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WO1996037535A1 - Procede de fabrication de poly(phenylene oxydes) dans du dioxyde de carbone - Google Patents

Procede de fabrication de poly(phenylene oxydes) dans du dioxyde de carbone Download PDF

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Publication number
WO1996037535A1
WO1996037535A1 PCT/US1996/007268 US9607268W WO9637535A1 WO 1996037535 A1 WO1996037535 A1 WO 1996037535A1 US 9607268 W US9607268 W US 9607268W WO 9637535 A1 WO9637535 A1 WO 9637535A1
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Prior art keywords
phenol
carbon dioxide
process according
polymerization
poly
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PCT/US1996/007268
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English (en)
Inventor
Joseph M. Desimone
Chad D. Mistele
Kerstin K. Kapellen
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The University Of North Carolina At Chapel Hill
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Application filed by The University Of North Carolina At Chapel Hill filed Critical The University Of North Carolina At Chapel Hill
Priority to AU58657/96A priority Critical patent/AU5865796A/en
Publication of WO1996037535A1 publication Critical patent/WO1996037535A1/fr

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    • 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
    • C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
    • 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
    • C08G65/44—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 by oxidation of phenols
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a method of preparing poly(phenylene oxides), and particularly to a method of preparing poly ⁇ henylene oxides) in a medium comprising carbon dioxide.
  • Poly(phenylene oxide) polymers are known to possess desirable physical and chemical properties for a variety of applications, and various methods for their preparation have been proposed.
  • U.S. Patent No. 3,236,807 to Stamatoff proposes a method for preparing high molecular weight poly(unsymmetrically-2,6-disubstituted phenylene ether) including polymerizing a halophenol in the presence of oxygen and a free radical initiator in an organic solvent such as aromatic hydrocarbons, ethers, and halogenated hydrocarbons.
  • U.S. Patent Nos. 3,306,874 and 3,306,875 to Hay propose methods of oxidizing phenols for the preparation of poly(phenylene oxides) with oxygen and an amine-basic cupric salt complex is solubilized with the phenol.
  • U.S. Patent No. 3,431,238 to Borman proposes a method of oxidizing halophenols using a basic cupric salt and an amine in a solvent such as benzene or toluene.
  • U.S. Patent No. 3,573,257 to Nakashio et al. proposes a process for producing poly(phenylene oxides) which includes polymerizing a phenol in the presence of a copper compound, an alcoholate and/or phenolate of an alkali metal, preferably in an organic solvent.
  • the present invention provides a process for making poly(phenylene oxide) polymers.
  • the process includes (a) providing a polymerization medium comprising carbon dioxide (b) contacting a phenol monomer with a catalyst capable of catalyzing the polymerization of the phenol monomer, in the polymerization medium; and (c) polymerizing the monomer in the polymerization medium.
  • phenol monomer refers to substituted phenol compounds.
  • Substituted phenol compounds which are useful as phenol monomers include phenol compounds subsituted one or more times with any of H, halogen, alkyl, substituted alkyl, alkoxy, phenyl, phenoxy, carboxy, alkyl substituted carboxy, and perfluoroalkyl.
  • the phenol monomers useful in the methods of the present invention typically have the formula (I):
  • R l5 R 2 , R 4 , and R $ are independently selected from the group consisting of H, halogen, alkyl, substituted alkyl, alkoxy, phenyl, phenoxy, carboxy, alkyl substituted carboxy, and perfluoroalkyl; and R 3 is selected from the group consisting of H and halogen.
  • the carbon dioxide useful as the polymerization medium may be in the form of liquid, supercritical, or gaseous carbon dioxide.
  • Catalysts useful in the methods of the present invention are typically multi- component systems comprising (1) a transition metal salt, (2) an amine, and (3) oxygen.
  • the polymerization is carried out in the presence of a surfactant.
  • the process may also include the steps of separating the poly(phenylene oxide) polymer from the polymerization medium.
  • the present invention provides a process for preparing a poly(phenylene oxide) copolymer.
  • the process includes (a) contacting a phenol monomer and a comonomer with a catalyst capable of catalyzing the copolymerization of the phenol monomer and comonomer, and a polymerization medium including carbon dioxide; and (b) copolymerizing the phenol monomer and comonomer.
  • the present invention provides a polymerization reaction mixture useful for carrying out the polymerization of a phenol monomer.
