PREPARATION OF AROMATIC POLYMERS

Abstract: A process for producing an aromatic polyketone which comprises polymerizing an appropriate monomer or monomers by a Friedel-Crafts polymerization reaction using a Lewis acid catalyst. A controlling agent such as a Lewis base may be added to the reaction medium and/or the reaction is conducted under specified conditions to control the reaction. The reaction medium comprises, for example, aluminum trichloride as the Lewis acid, an organic Lewis base such as N, N-dimethylformamide or an inorganic Lewis base such as sodium or lithium chloride, and a diluent such as methylene chloride or dichloroethane. The amount of Lewis acid, the amount of Lewis base, the temperature of the reaction and the monomer to diluent molar ratio are varied depending on the monomer system to obtain melt-processable, high molecular weight, substantially linear polymers, for example poly(carbonyl-p-phenylene-oxy-p-phenylene), poly(carbonyl-p-phenylene-oxy-p-phenylene-oxy-p-phenylene), and the like. Copolymers containing up to 30% by weight of an aromatic sulfonyl halide comonomer can also advantageously be produced by this process.

Description: Backqround of the Invention PREPJ-RATION OF AROMATIC POLYMERS This invention relates to a method of preparing poly( ar-ylene ketones) and in particular to an electro¬ philic pol merization process for preparing such polymers. Poly(arylene ketones), in particular, all para- linked poly(aryl ether ketones), possess many desirable properties, for example, high temperature stability, mechani¬ cal strength , and resistance towards common solvents. The r oaration of pαly(arylene ether ketones) by two different ε laches has been described in the literature. The first ap r .-αach is an electrophilic synthesis in which an aryl ketone linkage is formed. The second is a nucleophilic synthesis in which an aryl ether linkage is formed. This invention is directed to an improved electrophilic synthesis fσr preparing poly(arylene ketones), in particular para- linked pαly(aryl ether ketones). In such an electrophilic synthesis, the polymer- ir on step involves the formation of an aryl ketone group f: a carboxylic acid or acid derivative group and an aromatic compound containing an aromatic carbon bearing an activated hydrogen atom, i.e. a hydrogen atom displaceable under the electrophilic reaction conditions. The monomer •system employed in the pol merization can be, for example, (a) a single aromatic compound containing both a carboxylic OMPI acid or acid derivative group as well as an activated hydrogen atom on an aromatic carbon for example, p-phenoxy- benzoyl chloride; or (b) a two-component- system of a dicar¬ boxylic acid or acid derivative and an aromatic compound containing two activated hydrogen . atoms, for example, 1 ,4-diphenoxybenzene and terephthaloyl chloride. Electrophilic polymerization of this type is often referred to as Friedel-Crafts polymerization. Typically, such polymerizations are carried out in a reaction medium comprising the reactant(s), a catalyst, such as anhydrous aluminum trichloride, and solvent such as ethylene chloride, carbon disulfide, nitromethane, nitrobenzene, or ortho- ichlorobenzene. Because the carbonyl groups of the reactant(s) and products complex with aluminum trichloride and thereby deactivate it, the aluminum trichloride catalyst is generally employed in an amount greater than one equivalent far each equivalent of carbonyl groups in the reaction medium. Other inorganic halides such as ferric chloride may be employed as the catalyst. Such Friedel-Crafts polymerizations generally have produced an intractable reaction product difficult to remove from the reaction vessel and purify. Further, such processes have tended to produce polymer of undesirably low molecular weight and/or of poor thermal stability. The all para-linked polyCarylene ether ketones) have been particularly difficult to prepare under such Friedel-Craf s conditions. One factor that appears to contribute to the unsatis¬ factory ' results reported in the literature is that the para-linked polymers are