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WO1986002368A1 - Poly(ether cetones) aromatiques possedant des groupes imide, amide, ester, azo, quinoxaline, benzimidazole, benzoxazole ou benzothiazole et procede de preparation - Google Patents

Poly(ether cetones) aromatiques possedant des groupes imide, amide, ester, azo, quinoxaline, benzimidazole, benzoxazole ou benzothiazole et procede de preparation Download PDF

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Publication number
WO1986002368A1
WO1986002368A1 PCT/US1985/002013 US8502013W WO8602368A1 WO 1986002368 A1 WO1986002368 A1 WO 1986002368A1 US 8502013 W US8502013 W US 8502013W WO 8602368 A1 WO8602368 A1 WO 8602368A1
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Prior art keywords
phenylene
polymer according
repeat unit
polymer
chloride
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PCT/US1985/002013
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English (en)
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Klaus Joachim Dahl
Patrick James Horner
Heinrich Carl Gors
Viktors Jansons
Richard Harold Whiteley
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Raychem Corporation
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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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/18—Polybenzimidazoles
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/127—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from carbon dioxide, carbonyl halide, carboxylic acids or their 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0677—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08G75/32—Polythiazoles; Polythiadiazoles

Definitions

  • This invention relates to novel aromatic poly(ether ketones) having imide, amide, ester, azo, quinoxaline, benzimidazole, benzoxazole, or benzothiazole groups and to methods for their preparation, particularly to electrophilic polymerization in the presence of a Lewis acid and a complex between a Lewis acid component and a Lewis base component and, optionally, a diluent.
  • Aromatic poly(ether ketones) can be prepared by Friedel Crafts synthesis in which an aryl ketone linkage is formed from a carboxylic acid halide and an aromatic compound having an activated hydrogen, i.e., a hydrogen atom displaceable under the electrophilic reaction conditions.
  • the monomer system employed in the reaction can be, for example, (a) a single aromatic compound containing a carboxylic acid halide as well as an aromatic carbon bearing a hydrogen activated towards electrophilic substitution; or (b) a twomonomer system of a dicarboxylic acid dihalide and an aromatic compound containing two such activated hydrogens.
  • a common medium for such Friedel Crafts reactions consists of the reactant(s), a catalyst, such as anhydrous aluminum chloride, and an inert solvent such as methylene chloride. Because carbonyl groups complex with aluminum trichloride and thereby deactivate it, the aluminum chloride catalyst is generally employed in the preparation of arylene ketones in an amount slightly more than one equivalent for each equivalent of carbonyl groups in the reaction medium. The slight excess assures that enough free aluminum chloride will be present to fulfill its catalytic role. Other metal halides such as ferric chloride may be employed as the catalyst, but generally with less satisfactory results.
  • This invention provides polymers comprising a repeat unit
  • R 1 is independently p-phenylene or 4,4'-biphenylene;
  • R 2 is
  • R 3 is independently C 1 to C 12 alkylene or fluorinated alkylene or substituted or unsubstituted p-phenylene, m-phenylene, 1,4naphthylene, 2,6-naphtnylene, 2,6-pyridinediyl, 2,5-pyridinediyl, or
  • R 4 is substituted or unsubstituted
  • R 5 is independently substituted or unsubstituted X X is independently ester, amide, or azo; Y is independently
  • A is independently ether, ketone, sulfone, C 1 to C 12 alkylene or fluorinated alkylene, thioether, hexafluoroisopropylidene, isopropylidene, or a direct bond;
  • Z is independently hydrogen, phenyl, or lower alkyl; and n is 1 or 2.
  • a process for preparing aromatic poly(ether ketones) having an imide, anide, ester, azo, quinoxaline, benzimidazole, benzoxazole, or benzothiazole group comprising polymerizing a monomer system selected from the group consisting of
  • This invention provides aromatic poly(ether ketones) having imide, amide, ester, azo, quinoxaline, benzimidazole, benzoxazole, or benzothiazole groups.
  • a preferred method for making these polymers is Friedel Crafts polymerization, in which the polymerization step consists of the reaction of a carboxylic acid halide with an aromatic group having a hydrogen activated towards electrophilic substitution to form a diaryl ketone.
  • Particularly preferred is Friedel Crafts polymerization in the presence of excess Lewis acid and a complex between a Lewis acid and a Lewis base.
  • Monomer systems suitable for the preparation of the polymers of this invention by Friedel Crafts polymerization are of two general types.
  • the first which will be called the one monomer system, comprises an aromatic compound having both a carboxylic acid halide and a hydrogen atom activated towards electrophilic substitution.
  • Such a monomer is called an EN monomer because it has both an electrophillic group (the carboxylic acid halide) and a nucleophilic group (the aromatic group having the activated hydrogen).
  • EN monomers are illustrative but not exhaustive:
  • X is independently amide, ester, or azo and where Y is independently where Z is independently hydrogen, phenyl, or lower alkyl.
  • Polymers of this invention which can be prepared fr ⁇ n EN monomers include, for example
  • the second monomer system which will be called the two monommr system, comprises a dicarboxylic acid dihalide and an aromatic compound having two hydrogen atoms activated towards electrophilic substitution.
  • these are called the EE and NN monomers, respectively.
  • the EE and NN monomers should be present in substantially stoichiometric amounts.