  • the reaction mixture includes (a) a phenol monomer, (b) a catalyst capable of catalyzing the polymerization of a phenol monomer, and (c) a polymerization medium comprising carbon dioxide.
  • the present invention provides a mixture produced by the polymerization of a phenol monomer.
  • the mixture includes (a) a poly ⁇ henylene oxide) polymer, and (b) a polymerization medium comprising carbon dioxide.
  • Carbon dioxide has been employed as a reaction medium for the polymerization of various monomers.
  • U.S. Patent No. 3,522,228 to Fukui et al. proposes the polymerization of vinyl monomers in liquid carbon dioxide using hydrocarbon polymerization initiators.
  • U.S. Patent No. 5,328,972 to Dada et al. proposes a process for preparing low molecular weight polymers in supercritical carbon dioxide.
  • alkyl refers to linear or branched, saturated or unsaturated Cj to C 10 hydrocarbon groups, such as for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, octyl, and the like.
  • This definition also applies to the alkoxy moiety, thus examples of alkoxy substituents include methoxy, ethyoxy, propoxy, butoxy, and the like.
  • halogen or “halo” or “halide” as used herein refers to a halogen such as fluorine, chlorine, bromine and iodine.
  • supercritical has its conventional meaning in the art.
  • a supercritical fluid (SCF) is a substance above its critical temperature and critical pressure (or
  • critical point Compressing a gas normally causes a phase separation and the appearance of a separate liquid phase. However, if the fluid is in a supercritical state, compression will only result in density increases; no liquid phase will be formed.
  • the critical temperature of carbon dioxide is about 31°C.
  • fluoropolymer as used herein has its conventional meaning in the art.
  • the phenol monomers useful in the processes of the present invention include phenol monomers which are known to those skilled in the art.
  • the phenol monomers useful in the methods of the present invention include monomers having the Formula (I):
  • R*,, R 2 , R 4 , and R 5 are independently selected from the group consisting of H, halogen, alkyl, substituted alkyl, alkoxy, phenyl, phenoxy, carboxy, alkyl substituted carboxy, and perfluoroalkyl; and R 3 is selected from the group consisting of H and halogen.
  • sutiable phenol monomers having the formula (I) include, but are not limited to 2,6-dimethyl phenol, 2,6-diethyl phenol, 2,6-dibutyl phenols, 2,6-dilauryl phenol, 2,6-dipropyl phenols, 2,6- diphenyl phenol, 2-methyl-6-ethyl phenol, 2-methyl-6-propargyl phenol, 2- methyl-6-cyclohexyl phenol, 2-methyl-6-benzyl phenol, 2-methyl-6-tolyl phenol, 2-methyl-6-methoxy phenol, 2-ethyl-6-phenylethyl phenol, 2,6-dimethoxy phenol, 2,3,6-trimethyl phenol, 2,3,5,6-tetramethyl phenol, 2,6-diethoxy phenol, 2-methoxy-6-ethoxy-phenol, 2-ethyl-6-stearyloxy phenol, 2,6-di- (chlorophenoxy) phenols, 2-6-di
  • the poly(phenylene oxide) polymers produced according to the methods of the present invention include homopolymers of any of the foregoing phenol monomers, or in the embodiment wherein one or more comonomers are employed in combination with the phenol monomer, the resulting poly henylene oxide) polymers may be copolymers.
  • the poly(phenylene oxide) polymers typically have the Formula (II):
  • R l5 R 2 , R 4 , and R 5 are as defined above in connection with Formula
  • homopolymers produced according to the methods of the present invention include but are not limited to poly(2,6- dimethyl phenol) and poly(2,6-diphenyl phenol).
  • the comonomers useful in the methods of the present invention are typically other phenol monomers, such as for example any of the phenol monomers recited above.
  • Copolymers which may be produced according to the processes of the present invention include but are not limited to:
  • the processes of the present invention are generally carried out in the presence of a catalyst capable of catalyzing the polymerization of the phenol monomer, or monomer and comonomer, to produce the poly(phenylene oxide) polymer.
  • Suitable catalysts are known to those skilled in the art, and generally include catalysts for polymerization via oxidative coupling, and catalysts for polymerization via radical-initiated displacement.
