carbon atoms
• a and b are integers having a value of from 0 to 4, inclusive
• R 1 is representative of a bond between aromatic carbon atoms as in a dihydroxy-diphenyl, such as 4,4', 3,3', or
• radicals such as -C-, -O-, -S-, -SO-, -S-S-, -SO 2
• divalent hydrocarbon radicals such as alkylene, alkylldene, cycloalkylene, cycloalkylidene, or the halogen, alkyl, aryl or like substituted alkylene, alkylldene and cycloallphatic radicals or an aromatic radical; it may also represent rings fused to both Ar groups.
• Examples of specific dihydric polynuclear phenols include among others the bis-(hydroxyphenyl) alkanes such as 2,2-bis-(4-hydroxyphenyl)propane , 2 , 4 ' -dihydroxydiphenylme thane , bis-(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)methane, bis(4-hydroxy-2,6-dimethnl-3-methoxyphenyl)methane, 1,1-bis-(4-hydroxyphenyl)ethane,
• di(hydroxyphenyl)sulfones such as bis-(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, 5-chloro-2,4'-dihydroxydiphenyl sulfone, 5'-chloro-4,4'-dihydroxydiphenyl sulfone, and the like; di(hydroxyphenyl)ethers such as bis-(4-hydroxyphenyl)ether, the 4,3', 4,2'-2,2'-2,3'-,dihydroxydiphenyl ethers, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether,bis-(4-hydroxy-3-isobutylphenyl)ether, bis-(4-hydroxy-3-isopropylphenyl)ether, bis-(4-hydroxy-3-chlorophenyl)ether
• dlhydroxydiphenyl)ketones such as the 4,3'-,4,4'-,4,2'-,2,2'-, and 2,3'- dihydroxybenzophenones; dlhydroxy-diketones such as 1,4-bis(4'-hydroxybenzoyl)benzene, 4,4'-bis(4"-hydroxybenzoyl)diphenyl ether, 1,3-bis(4'-hydroxybenzoyl)benzene; mononuclear diphenols such as resorclnol; fused ring polynuclear diphenols such as the dihydroxynaphthalenes, dihydroxyanthracenes, and dihydroxyphenathrenes.
• Both the precursors and the final polymers are prepared in solution, using the nucleophllic polycondensation reaction.
• the reactions are carried out. by heating a mixture of the said monomers or precursor (or precursors) with the appropriate monomers at a temperature of from about 100 to about 400°C.
• the reactions are conducted in the presence of an alkali metal carbonate or bicarbonate.
• an alkali metal carbonate or bicarbonate Preferably a mixture of alkali metal carbonates or bicarbonates is used.
• the mixture comprises sodium carbonate or bicarbonate with a second alkali metal carbonate or bicarbonate wherein the alkali metal of the second carbonate or bicarbonate has a higher atomic number than that of sodium.
• the amount of the second alkali metal carbonate or bicarbonate is such that there is from 0.001 to about 0.20 gram atoms of the second alkali metal per gram atom of sodium.
• the higher alkali metal carbonates or bicarbonates are thus selected from the group consisting of potassium, rubidium and cesium carbonates and bicarbonates. Preferred combinations are sodium carbonate or bicarbonate with potassium carbonate or cesium carbonate.
• the alkali metal carbonates or bicarbonates should be anhydrous although, if hydrated salts are employed, where the polymerization temperature is relatively low, e.g. 100 to 250oC, the water should be removed, e.g. by heating under reduced pressure, prior to reaching the polymerization temperatures.
• the total amount of alkali metal carbonate or bicarbonate employed should be such that there is at least 1 atom of alkali metal for each phenol group. Hence, when using the monomeric or ollgomerlc diphenols of the instant invention there should be at least 1 mole of carbonate, or 2 moles of bicarbonate, per mole of the aromatic diol.
• An excess of carbonate or bicarbonate may be employed. Hence there may be 1 to 1.2 atoms of alkali metal per phenol group. While the use of an excess of carbonate or bicarbonate may give rise to faster reactions, there is the attendant risk of cleavage of the resulting polymer, particularly when using high temperatures and/or the more active carbonates.
• the amount of the second (higher) alkali metal carbonate or bicarbonate employed is such that there are 0.001 to about 0.2 grams atoms of the alkali metal of higher atomic number per gram atom of sodium.
• a mixed carbonate for example sodium and potassium carbonate, may be employed as the second alkali metal carbonate.
• one of the alkali metal atoms of the mixed carbonate is sodium
• the amount of sodium in the mixed carbonate should be added to that in the sodium carbonate when determining the amount of the mixed carbonate to be employed.
• the alkali metal of the second alkali metal carbonate or bicarbonate per gram atom of sodium is used.