  • Illustrative but not exhaustive examples of EE monomers are:
  • X and Y are as hereinbefore defined and A is independently ether, ketone, sulfone, C 1 to C 12 alkylene or fluorinated alkylene, thioether, isopropylidene, hexafluoroisopropylidene, or a direct bond and where
  • NN monomers Illustrative but not exhaustive examples of NN monomers are:
  • EE monomer having no X or Y groups it should be polymerized with an NN monomer having an X or Y group, and vice-versa.
  • both EE and NN can have an X or Y group. Examples of polymers which can be prepared in such a manner include
  • the carboxylic acid halides were consistently represented as the chloride as a matter of convenience. It will be apparent to one skilled in the art that the acid fluoride and the acid bromide are also suitable. Also, as a matter of convenience, aromatic rings have been drawn as unsubstituted, although it will be apparent to one skilled in the art that they may have one or more substituents which are inert under the polymerization conditions and which do not interfere with the polymerization. Examples of such substituents include lower alkyl, particularly methyl; cyano; halogen, particularly fluoro, bromo and chloro; nitro; and benzoyl.
  • the polymers of this invention include copolymers.
  • two or more different EN monomers may be copolymerized.
  • a single EE monomer can be copolymerized with two or more different NN monomers.
  • one or more EN monomers can be polymerized with combinations of EE and NN monomers.
  • polymers of this invention include copolymers with prior art poly(ether ketones).
  • the repeat units of particular interest for incorporation into copolymers are
  • the monomer(s) used should be relatively free of any impurities which would interfere with the polymerization.
  • a "hydrogen activated towards electrophilic substitution” is a hydrogen bonded to an aromatic carbon atom and displaceable by an acyl group under the well-known conditions for Friedel Crafts acylation to occur. In particular, it is displaceable under the reaction conditions of this invention.
  • a hydrogen is activated for a Friedel Crafts reaction by the presence of an electron donating group ortho or para to it.
  • Particularly desirable activated hydrogen bearing aromatic moieties are phenoxy (C 6 H 5 O-) and p-biphenyloxy (C 6 H 5 -p-C 6 H 4 -O-).
  • a phenoxy group is deemed to have only one activated hydrogen. It has been our experience that reaction generally takes place at the para- position (i.e., it is the para- hydrogen that is "activated"), particularly where the polymerization is run in the presence of a Lewis acid and a complex between a Lewis acid and a Lewis base, as taught hereinafter.
  • a preferred process for preparing the polymers of the instant invention comprises the use of a reaction medium comprising free Lewis acid and a complex between a Lewis acid and a Lewis base and, optionally, a diluent.
  • the term "complex" is used to mean any product of the reaction between the Lewis acid and the Lewis base.
  • a diluent is employed if the complex is a solid at polymerization temperatures and can be present, if desired, when the complex is liquid.
  • Lewis acid is used herein to refer to a substance which can accept an unshared electron pair fr ⁇ n another molecule.
  • Lewis acids which can be used in the practice of this invention include, for example, aluminum trichloride, aluminum tribromide, antimony pentachloride, antimony pentafluoride, indium trichloride, gallium trichloride, boron trichloride, boron trifluoride, zinc chloride, ferric chloride, stannic chloride, titanium tetrachloride, and molybdenum pentachloride.
  • substantially anhydrous aluminum trichloride as the Lewis acid is preferred.
  • the amount of Lewis acid used in the practice of this invention varies depending on the particular monomers and reaction medium selected. In all instances at least about one equivalent of Lewis acid per equivalent of carbonyl groups present in the monomer system is used plus an amount effective to act as a catalyst for the reaction (also referred to herein as a catalytic amount). Generally a catalytic amount added is from about 0.05 to about 0.3 equivalents of Lewis acid per equivalent of acid halide in the reaction mixture. Additional amounts of Lewis acid are also required depending on the nature of the monomers and the reaction conditions in a manner as set forth below. Further, if a cxmon ⁇ ner containing other basic species is used, additional Lewis acid may be required.
  • the reaction is controlled by the addition of a controlling agent which, inter alia, suppresses undesirable side reactions, particularly alkylation and/or ortho substitution of activated aryl groups. Suppression of side reactions results in polymer that can that will be more readily melt processable because it will be less likely to degrade or cross-link when subjected to elevated temperatures, e.g. temperatures above its melting point. For a polymer of this type to be suitable for melt processing, it must be able to withstand the processing temperatures for the required processing time.
  • these conditions require that the polymer can withstand temperatures up to about 30°C above the melting or softening point of the polymer for periods of at least 30 minutes, preferably at least 60 minutes and most preferably at least 90 minutes, without undesired gel formation or substantial change in inherent viscosity.
  • Lewis bases are Lewis bases.
  • the term "Lewis base” is used herein to refer to a substance capable of donating an unshared electron pair to a Lewis acid.
  • the Lewis base forms a complex with the Lewis acid used in the reaction medium.
  • Lewis bases which form a 1:1 c ⁇ nplex having a heat of association at least about that of diphenyl ether with the Lewis acid are preferred.
  • aluninum trichloride is the Lewis acid the Lewis base used should form a 1:1 c ⁇ nplex having a heat of association of at least about 15 kcal/faole, preferably at least about 20 kcal/mole and most preferably at least about 30 kcal/mole. While the heats of association are for a 1:1
  • Lewis acid /Lewis base complex consisting solely of these two components, the actual complex formed in the reaction medium need not be a 1:1 complex.