  • catalysts which polymerize via oxidative coupling include multi-component catalyst systems such as those described in U.S. Patent Nos. 3,306,874 and 3,306,875 to Hay, 3,431,238 to Borman, 3,573,257 to Nakashio et al. , 3,639,656 to Bennett et al.
  • the multi-component catalyst system typically includes a transition metal salt, an amine, and oxygen.
  • the transition metal salt is typically a transition metal halide, such as a transition metal halide of copper, manganese, or cobalt, with copper halides currently being preferred.
  • Preferred copper halide transition metal salts include copper (I) bromide and copper (I) chloride.
  • transition metal halides include manganese bromide, manganese chloride, manganese fluoride, manganese iodide, cobalt bromide, cobalt chloride, cobalt fluoride, and cobalt iodide.
  • suitable transition metal salts include, for example, copper (I) oxide, copper sulfate, manganese (II) carbonate, manganese
  • the transition metal salt is selected from copper (I) bromide and copper (I) chloride.
  • Amines which may be useful as a second component of the multi- component catalyst system include aliphatic monoamines, aliphatic diamines, pyridine, polymeric amines, and copolymers of any of the foregoing with a fluorinated monomer.
  • suitable aliphatic monoamines are known in the art and include those described in U.S. Patent No. 3,431,238, already incorporated herein by reference.
  • suitable aliphatic monoamines include dimethylamine, diethylamine, diisopropylamine, di-n- butylamine, methylethylamine, methylbenzylamine, dibenzylamine, dioctylamine, trimethylamine, triethylamine, trihexylamine, dimethylbenzylamine, methyethylbenzylamine, /.-diethylaminoethanol, dimethylaniline, and the like,.
  • Suitable aliphatic diamines include N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetraamyl-l,2- ethylenediamine, N'-benzyl-N,N-dimethyl-l,2-ethylenediamine, dibenzyl- dimethyl-l,2-ethylenediamine, l,2-ethylene-N,N'-dimorpholine, N,N,N',N'- tetramethyl-1 ,3-propanediamine, N,N,N' ,N' -tetramethyl-1 ,3-butanediamine, and N,N,N',N'-tetramethyl-l,4-butanediamine.
  • suitable polymeric amines include but are not limited to polyvinylpyridine, and dialkylamino substituted styrenes.
  • suitable copolymers of amines and fluorinated monomers include but are not limited to poly(2-
  • Preferred amines include dibutylamine, pyridine, poly(2-(dimethylamino)ethyl-acrylate-co-perfluorooctylacrylate), and poly(vinylpyridine-co-perfluorooctylacrylate).
  • catalyst systems include copper (I) bromide, dibutylamine, and oxygen; copper (I) bromide, pyridine, and oxygen; copper (I) bromide, poly(2-(dimethylamino)ethylacrylate-co- perfluorooctylacrylate), and oxygen; and copper (I) bromide, poly(vinylpyridine-co-perfluorooctylacrylate), and oxygen.
  • Other suitable catalyst systems known to those skilled in the art include catalyst systems for polymerization via radical-initiated displacement. Such catalyst systems are known in the art, and include those catalysts described in the H. Mark, Encyclopedia of Polvmer Science and Engineering.
  • catalysts include but are not limited to potassium ferricyanide, lead dioxide, iodine, and 2,4,6-tri-t- butylphenoxy radicals.
  • the catalyst is used in an amount conventionally employed for polymerization.
  • the amount of catalyst employed depends on several factors, including the specific monomers and comonomers to be polymerized, the reactivity of the monomers or comonomers, the reaction conditions, and the particular catalyst chosen.
  • the phenol monomer is present in an amount of from about 0.1 to about 80 percent by weight
  • the molar ratio of copper halide to phenol monomer is from about 1:20 up to about 1:300
  • the molar ratio of amine to copper halide is from about 1:10 up to about 1:100.
  • the oxygen is present in an amount sufficient to achieve a molar ratio of monomer of oxygen of at least about 1:0.5, and may be added alone or in admixture with the carbon dioxide polymerization medium.
  • the processes of the invention are carried out in a polymerization medium comprising carbon dioxide.
  • the carbon dioxide may be in a gaseous, liquid or supercritical state.
  • the polymerization medium may also include one or more cosol vents.