• oligomeric bisphenol or the ollgomerlc dlhalobenzenoid compound are employed, they should be used in substantially equimolar amounts with respect to the monomerlc chain extending reagent. Excesses lead to the production of lower molecular weight products. However, a slight excess, up to 5 mole %, of any of the reagents may be employed if desired.
• the reaction is carried out in the presence of an inert solvent.
• the solvent employed is an aliphatic or aromatic sulfoxlde or sulfone of the formula
• R-S(O) x -R' where x is 1 or 2 and R and R' are alkyl or aryl groups and may be the same or different. R and R' may together form a divalent radical.
• Preferred solvents include dimethyl sulfoxide, dimethyl sulfone, sulfolane (1,1 dloxothiolan), or aromatic sulfones of the formula:
• R 2 is a direct link, an oxygen atom or two hydrogen atoms (one attached to each benzene ring) and R 3 and R' 3 , which may be the same or different, are hydrogen atoms and alkyl or phenyl groups.
• aromatic sulfones include diphenylsulfone, dibenzothiophen dioxide, phenoxathiln dioxide and 4-phenylsulfonyl biphenyl.
• Diphenylsulfone is the preferred solvent.
• Other solvents that may be used include N,N' -dimethyl acetamide, N,N-dimethyl formamide and N-methyl-2-pyrrolidone.
• the polymerization temperature is in the range of from about 100° to about 400°C and will depend on the nature of the reactants and the solvent, if any, employed. The preferred temperature is above 270°C.
• the reactions are generally performed under atmospheric pressure. However, higher or lower pressures may be used.
• it may be desirable to commence polymerization at one temperature, e.g. between 200° and 250°C and to increase the temperature as polymerization ensues. This is particularly necessary when making poiymers having only a low solubility in the solvent. Thus, it is desirable to Increase the temperature progressively to maintain the polymer in solution as its molecular weight increases.
• the maximum polymerization temperature be below 350°C.
• the polymerization reaction may be terminated by mixing a suitable end capping reagent, e.g. a mono or polyfunctlonal halide such as methyl chloride, t-butyl chloride or 4,4-dichlorodiphenylsulphone with the reaction mixture at the polymerization temperature, heating for a period of up to one hour at the polymerization temperature and then discontinuing the polymerization.
• a suitable end capping reagent e.g. a mono or polyfunctlonal halide such as methyl chloride, t-butyl chloride or 4,4-dichlorodiphenylsulphone
• This invention is also directed to an improved process for making the chain-extended polymers in comparatively shorter reaction times overall than by using potassium fluoride alone or by using a combination of sodium carbonate or bicarbonate and a second higher alkali metal carbonate or bicarbonate.
• this process is directed to preparing the poly(aryl ether ketone) precursors and the chain-extended polymers by the reaction of a mixture of the hydroquinone and 1,4-bis(p-fluorobenzoyl)benzene (to make the precursor), or the reaction of the precursor to make the chain-extended polymer either one or both in the presence of a combination of sodium carbonate and/or bicarbonate an alkali metal halide selected from potassium, rubidium, or cesium fluoride or chloride, or combinations thereof.
• the reaction is carried out by heating a mixture of the monomeric reactants or the block precursor and the monomeric coupling agent as described herein, at a temperature of from about 100 to about 400°C.
• the reaction is conducted in the presence of added sodium carbonate and/or bicarbonate and potassium, rubidium or cesium fluorides or chlorides.
• the sodium carbonate or bicarbonate and the chloride and fluoride salts should be anhydrous although, if hydrated salts are employed, where the reaction temperature is relatively low, e.g. 100 to 250°C, the water should be removed, e.g. by heating under reduced pressure, prior to reaching the reaction temperature.
• an entraining organic medium can be used to remove water from the reaction such as toluene, xylene, chlorobenzene, and the like.
• the total amount of sodium carbonate or bicarbonate and potassium, rubidium or cesium fluoride or chloride, or combinations thereof employed should be such that there is at least 1 atom of total alkali metal for each phenol group, regardless of the anion (carbonate, bicarbonate or halide).
• each phenol group is used.
• from 0.001 to about 0.5 atoms of alkali metal (derived from a higher alkali metal halide) is used for each phenol group.
• the sodium carbonate or bicarbonate and potassium fluoride are used such that the ratio of potassium to sodium therein is from about 0.001 to about 0.5, preferably from about 0.01 to about 0.25, and most preferably from about 0.02 to about 0.20.
• An excess of total alkali metal may be employed. Hence there may be about 1 to about 1.7 atoms of alkali metal per phenol group. While the use of a large excess of alkali metal may give rise to faster reactions, there is the attendant risk of cleavage of the resulting polymer, particularly when using high temperatures and/or the more active alkali metal salts.
• cesium is a more active metal and potassium is a less active metal so that less cesium and more potassium are used.