  • a discussion on heats of association for Lewis acid/Lewis base complex is found in J. Chem Sec. (A), 1971, pages
  • the Lewis base used should not be an acylating, alkylating or arylating agent nor should it be acylatable under the reaction conditions. Mixtures of two or more Lewis bases can be used if desired.
  • the Lewis base used as a cootrolling agent in the practice of this invention is an additional component added to the reaction medium. This does not include basic species formed in situ during the reaction.
  • Typical Lewis bases which can be employed include, for example, amides, amines, esters, ethers, ketones, nitriles, nitro compounds, phosphines, phosphine oxides, phosphoramides, sulfides, sulfones, sulfonamides, sulfoxides and halide salts.
  • Examples of specific organic Lewis bases that can be used in the practice of this invention are acetone, benzophenone, cyclohexanone, methyl acetate, ethylene carbonate, N-methyl-formamide, acetamide,
  • N-acetylmorpholine dimethyl sulfoxide, N,N-dimethylformanide, diphenyl sulfone, N,N-dimethylmethane-sulfonamide, phosphoryl chloride, phenylphosphonyl chloride, pyridine-N-oxide, triphenylphosphine oxide, trioctylphosphine oxide, nitropropane, nitrobenzene, benzonitrile, n-butyronitrile, methyl ether, tetrahydrofuran, dimethyl sulfide, trimethylamine, N,N,N",N'tetramethylethylenediamine, N,N-dimethyldodecylamine, imidazole, pyridine, quinoline, isoquinoline, benzimidazole, 2,2'-bipyridine, o-phenanthroline, 4-dimethylaninopyridine, and the like.
  • suitable Lewis bases include inorganic salts which can form complexes with Lewis acids, for example, chlorides, such as trimethylammonium chloride, tetramethylammonium chloride, sodiun chloride or lithiun chloride, perchlorates, trifluoro-methanesulfonates and the like.
  • Preferred Lewis bases for the reaction median of this invention are N-methylformamide, N,N-dimethyl-formamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, tetrartethylene sulfone (also known as sulfolane), n-butyroni-trile, dimethyl sulfide, imidazole, acetone, benzophenone, trimethylamine, trimethylamine hydrochloride, tetramethyl-ammonium chloride, pyridine-N-oxide, 1-ethylpyridinium chloride, lithium chloride, lithiun bromide, sodiun chloride, sodium bromide, potassium chloride, potassium bromide and mixtures thereof.
  • the amount of Lewis base present should be fr ⁇ n 0.01 to about 4 equivalents per equivalent of acid halide groups present in the mon ⁇ ner system. Preferably at least about 0.05 and most preferably at least about 0.5 equivalents of Lewis base per equivalent of acid halide groups present should be used. Anounts greater than 4 equivalents could be employed, if desired. However, no additional controlling effect is usually achieved by adding larger amounts.
  • the temperature at which the reaction is conducted can be from about -50oC to about +150oC. It is preferred to start the reaction at lower temperatures, for example at about -50 to about -10°C particularly if the mon ⁇ ner system contains highly reactive monomers. After reaction has c ⁇ nmenced, the temperature can be raised if desired, up to 150°C or even higher, for example, to increase the rate of reaction. It is generally preferred to carry out the reaction at temperatures in the range of between about -30°C and +25°C (room temperature).
  • Lewis base acts to control the reaction, it is believed that one or more of the following factors may be involved.
  • the Lewis acid/Lewis base complex appears to influence the catalytic activity of Lewis acid, so as to substantially eliminate all ortho or meta acylation.
  • the Lewis acid/Lewis base complex substantially reduces the tendency of the diluent to act as an alkylating agent by competing with the diluent for available Lewis acid and thereby suppressing alkylation of the polymer.
  • Alkylation of the polymer in the para position caps the reaction while alkylation in the ortho position introduces undesired reactive sites in the polymer chain which can lead to branching or cross-linking.
  • a non-protic diluent can also be employed, if desired.
  • the diluent should dissolve the Lewis acid/Lewis base c ⁇ nplex and the resulting olig ⁇ ner/Lewis acid complex but this is not an essential requirement of the diluent. It should also be relatively inert toward Friedel-Crafts reactions.
  • the diluent is used in an amount from 0 to about 93% by weight, based on the weight of the total reaction mixture.
  • the reactions can be run neat, that is without the presence of a diluent. This is true for the process of this invention whether or not a Lewis base is used.
  • a Lewis base is used.
  • the mon ⁇ ner to diluent molar ratio can contribute to control of the reaction to yield the desired product.
  • the molecular weight of the polymer, the degree of branching and amount of gelation can be controlled by the use of, for example, capping agents as described in U.S. Patent No. 4,247,682 to Dahl, the disclosure of which is incorporated herein by reference.
  • the molecular weight of the polymer can also be controlled by a reaction utilizing a two-monomer system as described above, by employing a slight excess of one of the monomers.
  • Capping agents when employed, are added to the reaction medium to cap the polymer on at least one end of the chain. This terminates continued growth of that chain and controls the resulting molecular weight of the polymer, as shown by the inherent viscosity of the polymer. Judicious use of the capping agents results in a polymer within a selected narrow molecular weight range, decreased gel formation during polymerization, and decreased branching of the polymer chains and increases melt stability. Both nucleophilic and electrophilic capping agents can be used to cap the polymer at each end of the chain.