  • Illustrative cosol vents include but are not limited to, organic solvents such as methanol, toluene, benzene, and halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, chloroform, trichlorethylene, tetrachloroethylene, and the like. It may be desirable for the cosol vent to be capable of solubilizing the catalyst such that the catalyst may be provided to the reaction in the solubilized form.
  • the catalyst may be added in neat form, or it may conveniently be added as a solution in a cosolvent.
  • the cosolvent may be a styrenic monomer which is capable of polymerization subsequent to the polymerization of the phenol monomer. The sequential polymerization of these components obviates the necessity of mixing in the preparation of polystyrene/poly(phenylene oxide) blends.
  • the polymerization reaction mixture may include other additives and reactants known to those skilled in the art.
  • the process of the invention includes the addition of surfactant for stabilizing the monomer and polymer in the polymerization medium.
  • the surfactant should be one that is surface active in carbon dioxide and thus partitions itself at the carbon dioxide-monomer or carbon dioxide-polymer interface. Suitable surfactants are described in detail in U.S. Patent No. 5,312,882 to DeSimone et al., the disclosure of which is incorporated herein by reference in its entirety. Such a surfactant may cause the formation of micelles in the carbon dioxide and thus create a dispersed phase.
  • the surfactant is generally present in the reaction mixture in a concentration of from about 0.001 up to about 30 percent by weight.
  • the surfactants can be nonreactive in the polymerization or can react with and thereby be included with the forming polymer. Suitable reactive surfactants include fluorinated and siloxane phenolic monomers.
  • the surfactant should contain a segment that is soluble in carbon dioxide ("CO 2 -philic"). Exemplary CO 2 -philic segments include a fluorine- containing segment, such as can be found in fluoropolymers or copolymers of fluoropolymers, or a siloxane-containing segment, such as can be found in siloxane polymers or copolymers of siloxane polymers. As used herein, a
  • fluoropolymer has its conventional meaning in the art.
  • exemplary fluoropolymers are those formed from: fluoroacrylate monomers such as 2-(N- ethylperfluorooctanesulfonamido) ethyl acrylate (“Et-FOSEA”), 2-(N- ethylperfluorooctanesulfonamido) ethyl methacrylate (“EtFOSEMA”), 2-(N- methylperfluorooctanesulfonamido) ethyl acrylate (“MeFOSEA”), 2-(N- methylperfluorooctanesulfonamido) ethyl methacrylate (“MeFOSEMA”), 1,1- Dihydroperfluorooctyl acrylate (“FOA”), and 1,1-Dihydroperfluorooctyl acrylate (“FOMA”); fluoroolefin monomers
  • the surfactant comprises a hydrophobic group, such as a polystyrene group or a poly(phenylene oxide) group, that is "CO 2 - phobic," along with a CO 2 -soluble group, such as a fluoropolymer.
  • a hydrophobic group such as a polystyrene group or a poly(phenylene oxide) group
  • CO 2 -soluble group such as a fluoropolymer.
  • Such copolymers can take many forms; two exemplary forms are graft copolymers having a CO 2 -soluble backbone and hydrophobic branches attached thereto and block copolymers, including diblock and triblock copolymers, having a central hydrophobic portion attached at opposite ends to one of a pair of CO 2 -soluble portions are preferred.
  • the CO 2 -soluble end portions extend into the CO 2 -continuous phase, but the hydrophobic portions can aggregate to form the core of a micelle.
  • the fluoropolymer segment be a fluorinated acrylate polymer such as dihydroperfluorooctyl acrylate.
  • a preferred block copolymer surfactant comprises poly (1,1 -dihydroperfluorooctyl acrylate) end blocks and a polystyrene center block.
  • Exemplary silicone-containing surfactants i.e., siloxane polymers or copolymers
  • the polymerization reaction may be carried out at a temperature of from about -57°C up to about 250°C, and is typically carried out at a temperature of between about 20°C and about 50°C.
  • the reaction may be carried out at a pressure ranging from about 20 psi to about 10,000 psi, and is typically carried out at a pressure of between about 500 psi and about 5,000 psi.
  • the polymerization is carried out for a period of time sufficient to achieve the polymerization of substantial fraction of the phenol monomer, or monomer and comonomers present. Typically, the reaction mixture is allowed to polymerize for a period of from about 1 to about 24 hours.
  • the polymerization can be carried out batchwise or continuously with thorough mixing of the reactants in any appropriately designed high pressure reaction vessel.