more highly crystalline than the ortho, meta or mixed isomeric members of this polymer family and are therefore generally more insoluble in the reaction OMPI media typically used in such Friedel-Crafts reactions. This tends to result in the premature precipitation of the polymer in low molecular weight form. Another factor that may lead to these poor results is d-eactivation of the terminal aryloxy groups by complexation with aluminum chloride or alkylation of the terminal group which prevents further growth of the polymer chain. Also, side reactions, particularly at the ortho position of activated aromatic rings can result in a polymer that is branched and/or is more likely to cross-link at elevated temperatures such as those required for melt processing the polymer. It is generally recognized that in Friedel-Crafts reactions, ortho substitution of the polymer is more likely to occur if the reaction is conducted at elevated temperatures and/or for a relatively long reaction time. U.S. Patents No. 3,065,205 to Bonner, U.S. Patent No. 3,767,620 to Angelo et al , 3,516,966 to Berr, 3,791,890 to Gander et al, 4,008,203 to Oo ' nes and U.K. Patents No. 971 ,227 and 1,086,021 both to Imperial Chemical Industries, Limited, disclose the prepara¬ tion of polyCarylene ketones) by Friedel-Crafts polymeriza¬ tion and generally acknowledge some of the difficulties in producing tractable, melt-stable polymers. For example, Gander et al provide a method of producing the polymers in granular form by special treatment of the reaction mixture before gellation can occur and Angelo et al provide a method of treating the polymer to reduce undesired end groups which •result from side reactions during pol merization and which cause thermal instability of the polymer. To overcome the disadvantages encountered in - producing polyCarylene ketones) by the above described Friedel-Crafts polymerization, it has been proposed to use boron trifluoride catalyst in anhydrous hydrogen fluoride. OMPI See for example, U.S. Patents 3,441,538 to Marks, 3,442,857 to Thornton, 3,953,400 to Dahl, and 3,956,240 to Dahl et al. This general process has been used commercially to produce polymer" of the desired high molecular weight and -thermal stability. However, the use of boron trifluoride and hydrogen fluoride requires special techniques- and equipment making this process difficult to practice on a commercial scale. We have now discovered an improved process for the production of polyCarylene ketones) by an electrophilic synthesis which results in high molecular weight, thermally- stable polymers using reaction media that are readily handled on a commercial scale. The process of this invention provides a high reaction rate which enables the reaction to be carried out at relatively low temperatures over a relatively short period of time. Further, the polymer is maintained in the reaction medium, for example in solution or in a reactive gel state, until high molecular weight polymer is obtained. Further, the polymer produced is essentially linear with little, if any, ortho substitution of the aromatic rings in the polymer backbone. Since the process of this invention maintains , the polymer in solution or in a more tractable state, recovery and purification of the polymer is greatly facilitated. Brief Description of the Drawing Figure 1 is a graph illustrating the effect of the amount of Lewis acid present during the polymerization on the inherent viscosity of polyCcarbonyl-p-phenylene-oxy- p-phenylene) . Summary of the Invention In accordance with the process of this invention, the Friedel-Crafts polymerization of appropriate monomer systems-, as defined more fully hereinafter, is. controlled to suppress side reactions including ortho substitution, alkylation and chain branching and/or to solubilize or swell the polymer, by conducting the reaction under select reaction conditions and proportions of reactants not taught or suggested by the prior art or by the addition of a controlling agent, such as a Lewis base, to the reaction medium or both. One aspect of this invention comprises a method