  • Preferred nucleophlic capping agents are 4-phenoxybenzophenone, 4-(4-phenoxyphenoxy)benzophenone, 4,4'-diphenoxybenzophenone, and the like.
  • Typical electrophilic capping agents are compounds of the formula
  • Ar is phenyl, 3-chlorophenyl, 4-chlorophenyl, 4-cyanophenyl, 4-methylphenyl or an aromatic group substituted with an electron withdrawing substituent and E is halogen or other leaving group.
  • Preferred electrophilic capping agents include benzoyl chloride, benzenesulfonyl chloride and the like.
  • Decomplexation of the polymer from the catalyst can be accomplished by treating the reaction mixture with a decomplexing base after completion of polymerization.
  • the base can be added to the reaction medium or the reaction medium can be added to the base.
  • the decomplexing base must be at least as basic towards the Lewis acid as the basic groups on the polymer chain. Such deccmplexation should be effected before isolation of the polymer from the reaction mixture.
  • the amount of decomplexing base used should be in excess of the total amount of bound (complexed) and unbound Lewis acid present in the reaction mixture and is preferably twice the total amount of Lewis acid.
  • Typical dec ⁇ mplexing bases which can be used include water, dilute aqueous hydrochloric acid, methanol, ethanol, acetone, N,Ndimethyl-formamide, N,N-dimethylacetamide, pyridine, dimethyl ether, diethyl ether, tetrahydrofuran, trimethylamine, trimethylamine hydrochloride, dimethyl sulfide, tetramethylenesulfone, benzophenone, tetramethylammoniun chloride, isopropanol and the like.
  • the deccmplexed polymer can then be removed by conventional techniques such as adding a nonsolvent for the polymer which is a solvent for or miscible with the Lewis acid/Lewis base complex and the Lewis acid; spraying the reaction medium into a non-solvent for the polymer; separating the polymer by filtration; or evaporating the volatiles fr ⁇ n the reaction medium and then washing with an appropriate solvent to remove any remaining base/catalyst complex and diluent fr ⁇ n the polymer.
  • a method for removing the catalyst residue is described in Dahl, U.S. Patent No. 4,239,884, the disclosure of which is incorporated by reference.
  • the polymers of this invention can be used in any number of ways. Because of their predominantly or wholly aromatic nature, they possess outstanding thermal stability, as evidenced by their thermogravimetric (TGA) 1% weight loss temperatures being generally above 400°C and often above 500°C. They also possess superior mechanical properties, which are retained at elevated temperatures in view of their glass transition temperatures (Tg's) of above 150°C. Furthermore, many of these polymers are crystalline, also contributing to the maintenance of mechanical properties at elevated temperatures. Also, they possess resistance to many common solvents. Thus, the polymers of this invention are particularly suitable for use in those applications generally reserved for the so-called "heat stable" or "high performance” polymers.
  • the polymers of this invention can be used in films, filaments, electrical insulation, coatings, molded articles, and like applications. Generally, conventional fabrication techniques such as injection molding and extrusion can be used.
  • high molecular weight polymer we mean one having an inherent viscosity of 0.6 or greater. While the process of this invention is particularly suitable for the preparation of high molecular weight polymers, low molecular weight polymers — which may be desirable for certain applications — can readily be prepared, for example by appropriate use of a capping agent or stoichi ⁇ netric imbalance. The lower molecular weight polymers may be desirable for certain applications, such as adhesives or as powder coatings.
  • the bis-amide of p-phenylene diamine with p-phenoxybenzoic acid was prepared as follows.
  • DMAc N,N-dimethylacetamide
  • N,N-Dimethylformamide (DMF, 2.3 mL, 2.19 g, 0.03 mole) was added with stirring and cooling to a mixture of aluninun chloride (10.3 g, 0.077 mole) in methylene chloride (50 mL).
  • the bis-amide prepared in Example 1 (5.0032 g, 0.01000 mole) was then added.
  • the mixture was cooled to -6°C and terephthalcyl chloride (2.0300 g, 0.009998 mole) was added, with stirring.
  • An intense yellcw-brown colored solution with an orange-brown precipitate resulted. It was stirred at -6°C for 15 min and then allowed to warm up to room temperature. The reaction mixture gelled after another 8 min.
  • the polymerization mixture was worked up by blending it with methanol (ca. 250 mL) in a Waring blender, filtering, washing with methanol (2 x 75 mL), and drying at 140oC for 4 hours in vacuum, to yield 6.00 g (95%) of fibrous pale yellow green polymer with the repeat unit
  • the polymer was also partially soluble in DMAc/lithium bromide. GPC of such a solution showed a molecular weight spread between 30,000 and 3,000,000 (poly(ethylene oxide) equivalent molecular weight).
  • the bis-amide of m-phenylene dianine and p-phenoxybenzoic acid was prepared according to the procedure of Example 1.
  • the product had a mp of 222-23oC and was shown to be 99.99% pure by DSC.
  • the polymer could be hot pressed into a tough amber translucent slab at about 260°C.
  • a sample cut fr ⁇ n the slab had the following mechanical properties: modulus, 140,000 psi; elongation to break, 21%; ultimate tensile strength, 12,000 psi; and no yield point.