  • the pressure apparatus includes a cooling system. Additional features of the pressure apparatus used in accordance with the invention include heating means such as an electric heating furnace to heat the reaction mixture to the desired temperature and mixing means, i.e., stirrers such as paddle stirrers, impeller stirrers, or multistage impulse countercurrent agitators, blades, and the like.
  • the polymerization can be carried out, for example, by feeding a mixture of phenol monomer and transition metal salt into a pressure apparatus.
  • the reaction vessel is closed and the amine is added through an injector loop together with a mixture of oxygen and carbon dioxide. Thereafter, the reaction mixture brought to the polymerization temperature and pressure.
  • a cosolvent, and/or surfactant may be added to the reaction vessel with the transition metal salt and phenol monomer. It is also possible to add the carbon dioxide, and heat the reaction mixture prior to the addition of the amine and oxygen. Alternatively, only a part of the reaction mixture may be introduced into an autoclave and heated to the polymerization temperature and pressure, with additional reaction mixture being pumped in at a rate corresponding to the rate of polymerization.
  • some of the phenol monomers are initially taken into the autoclave in the total amount of carbon dioxide and the phenol monomers or comonomers are pumped into the autoclave together with the catalyst at the rate at which the polymerization proceeds.
  • the transition metal halide, amine, oxygen, and a portion of the carbon dioxide are added to the reaction vessel, and the mixture is heated prior the addition of the phenol monomer as a solution in carbon dioxide, which brings the reaction mixture to the required reaction temperature and pressure.
  • the polymer may be separated from the reaction mixture. Any suitable means of separating the polymer from the reaction mixture may be employed. Typically, according to the process of the present invention, the polymer is separated from the reaction mixture by venting the polymerization medium to the atmosphere. Thereafter the polymer may be collected by physical isolation. It may be desirable, for some applications to wash the resulting polymer prior to further processing.
  • the polymer may be washed in wash fluids which are conventionally known in the art.
  • suitable wash fluids include mixtures of methanol and acid such as acetic acid or hydrochloric acid.
  • the polymer may be washed in a wash fluid comprising carbon dioxide.
  • the poly henylene oxide) polymers produced according to the processes of the present invention are useful in a variety of conventionally known applications.
  • the poly(phenylene oxide) polymer are useful for the production of molded articles including automotive body parts such as instrument panels, interior trim, speaker grills, consoles, glove compartments, exterior trim, cowl tops, wheel covers, headlight housings, mirror cases, electrical connectors, and fuse boxes.
  • poly(phenylene oxide) polymers are useful for the production of various small appliances such as hair dryers, coffee makers, and steam irons; and large appliances such as refrigerators and ranges.
  • the poly(phenylene oxide) polymers produced according to the methods of the present invention may be combined with other known polymers such as polystyrene for the production of molded articles such as automotive parts and appliances as described above.
  • Example 1 A 10 ml high pressure reactor is purged with argon. Cupric bromide (0.024 g) and 0.6 ml dibutyl amine are added and the reactor is closed. Oxygen is added to a pressure of 274 psi, followed by the addition of carbon dioxide to a pressure of 1600 psi. The solution is stirred while 2,6- dimethyl phenol (DMP), dissolved in carbon dioxide, is added from a variable volume cell. During the addition of the monomer (0.77 g; Cu: amine: DMP
  • Example 2 A 10 ml high pressure reactor is purged with argon. Cupric bromide (0.024 g) and 0.6 ml dibutyl amine are added, and the reactor is closed. Oxygen is added to a pressure of 266 psi, followed by the addition of carbon dioxide to a pressure of 850 psi. The solution is stirred while 2,6- dimethyl phenol (DMP), dissolved in carbon dioxide, is added from a variable volume cell. During the addition of the monomer (1.55 g; Cu:amine:DMP 1:22:75) the pressure increases to 4800 psi. After 18 hours stirring at room temperature the carbon dioxide is vented and the product washed with a mixture of 1 % acetic acid in methanol.
  • DMP 2,6- dimethyl phenol
  • the product is filtered and precipitated from toluene into methanol.