of producing a polyCarylene ether ketone) which comprises polymerizing (I) phosgene or an aromatic diacid dihalide together with a polynuclear aromatic comono er. containing two active hydrogen atoms or (II) a polynuclear aromatic comonomer containing both an acid halide group and an active hydrogen atom, in the presence of a Lewis acid, optionally a controlling agent and optionally a non-protic diluent, the various components being present in such proportions and the polymerization being conducted under such reaction conditions that a thermally stable, linear polyCarylene ether ketone) substantially free of pendant groups resulting from ortho substitution of para-linked aromatic rings in the polymer ■backbone is obtained. Another aspect of this invention comprises a method of producing polyCarylene ether ketones) which comprises polymerizing a monomer system comprising: I) Ci) phosgene or an aromatic diacid dihalide together with (ii) a polynuclear aromatic comonomer comprising: (a) H-Ar-O-Ar-H wherein n is 2 or 3 (c) H-Ar-O-Ar-(CO-Ar-O-Ar)m-H wherein m is 1 , 2 or 3 or Cd) H-(Ar-O)n-Ar-CO-Ar-(O-Ar)m-H wherein m is 1 , 2 or 3, and n is 2 or 3 or II) an acid halide of the formula: H-Ar-O-C(Ar-CO)p-(Ar-0)q-(Ar-CO)r],K-Ar-C0-Z wherein Z is halogen, k is 0, 1 or 2, p is 1 or 2, q is 0, 1 or 2 and r is 0, 1 or 2; or -III) an acid halide of the formula: H-(Ar-O) n -Ar-Y wherein n is 2 or 3 and Y is CO-Z or CO-Ar-CO-Z where Z is halogen; OMP wherein each Ar is independently selected from substituted or unsubstituted phenylene, and substituted and unsubsti- - tuted polynuclear aromatic moieties- free of ketone carbonyl or ether oxygen groups; in a reaction medium comprising A) a Lewis acid in an amount of about one equivalent per equivalent of carbonyl groups present plus about one equivalent per equivalent of Lewis base, plus an amount effective to act as a catalyst for the polymerization; B) a Lewis base in an amount from 0 to about 4 equivalents per equivalent of acid halide groups present in the monomer system; and C) a non-protic diluent in an amount from 0 to about 93Λ by weight, based on the weight of the total reaction mixture; with the provisio that in the substantial absence of Lewis base and: i) the monomer system includes a, diacid dihalide and a comonomer as defined in I(ii.)Ca) , I(ii)Cb) or I(ii)(d) : (aa) the Lewis acid is present in excess of the minimum specified in A) above by an amount of up to about 0.8 equivalents per equivalent of undeactivated aryloxy groups in the monomers, and, if the acid halide groups are situated on separate non-fused aromatic rings, by an additional amount of up to about 0.5 equivalents per equivalent of acid halid groups; and (bb) the -concentration- of monomers in the reaction mixture is at at least about 7 % by weight, based on the total weight of the reaction mixture; with the further proviso that when the monomer system includes a comonomer as defined in I(ii)(a) and the diacid dihalide is benzene dicarbonyl dichloride or diphenyl ether dicarbonyl dichloride, the polymer produced is at least partially crystalline; ii) the monomer system is III, the Lewis acid is present in excess of the minimum specified in CA) above by an amount of up to 0.8 about equivalent per equivalent of undeactivated aryloxy groups in the monomers; or iii) the monomer system is ICc) or II, the Lewis acid is present in an amount in excess of the minimum specified in A) above by at least about 0.6 +[0.25 X tεnh (50C0.1-D)] equivalents per equivalent of acid halide groups where D is the molar- ratio of monomer to diluent. C ?I_ Detailed Description of the Invention In the electrophilic polymerization. of this invention a poly(arylene ether ketone) is produced from an appropriate monomer " system. The polymers produced by the process of the invention have repeat units of the general formula • 0 II -Ar-0-Ar-C- wherein each Ar is independently selected from substituted and unsubstituted phenylene and substituted and unsubstituted polynuclear aromatic moieties. The term polynuclear aromatic moieties is used to mean aromatic moieties