  • modulus 140,000 psi
  • elongation to break 21%
  • ultimate tensile strength 12,000 psi
  • no yield point When a slab was pressed at 305oC, the polymer was brittle.
  • TGA in air showed a 1% weight loss at 430oC. No crystallinity was detected hy DSC or X-ray diffraction. A Tg of 220oC was detected by DSC and dynamic mechanical analysis.
  • N,N'-Bis(4-phenoxyphenyl)pyromellitimide was prepared as follows. p-Phenoxyaniline (19.45 g, 0.105 mole, mp 82.5 - 84.5°C, recrystallized from methanol-water after treatment with activated charcoal and zinc dust), pyromellitic dianhydride (10.91 g, 0.050
  • the pyromellitimide prepared in Example 5 (3.5915 g, 0.0065 mole) was polymerized with isophthaloyl chloride (1.3400 g, 0.0066 mole), with p-phenoxybenzophenone (0.0549 g, 0.0002 mole) as a capping agent.
  • the amounts of aluminum chloride and DMF used were 9.654 g (0.0724 mole) and 2.05 mL (0.0264 mole), respectively.
  • the bis-p-phenoxybenzoate of hydroquinone was prepared by the following procedure.
  • Hydroquinone (5.50 g, 0.0500 mole) was stirred with heating (oil bath at 185°C) with bis(tri-n-butyltin) oxide (29.81 g, 0.0500 mole) in xylene (225 mL). 50 mL of xylene was distilled off, using a DeanStark trap. The solution was then cooled to about 100°C and pphenoxybenzoyl chloride (24.43 g, 0.105 mole) in xylene (20 mL) was added. The mixture was stirred at 100°C for 2 hr. Upon cooling, the product crystallized out.
  • the reaction mixture was poured into methanol (1000 mL) and the product collected by filtration, washed with methanol (2 x 100 mL), and dried at 100°C for 90 min under vacuum.
  • the yield was 22.13 g of shiny white crystals, mp 195 - 197°C, 99.94% pure by DSC.
  • Example 7 The bis-ester of Example 7 (3.9699 g, 0.079 mole) and terephthaloyl chloride (1.5836 g, 0.0078 mole) were polymerized by the procedure of Example 4. The amounts of aluninun chloride and DMF used were 9.19 g (0.0689 mole) and 2.40 mL (0.0312 mole), respectively.
  • Example 10 The polymerization of Example 4 was repeated, but with lithium chloride (1.20 g, 0.0284 mole) used instead of DMF. The polymer (4.19 g, 93.5% yield) was obtained as cream colored fibers. Its RV was 2.17, with substantial amounts of undissolved material.
  • Example 10 The polymerization of Example 4 was repeated, but with lithium chloride (1.20 g, 0.0284 mole) used instead of DMF. The polymer (4.19 g, 93.5% yield) was obtained as cream colored fibers. Its RV was 2.17, with substantial amounts of undissolved material.
  • Example 8 The polymerization of Example 8 was repeated, but with a 1:1 mixture of terephthaloyl chloride and isophthaloyl chloride instead of terephthaloyl chloride, to yield a polymer with the repeat unit
  • Bis-(p-phenoxyphenyl) terephthalate was prepared from p-phenoxyphenol and terephathloyl chloride by the method of Example 7. The product was obtained in 90.6% yield, mp 192.9 - 193.8°C, DSC purity 99.87%.
  • Bis-(p-phenoxyphenyl) terephthalate from Example 11 (3.8946 g, 0.00775 mole) was polymerized with a 1:1 mixture of terephthaloyl and isophthaloyl chlorides (1.5988 g total, 0.007875 mole total), with p-phenoxybenzophenone (0.0686 g, 0.00025 mole) as a capping agent by the procedure of Example 4.
  • the amounts of aluminum chloride and DMF used were 9.20 g (0.069025 mole) and 2.43 mL (0.0315 mole), respectively.
  • the polymer was partly soluble in concentrated sulfuric acid, RV 0.76 dl/g.
  • N,N'-Bis-(4-phenoxyphenyl)-3,3',4,4'-benzophenone tetracarboxylic di-imide was prepared was follows.
  • BPTCDA 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride
  • BPBPTCDI was polymerized with a 7:3 mixture of iso- and terephthaloyl chlorides as follows.
  • Example 4 The general procedure was of Example 4 was followed, using the following materials: BPBPTCDI (0.0150 mole, 9.8498 g), terephthaloyl chloride (0.0046 mole, 0.9319 g), isophthaloyl chloride (0.0107 mole, 2.1744g vacuum distilled and recrystallized from hexane, mp 42.543.8°C, DSC purity 99.75%), 4-phenoxybenzophenone (capping agent, 0.0006 mole, 0.1646 g), DMF (0.0612 mole, 4.71 mL), aluninun chloride (0.1842 mole, 24.56 g), and DCE (120 mL). The acid chlorides were added at -26oC. The mixture was dark brown.
  • the polymer had an inherent viscosity of 1.68. It was partially soluble, with difficulty, in hot o-chlorophenol.
  • Al residue determined by atomic absorption spectroscopy was 320 ppm.