  • DMP 2,6-dimethyl phenol
  • a 10 ml high pressure reactor is purged with argon. Cupric bromide (0.024 g) and 1.52 g 2,6-dimethyl phenol are added and the reactor is closed. Oxygen is added to a pressure of 360 psi, followed by the addition of carbon dioxide to a pressure of 1500 psi. The cell is heated to 40 °C, resulting in a pressure of 1850 psi. The solution is stirred while 0.6 ml dibutyl amine (Cu: amine: DMP 1:22:75) are added through a injector loop with carbon dioxide, to a final pressure of 5000 psi.
  • a 10 ml high pressure reactor is purged with argon. Cupric bromide (0.024 g) and 1.52 g 2,6-dimethyl phenol are added and the reactor is closed. Oxygen is added to a pressure of 314 psi, followed by the addition of carbon dioxide up to a pressure of 1280 psi. The cell is heated to 40°C, resulting in a pressure of 1680 psi. Carbon dioxide is added up to a pressure of 3000 psi. The solution is stirred while 0.3 ml pyridine (Cu:amine:DMP 1:22:75) are added through an injector loop with carbon dioxide, to a final pressure of 5000 psi. After 1 hour stirring at 40 °C the carbon dioxide is vented and the product washed with a mixture of 1 % acetic acid in methanol.
  • a 10 ml high pressure reactor is purged with argon. Cupric bromide (0.024 g) and 1.55 g 2,6-dimethyl phenol are added and the reactor is closed. Oxygen is added to a pressure of 300 psi, followed by the addition of carbon dioxide up to a pressure of 1600 psi. The cell is heated to 40°C and carbon dioxide is added to a pressure of 3000 psi. The solution is stirred while 0.3 ml pyridine (Cu:amine:DMP 1:22:75) are added through an injector loop to a final pressure of 5000 psi.
  • a 10 ml high pressure reactor is purged with argon. Cupric bromide (0.024 g) and 1.58 g 2,6-dimethyl phenol are added and the reactor is closed. Oxygen is added to a 30 ml variable volume cell to achieve a pressure of 180 psi, followed by the addition of carbon dioxide up to a final pressure of 700 psi. The solution is stirred while 0.6 ml pyridine (Cu: amine: DMP 1:44:75) are added through an injector loop with the oxygen/carbon dioxide mixture from the variable volume cell, resulting in a pressure of 3000 psi in the reactor.
  • a 10 ml high pressure reactor is purged with argon.
  • Cupric bromide (0.012 g), 0.77 g 2,6-dimethyl phenol, and 1.02 g poly(perfluorooctylacrylate-co-vinylpyridine) with a content of 6.1 wt. % vinylpyridine are added and the reactor is closed.
  • the molar ratio of copper:amine:2,6-dimethyl phenol is 1:22:75.
  • Oxygen is added to a pressure of 240 psi, followed by the addition of carbon dioxide to a pressure of 2300 psi.
  • the reactor is heated to 40 °C and carbon dioxide is added again to a final pressure of 4700 psi at 40°C.
  • a 10 ml high pressure reactor is purged with argon.
  • Cupric bromide (0.024 g), 1.52 g 2,6-dimethyl phenol and 1.35 g poly (2- (dimethylamino)ethylacrylate-co-perfluorooctylacrylate) with a content of 13.1 wt. % 2-(dimethylamino)ethylacrylate are added and the reactor is closed.
  • the molar ratio of copper:amine:2,6-dimethyl phenol is 1:22:75.
  • Oxygen is added to a pressure of 330 psi, followed by the addition of carbon dioxide to a pressure of 2500 psi.
  • a 10 ml high pressure reactor is purged with argon.
  • Cupric bromide (0.024 g), 2.95 g 2,6-dimethyl phenol and 1.37 g poly(2- (dimethylamino)ethylacrylate-co-perfluorooctylacrylate) with a content of 13.1 wt. % 2-(dimethylamino)ethylacrylate are added and the reactor is closed.
  • the molar ratio of copper:amine:2,6-dimethyl phenol is 1:22:150.
  • Oxygen is added to a pressure of 592 psi in the reactor, followed by the addition of carbon dioxide to a pressure of 2000 psi.
  • Example 11 A 10 ml high pressure reactor is purged with argon. Cupric bromide (0.024 g), 1.66 g 2,6-dimethyl phenol and 1.37 g poly(2- (dimethylamino)ethylacrylate-co-perfluorooctylacrylate) with a content of 13.1 wt. % 2-(dimethylamino)ethylacrylate are added and the reactor is closed. The molar ratio of copper: amine: 2,6-dimethyl phenol is 1:22:75. Oxygen is added to a pressure of 310 psi in the reactor, followed by the addition of carbon dioxide up to a pressure of 4700 psi.