• the chloride salts are less active than the fluoride salts so that more chloride and less fluoride is used.
• the blsphenol and the dlhalobenzenoid (or dinitrobenzenoid) compound, one of which is ogllmeric, are employed in substantially equimolar amounts when maximum molecular weight is sought.
• a slight excess, up to 5 mole X, of any of the reactants may be employed if desired.
• An excess of one over the other leads to the production of low molecular weight products.
• the reactions are carried out in the presence of an inert solvent.
• the reaction temperature is in the range of from about 100° to about 400°C and will depend on the nature of the reactants and the solvent. The preferred temperature is above 250°C.
• the reactions are preferably carried out at ambient pressure. However, higher or lower pressure can also be used.
• the reaction is generally carried out in an inert atmosphere.
• the polymers of this invention may include mineral fillers such as carbonates including chalk, calcite and dolomite; silicates including mica, talc, wollastonite; silicon dioxide; glass spheres; glass powders; aluminum, clay; quartz; and the like. Also, reinforcing fibers such as fiberglass, carbon fibers, and the like may be used.
• the polymers may also include additives such as titanium dioxide; thermal stabilizers, untraviolet light stabilizers, plasticlzers, and the like.
• the polymers of this invention may be blended with one or more other polymers such as polyarylates, polysulfones, polyetherimides, polyamideimides, polyimldes, polyphenylene sulfides, polyesters, polycarbonates, polyamides, polyhydroxyethers and the like.
• polyarylates such as polyarylates, polysulfones, polyetherimides, polyamideimides, polyimldes, polyphenylene sulfides, polyesters, polycarbonates, polyamides, polyhydroxyethers and the like.
• the polymers of this invention may be fabricated into any desired shape, i.e., moldings, coatings, films, or fibers. They are particularly desirable for use as electrical insulation for electrical conductors.
• the polymers may be woven into monofilament threads which are then formed into industrial fabrics. by methods well known in the art as exemplified by U.S. Patent 4,359,501. Further, the polymers may be used to mold gears, bearings and the like.
• a 250 ml. 3-neck flask with slanted side arms fitted with a Claisen arm, nitrogen inlet tube, thermocouple probe, condenser, and stainless steel stirrer is charged with 1,4-bis(p-fluorobenzoyl)- benzene (0.1104 moles, 35.58 gm), hydroquinone (0.115 moles, 12.66gm), sodium carbonate (0.1173 moles, 12.43 gm; ground and dried), anhydrous potassium fluoride (0.0293 moles, 1.70 gm) and diphenyl sulfone (100 gm).
• the apparatus is evacuated and filled with argon by means of a Firestone valve connected to the top of the condenser.
• a flow of high purity nitrogen is started and the connection to the Firestone valve is replaced with a bubbler.
• the contents of the flask are heated carefully by means of a heating mantle and temperature controller to melt the diphenyl sulfone.
• the reaction mixture is stirred and heated to 200°C and held 30 minutes at that temperature; it is then held at 250°C for 1 hr., and finally at 270°C for 2 hours.
• the reaction mixture is poured from the reaction flask, cooled, ground to a fine powder, and a sample refluxed successively twice with acetone, once with 2% hydrochloric acid, once with water, and washed thoroughly with acetone. It is then dried until constant weight at 120°C under vacuum (about 20mm). Based on reactant stolchlometry this oligomer has the structure (3) as depicted above.
• Example 2 Coupling of the Hydroxyl-termlnated Oligomer (3) to High Polymer.
• the oligomer is prepared essentially as described in the foregoing example.
• 4,4'-difluoro- benzophenone (0.0058 moles, 1.27 gm) Is added to the stirred reaction mixture along with 8.0 gm of diphenyl sulfone.
• the reaction mixture is then heated to 290°C, held 30 minutes, and then heated to 320°C. After 1.6 hours the viscous reaction mixture is removed from the flask, cooled, and ground.
• reaction product is refluxed successively (500 ml., lhr.) with acetone (twice), water, 2% hydrochloric acid, water, and acetone and dried at 110-120oC in a vacuum oven overnight (about 15 hours).
• the polymer is compression molded and the film (20 mil) is tested for tensile strength and modulus according to ASTM-D-638, yield elongation and elongation at break according to ASTM-D-638, and pendulum impact strength according to ASTM-D-256. Excellent properties are noted.

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

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• 1986
  • 1986-05-01 JP JP50250686A patent/JPS63500666A/ja active Granted
  • 1986-05-01 EP EP19860903055 patent/EP0231198A1/de not_active Withdrawn
  • 1986-05-01 WO PCT/US1986/000903 patent/WO1987000539A1/en not_active Application Discontinuation
  • 1986-05-02 CA CA000508296A patent/CA1272344A/en not_active Expired

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