  • thermogravimetric curves at 2.5, 5, 10 and 20°C/m ⁇ inute gave the following parameters:
  • p-Phenoxybenzoyl chloride (36.77g, 0.158 mole) was added at room temperature to a stirred solution of hexamethylene diamine (8.75 g, 0.075 mole) in DMAc (230 mL). The temperature of the reaction mixture rose to about 75°C and a white precipitate formed. After standing overnight the mixture was heated at 100°C for 1 hour, allowed to cool then poured into a stirred mixture of 200 mL sodiun hydroxide (1 N) and water (1 L).
  • Bis-(p-phenoxyphenyl) isophthalate was prepared from pphenoxyphenol and isophthaloyl chloride by the method of Example 7. The product was obtained in 91.8% yield and recrystallized from a 2.5:1 v/v chlorobenzene-hexane (DSC purity 99.72%, mp 147.1-148.6°C).
  • This ester (10.5530g, 0.0210 moles) was polymerized with terephthaloyl chloride (4.3244g, 0.02130 moles) using the procedure of Example 16.
  • p-Phenoxybenzophenone (0.1646g, 0.0006 moles) was used as a capping agent.
  • the amounts of aluninun chloride and DMF used were 25.000g (0.1875 moles) and 6.56 mL (0.0852 moles), respectively.
  • the white fibrous polymer which was obtained had the repeat unit
  • BPBPTCDI (9.8498 g, 0.0150 moles) was polymerized with terephthaloyl chloride (3.1063 g, 0.0153 moles) using the other materials and the procedure of Example 16.
  • the lemon yellow fibrous polymer obtained was completely soluble in concentrated sulfuric acid (IV 1.45 dl/g).
  • Example 20 was repeated using isophthaloyl chloride instead of terephthaloyl chloride.
  • the lemon yellow fibrous polymer (11.48 g, 95.6% yield) which was obtained was completely soluble in concentrated sulfuric acid (IV 1.12 dl/g).
  • DSC showed a Tg at 215°C, a crystallization exotherm at 260-320°C (maximum 302oC) and a melting endotherm at 340-370°C (maximun 358°C).
  • TGA analysis indicated a 1% loss in nitrogen at 486°C (459°C in air). It had the repeat unit
  • Example 20 was repeated using a 1:1 w:w mixture of isophthaloyl and terephthaloyl chlorides.
  • the lemon yellow fibrous polymer was completely soluble in concentrated sulfuric acid (IV 1.09 dl/g).
  • DSC showed a Tg at 220°C, a crystallization exotherm at 240-280oC (maximum 255°C) and a melting endotherm at 360-390°C (maximum 382°C).
  • TGA analysis indicated a 1% loss in nitrogen at 507oC (469°C in air).
  • Example 20 was repeated using a 3:7 w:w mixture of isophthaloyl and terephthaloyl chlorides.
  • the lemon yellow fibrous polymer was completely soluble in concentrated sulfuric acid (IV 0.79 dl/g).
  • DSC showed a Tg at 219°C, a crystallization exotherm at 230-280°C (maximum 248°C) and a melting endotherm at 350-390°C (maximum 381oC).
  • TGA analysis indicated a 1% loss in nitrogen at 502oC (465°C in air).
  • Example 16 was repeated except that a mixture of BPBPTCDI (1.9700 g, 0.0030 moles) and 4,4'-diphenoxybenzophenone (4.3970g, 0.0120 moles) was used.
  • the resultant copolymer had repeat units of the structures
  • DSC showed a Tg at 178°C and a melting endotherm at 300-370oC (maximum 340oC). TGA analysis indicated a 1% loss in nitrogen at 430°C (424°C in air).
  • BPDPBQ Bis-(p-phenoxyphenyl)diphenyl-6,6'-biquinoxaline
  • the IV of the polymer was 1.29 dl/g. It was partially soluble in o-chlorophenol (IV 0.85dl/g). DSC analysis showed a Tg of about 224°C. TGA indicated a 1% loss in nitrogen at 479°C (468°C in air).
  • N,N'-Bis-(4-phenoxyphenyl)isophthalamide was prepared by the reaction of p-phenoxyaniline with isophthaloyl chloride. This amide (10.5117 g, 0.0210 moles) was polymerized with terephthaloyl chloride (4.3243 g, 0.0213 moles) by the procedure of Example 27. The cream colored fibrous polymer which was obtained had the repeat unit
  • Example 28 was repeated except that isophthaloyl chloride was used in place of terephthaloyl chloride in the polymerization.
  • the light pink fibrous polymer which was obtained had the repeat unit
  • Example 28 was repeated except that the corresponding terephthalamide was used.
  • the light pink fibrous polymer which was obtained had the repeat unit
  • Example 27 was repeated except that the bis-amide of Example 1 was substituted for the bis-amide of Example 3.
  • the white fibrous polymer which was obtained had the repeat unit
  • Example 30 was repeated except that isophthaloyl chloride was used in place of terephthaloyl chloride in the polymerization.
  • the pink fibrous polymer which was obtained had the repeat unit
  • N,N'-Di-(4-phenoxyphenyl)hexafluoroglutaramide was prepared by reaction of p-phenoxyaniline with hexafluoroglutarpyl chloride.
  • This amide (6.0319g, 0.0105) was polymerized with terephthaloyl chloride (2.1624g, 0.01065 moles), with p-phenoxybenzophenone (0.1646g, 0.0006 moles) as capping agent and using the procedure of Example 27.
  • the amounts of aluninun chloride, DMF and DCE used were 12.49g (0.0937 moles), 3.3 mL (0.0426 moles) and 50 mL, respectively.