  • a 10 ml high pressure reactor is purged with argon. Cupric bromide (0.024 g), 1.58 g 2,6-dimethyl phenol, and 0.275 g polyperfluorooctylacrylate are added and the reactor is closed. Oxygen is added to a 30 ml variable volume cell, to achieve a pressure of 255 psi, followed by the addition of carbon dioxide to a pressure of 700 psi. The oxygen/carbon dioxide mixture is added to the high pressure reactor to achieve a pressure of 1000 psi. The pressure in the reactor is increased to 1300 psi by the addition of carbon dioxide.
  • the high pressure reactor is heated to 40 °C, resulting in a pressure of 1500 psi and further carbon dioxide is added to achieve a pressure of 2000 psi.
  • the solution is stirred while 0.6 ml pyridine (Cu:amine:DMP 1:44:75) is added through an injector loop to a final pressure of 5000 psi in the reactor.
  • After 20 hours stirring at 40°C the carbon dioxide is vented and the product washed with a mixture of 1 % HCl in methanol.
  • the product is filtered and precipitated from toluene into methanol.
  • Example 13 A 10 ml high pressure reactor is purged with argon. Cupric bromide (0.012 g), 0.72 g 2,6-dimethyl phenol, and 0.51 g poly(vinylpyridine- co-perfluorooctylacrylate) with a content of 6.1 wt. % vinylpyridine are added and the reactor is closed. Oxygen is added to a pressure of 270 psi, followed by the addition of carbon dioxide to a pressure of 2000 psi. The reactor is heated to 40 °C and the solution is stirred while 0.075 ml pyridine
  • a 10 ml high pressure reactor is purged with argon.
  • Cupric bromide (0.024 g), 1.72 g 2,6-dimethyl phenol, and 0.40 g poly(2- (dimethylamino)ethylacrylate-co-perfluorooctylacrylate) with a content of 13.1 wt. % 2(dimethylamino)ethylacrylate are added and the reactor is closed.
  • Oxygen is added to a 30 ml variable volume cell to a pressure of 110 psi, followed by the addition of carbon dioxide to a pressure of 1200 psi in this variable volume cell.
  • a 10 ml high pressure reactor is purged with argon.
  • Cupric bromide (0.024 g) 1.72 g 2,6-dimethyl phenol and 0.281 g polystyrene(4.5k)- b-polyperfluorooctylacrylate(24.5k) are added and the reactor is closed.
  • Oxygen is added to a 30 ml variable volume cell to achieve a pressure of 200 psi, followed by the addition of carbon dioxide to a final pressure of 795 psi.
  • the oxygen/carbon dioxide mixture is added to the high pressure reactor to achieve a pressure of 1173 psi in the reactor.
  • the reactor is heated to 40°C.
  • a 10 ml high pressure reactor is purged with argon.
  • Cupric bromide (0.024 g) 1.54 g 2,6-dimethyl phenol, 0.248 g polystyrene(4.5k)-b- polyperfluorooctylacrylate(24.5k) and 0.1 ml toluene are added and the reactor is closed.
  • Oxygen is added to a 30 ml variable volume cell to achieve a pressure of 200 psi, followed by the addition of carbon dioxide to a pressure of 780 psi.
  • the oxygen/carbon dioxide mixture is added to the high pressure reactor and the reactor is heated to 40 °C.
  • a 10 ml high pressure reactor is purged with argon. Cupric bromide (0.024 g), 1.69 g 2,6-dimethyl phenol and 0.035 g polystyrene(4.5k)- b-polyperfluorooctylacrylate(24.5k) are added, and the reactor is closed. Oxygen is added to a 30 ml variable volume cell to achieve a pressure of 188 psi, followed by the addition of carbon dioxide to a pressure of 710 psi. The oxygen/carbon dioxide mixture is added to the high pressure reactor to achieve a pressure of 1161 psi in the reactor.
  • the reactor is heated to 40 °C and more carbon dioxide is added to a pressure of 2300 psi at 40 °C.
  • the solution is stirred while 0.6 ml pyridine (Cu:amine:DMP 1:44:75) is added through an injector loop with carbon dioxide.