  • the polymer which was obtained as white powdery flakes had the repeat unit
  • Example 33 The polymerization of Example 33 was repeated using isophthaloyl chloride in place of terephthaloyl chloride.
  • the light pink polymer which was obtained had the repeat unit
  • N,N'-Bis-(4-phenoxyphenyl)adipamide was prepared by the reaction of p-phenoxyaniline with adipoyl chloride.
  • This amide (5.8625g, 0.0122 moles) was polymerized with terephthaloyl chloride (2.4969g, 0.0123 moles) using p-phenoxybenzophenone (0.0825g, 0.0003 moles) as capping agent and following the procedure of Example 27.
  • the amounts of aluminum chloride, DMF and DCE used were 14.48 g (0.1086 moles), 3.79 mLs (0.0492 moles) and 60 mL, respectively.
  • the light pink fibrous polymer which was obtained had the repeat unit
  • N,N'-Bis-(4-phenoxyphenyl)-2,3,5,6-tetrafluoroterephthalamide was prepared from p-phenoxyaniline and 2,3,5,6-tetrafluoroterephthaloyl chloride.
  • This amide (6.0108 g, 0.0105 moles) was polymerized with terephthaloyl chloride (2.1316 g, 0.0105 moles) by the procedure of Example 27.
  • the amounts of aluminum chloride, DMF and DCE used were 12.55 g (0.094 moles), 3.3 mL (0.042 moles) and 60 mL, respectively.
  • the white fibrous polymer which was obtained had the repeat unit
  • N,N'-Bis-(4-phenoxyphenyl)-2,6-pyridine dicairboxamide was prepared from p-phenoxyaniline and 2,6-pyridine dicarboxylic acid dichloride.
  • the amide (8.0248g, 0.016 moles) was polymerized with isophthaloyl chloride (3.2484g, 0.016) using the procedure of Example 27.
  • the amounts of aluninun chloride, DMF and DCE used were 21.33g (0.160 moles), 4.71 mL (0.061 mol) and 100 mL, respectively.
  • the offwhite fibrous polymer which was obtained had the repeat unit
  • N,N'-Bis-(4-phenoxyphenyl)pyromellitimide was prepared from pphenoxyaniline and pyromellitic dianhydride.
  • the imide (10.7745g, 0.0195 moles) was polymerized with a 7:3 w:w mixture of isophthaloyl chloride (2.8140g, 0.01386 moles) and terephthaloyl chloride (1.2060 g, 0.00594 moles) in the presence of p-phenoxybenzophenone (0.1647g, 0.0006 moles) as a capping agent.
  • the amounts of aluminum chloride, DMF and DCE used were 28.96g (0.2172 moles), 6.15 mL (0.0792 moles) and 120 mL, respectively.
  • the yellow fibrous polymer which was obtained had the repeat unit
  • the imide monomer of Example 38 (2.1549 g, 0.0039 moles) and 4,4'-diphenoxybenzophenone (5.7162 g, 0.0156 moles) were polymerized with terephthaloyl chloride (3.9589 g, 0.0195 moles).
  • the amounts of aluminum chloride, DMF and DCE used were 28.96 g (0.2172 moles), 6.15 mL (0.0792 moles) and 120 mL.
  • the yellow fibrous copolymer which was obtained had the repeat units
  • N-(4-phenoxyphenyl)-1,2-dicarboximidobenzene-5-carboxylic acid chloride was prepared from p-phenoxyaniline and trimellitic anhydride followed by readticn with thionyl chloride.
  • This imide-acid chloride (1.1501 g, 0.0345 moles) was polymerized by the procedure of example 27 except that no capping agent was used and lithium chloride (0.8521 g) was substituted for the DMF.
  • the amounts of aluninun chloride and DCE used were 4.6000g (0.0345 moles) and 30 mLs, respectively.
  • the polymer was obtained as yellow powdery flakes which was completely soluble in concentrated sulfuric acid (IV, 1.02 dl/g).
  • the repeat unit had the structure
  • 2,2'-Bis-(4-phenoxyphenyl)-5,5'-bibenzimidazole is prepared from 3,3'-diaminobenzidine and phenyl p-phenoxybenzoate in polyphosphoric acid.
  • the bibenzimidazole of Example 43 is polymerized with terephthaloyl chloride to produce a polymer with the repeat unit
  • the benzobisoxazole of 2,5-diaminoresorcinol dihydrochloride and p-phenoxybenzoic acid is prepared by condensation with polyphosphoric acid catalysis by the general procedure of Wolfe, Polym. Prep. 19(2), 1 (1978) and then polymerized with terephthaloyl chloride, following the general procedure of Example 4, to produce a polymer having the repeat unit
  • the benzobisthiazole of 2,5-diamino-1,4-benzenedithiol dihydrochloride and p-phenoxybenzoic acid is prepared by condensation with polyphosphoric acid catalysis by the general procedure of Wolfe, supra, and then polymerized with terephthaloyl chloride, following the general procedure of Example 4, to produce a polymer having the repeat unit
  • 4,4'-Azobis(benzoyl chloride) is polymerized with diphenyl ether following the general procedure of Example 4 to produce the polymer having the repeat unit
  • the mono p-phenoxyphenyl carboxamide of terephthaloyl chloride is prepared from p-phenoxyaniline and a large excess of terephthaloyl chloride, following the general procedure of Example 1. After treatment with thionyl chloride to reconvert to the acid chloride of any carboxylic acid groups produced by adventitious hydrolysis, the product is polymerized following the general procedure of Example 40 to produce a polymer having the repeat unit -TO-
  • 4-phenoxyphthalic anhydride is prepared by the condensation of 4-nitrophthalonitrile with sodiun phenoxide, followed by hydrolysis and thermal dehydration.