  • the final pressure in the reactor is 5000 psi.
  • After 20 hours stirring at 40 °C the carbon dioxide is vented and the product washed with a mixture of 1 % HCl in methanol.
  • the product is filtered and precipitated from toluene into methanol.

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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)

Abstract

L'invention porte sur un procédé permettant de fabriquer des polymères de poly(phénylène oxydes). Le procédé comprend les étapes suivantes: (a) mise en contact d'un monomère phénolé avec un catalyseur à même de catalyser la polymérisation du monomère phénolé, et préparation d'un milieu de polymérisation comprenant du dioxyde de carbone; et (b) polymérisation du monomère. Le milieu de polymérisation peut être constitué de dioxyde de carbone sous forme gazeuse, liquide ou supercritique.
PCT/US1996/007268 1995-05-25 1996-05-20 Procede de fabrication de poly(phenylene oxydes) dans du dioxyde de carbone WO1996037535A1 (fr)

Priority Applications (1)

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AU58657/96A AU5865796A (en) 1995-05-25 1996-05-20 Method of preparing poly(phenylene oxides) in carbon dioxide

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US45034395A 1995-05-25 1995-05-25
US08/450,343 1995-05-25

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6191215B1 (en) 1999-03-05 2001-02-20 Basf Aktiengesellschaft Process for the preparation of pulverulent polymers by polymerization in supercritical carbon dioxide in the presence of polyoxyalkylene-polysiloxane copolymers
WO2016033156A1 (fr) * 2014-08-27 2016-03-03 Sabic Global Technologies B.V. Polymérisation oxydative de phénols catalysée par le fer
US9546316B2 (en) 2012-11-12 2017-01-17 Saudi Arabian Oil Company Densifying carbon dioxide with a dispersion of carbon dioxide-philic water capsules

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0161484A1 (fr) * 1984-04-19 1985-11-21 Bayer Ag Poly(éthers d'aryle) liés essentiellement ortho
DE4109527A1 (de) * 1990-03-22 1991-09-26 Toyo Engineering Corp Verfahren zur reinigung eines polymers
US5312882A (en) * 1993-07-30 1994-05-17 The University Of North Carolina At Chapel Hill Heterogeneous polymerization in carbon dioxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0161484A1 (fr) * 1984-04-19 1985-11-21 Bayer Ag Poly(éthers d'aryle) liés essentiellement ortho
DE4109527A1 (de) * 1990-03-22 1991-09-26 Toyo Engineering Corp Verfahren zur reinigung eines polymers
US5312882A (en) * 1993-07-30 1994-05-17 The University Of North Carolina At Chapel Hill Heterogeneous polymerization in carbon dioxide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 88, no. 22, 29 May 1978, Columbus, Ohio, US; abstract no. 153255d, FUJINO ET AL: "Poly(phenylene oxide)" page 17; XP002010569 *
KAPELLEN K.K. ET AL: "Synthesis of poly(2,6-dimethylphenylene oxide) in carbon dioxide", MACROMOLECULES, vol. 29, no. 1, 1 January 1996 (1996-01-01), pages 495 - 496, XP002010568 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6191215B1 (en) 1999-03-05 2001-02-20 Basf Aktiengesellschaft Process for the preparation of pulverulent polymers by polymerization in supercritical carbon dioxide in the presence of polyoxyalkylene-polysiloxane copolymers
US9546316B2 (en) 2012-11-12 2017-01-17 Saudi Arabian Oil Company Densifying carbon dioxide with a dispersion of carbon dioxide-philic water capsules
US10047276B2 (en) 2012-11-12 2018-08-14 Saudi Arabian Oil Company Densifying carbon dioxide with a dispersion of carbon dioxide-philic water capsules
US10400158B2 (en) 2012-11-12 2019-09-03 Saudi Arabian Oil Company Densifying carbon dioxide with a dispersion of carbon dioxide-philic water capsules
US11060014B2 (en) 2012-11-12 2021-07-13 Saudi Arabian Oil Company Densifying carbon dioxide with a dispersion of carbon dioxide-philic water capsules
WO2016033156A1 (fr) * 2014-08-27 2016-03-03 Sabic Global Technologies B.V. Polymérisation oxydative de phénols catalysée par le fer

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