  • the anhydride is reacted with p-phenylene diamine to form the bisimide, following the general procedure of Example 5.
  • the bisimide is then polymerized with terephthaloyl chloride following the general procedure of Example 4, to produce a polymer with the repeat unit
  • the imide of trimellitic anhydride and p-aminobenzoic acid is prepared and converted to the corresponding diacid chloride following the general procedures of Examples 5 and 40.
  • the diacid chloride is polymerized with diphenyl ether by the general procedure of Example 4 to produce a polymer with the repeat unit
  • the bisimide of pyromellitic anhydride and p-aminobenzoic acid prepared by the general procedure of Example 5 and converted to the corresponding diacid chloride with thionyl chloride, is polymerized with diphenyl ether following the general procedure of Example 4 to produce a polymer having the repeat unit
  • the bisimide of trimellitic anhydride and p-phenylene diamine prepared by the general procedure of Example 5 and converted to the corresponding diacid chloride with thionyl chloride, is polymerized with diphenyl ether following the general procedure of Example 4 to produce a polymer having the repeat unit
  • 4,4'-Azobis(benzoyl chloride) is polymerized with 1,4diphenoxybenzene following the general procedure of Example 4 to produce a polymer having the repeat unit
  • 4,4'-Azobis(benzoyl chloride) is polymerized with 4-biphenylyl ether following the general procedure of Example 4 to produce a polymer having the repeat unit

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Abstract

De nouveaux poly(éther cétones) aromatiques possédant des groupes imide, amide, ester, azo, quinoxaline, benzimidazole, benzoxazole ou benzothiazole, comprenamt par ex. une unité répétitive (I) sont préparés par une réaction de polymérisation de Friedel Crafts.
PCT/US1985/002013 1984-10-11 1985-10-11 Poly(ether cetones) aromatiques possedant des groupes imide, amide, ester, azo, quinoxaline, benzimidazole, benzoxazole ou benzothiazole et procede de preparation WO1986002368A1 (fr)

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EP0315441A3 (fr) * 1987-11-04 1990-07-18 Raychem Limited Polyarylène-éther-cétones
US5098985A (en) * 1988-10-11 1992-03-24 The Dow Chemical Company Copolymers containing polybenzoxazole, polybenzothiazole and polybenzimidazole moieties
US5110894A (en) * 1988-10-11 1992-05-05 The Dow Chemical Company Copolymers containing polybenzazole mer units and poly(aromatic ketone) or poly(aromatic sulfone) mer units
US5151489A (en) * 1988-10-11 1992-09-29 The Dow Chemical Company Copolymers containing polybenzoxazole, polybenzothiazole and polybenzimidazole moieties
US5225515A (en) * 1991-04-17 1993-07-06 The Dow Chemical Company Poly(aryl ether) polymers containing perfluorocyclobutane rings
US5244617A (en) * 1992-02-05 1993-09-14 The Dow Chemical Company Consolidation and molding of polybenzazole-containing materials
CN103642032A (zh) * 2013-11-15 2014-03-19 吉林大学 含苯并噁唑环侧基的支化磺化聚芳醚酮、制备方法及其应用
US10450408B2 (en) 2014-09-10 2019-10-22 Ketonex Limited Method for making polyarylaliphaticetherketone polymers and copolymers thereof
US10800876B2 (en) 2014-05-22 2020-10-13 Ketonex Limited Amine and non-amine derivatized polyaryletherketone random and block copolymers

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US5098985A (en) * 1988-10-11 1992-03-24 The Dow Chemical Company Copolymers containing polybenzoxazole, polybenzothiazole and polybenzimidazole moieties
US5110894A (en) * 1988-10-11 1992-05-05 The Dow Chemical Company Copolymers containing polybenzazole mer units and poly(aromatic ketone) or poly(aromatic sulfone) mer units
US5151489A (en) * 1988-10-11 1992-09-29 The Dow Chemical Company Copolymers containing polybenzoxazole, polybenzothiazole and polybenzimidazole moieties
US5225515A (en) * 1991-04-17 1993-07-06 The Dow Chemical Company Poly(aryl ether) polymers containing perfluorocyclobutane rings
US5244617A (en) * 1992-02-05 1993-09-14 The Dow Chemical Company Consolidation and molding of polybenzazole-containing materials
CN103642032A (zh) * 2013-11-15 2014-03-19 吉林大学 含苯并噁唑环侧基的支化磺化聚芳醚酮、制备方法及其应用
CN103642032B (zh) * 2013-11-15 2015-10-28 吉林大学 含苯并噁唑环侧基的支化磺化聚芳醚酮、制备方法及其应用
US10800876B2 (en) 2014-05-22 2020-10-13 Ketonex Limited Amine and non-amine derivatized polyaryletherketone random and block copolymers
US10450408B2 (en) 2014-09-10 2019-10-22 Ketonex Limited Method for making polyarylaliphaticetherketone polymers and copolymers thereof

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