containing at least two aromatic rings. The rings can be fused, joined by a direct bond or by a linking group. In certain of the monomers, e.g. the polynuclear aromatic comono ers, the acid halide monomers and certain diacid dihalides, at least two of the aromatic rings are linked by an ether oxygen linkage. Other linking groups which can join aromatic rings in the aromatic moieties include for example, carbonyl, sulfone, sulfide, amide, imide, azo, alkylene, per fluoroalkylene and the like. The phenylene and polynuclear aromatic moieties can contain substitutents on the aromatic rings. These substi- tuents should not inhibit or otherwise interfere with the polymerization reaction to any significant extent. Such ' acceptable substituents include, for example, phenyl, halogen, nitro, cyano, alkyl, 2-aralkenyl, alkynyl and the like. OMPI These polymers are prepared in accordance with this invention by polymerizing an appropriate monomer system. Such monomer systems comprise: I) Ci) phosgene or an aromatic diacid dihalide together with (ii) a polynuclear aromatic comonomer selected from (a) H-Ar-O-Ar-H wherein n is 2 or 3 (c) K-Ar-O-Ar-(CO-Ar-O-Ar)m-H wherein m is 1 , 2 or 3 or (d) H-(Ar-O)π-Ar-CO-Ar-(O-Ar)m-H wherein m is 1 , 2 or 3, and n is 2 or 3 or II) an acid halide of the formula: H-Ar-0-[(Ar-C0)p-(Ar-0)q-(Ar-CO)r],k-Ar-CO-Z wherein Z is halogen, k is 0, 1 or 2, p is 1 or 2, q is 0, 1 or 2 and r is 0, 1 or 2; or PI III) an acid halide of the formula: H-(Ar-O) -Ar-Y n wherein n is 2 or 3 and Y is CO-Z or CO-Ar-CO-Z wherein Z is halogen; wherein each Ar is independently selected from substituted or unsubstituted phenylene, and substituted and unsubstituted polynuclear aromatic moieties free of ketone carbonyl or ether oxygen groups. Aromatic diacid dihalide employed is preferably a dichloride or dibromide. Illustrative diacid dihalides which can be used include, for example whe r e in a i s 0 - 4 . Illustrated polynuclear aromatic comonomers which can be used with such diacid halides are: (a) H-Ar-0-Ar-H, which includes, for example: (b) H-(Ar-O)n-Ar-H, which include, for example: O-O-G and (c) H-Ar-O-Ar-(CO-Ar-O-Ar)m-H, 7 which includes, for example: (d) H-(Ar-O)n-Ar-CO-Ar-(O-Ar) -H which includes, for example: Monomer systems II and III comprise an acid halide. CThe term acid halide is used herein to refer to a monoacid monohalide.) In monomer system II, the acid halide is of the formula H-Ar-O-C(Ar-O)p-(Ar-0)q(Ar-CO)r]. -Ar-C0-Y Such monomers include for example, where k = 0 and whe r e k = 1 Iπ monomer system III, the acid halide is of the formula Examples of such acid halides include It is to be understood that combinations of monomers which fall within the same proviso clause, as set forth above, can be employed. For example, one or more diacid dihalides can be used with one or more polynuclear aromatic comonomers as long as the correct stoichiometry is maintained Further, one or more acid halides can be included. In addition monomers which do not contain an ether linkage can be employed as long as one or more of the comonomers used contains at least one ether oxygen linkage. Such comonomers include for example: which can be used as the sole comonomer with an ether containing diacid dihalide or with phosgene or any diacid dihalide when used in addition to a polynuclear aromatic comonomer as defined in I(ii)(a), I(ii)(b), I(ii)Cc) or I(ii) (d) . Similarly can be used as a comonomer together with an ether-containing polynuclear aromatic acid halide or as an additional comonomer together with a monomer system as defined in I. The monomer system is polymerized in the presence of a reaction medium comprising: A) a Lewis acid in an amount of one equivalent per equivalent of carbonyl groups present, plus one equivalent per equivalent of Lewis base, plus an amount effective to act as a catalyst for the polymerization; B) a Lewis base in an amount from 0 to about 4 equivalents per equivalent of acid halide groups present in the monomer system; and C) a non-protic diluent in an amount from 0 to about 93Λ by weight, based on the weight of the total reaction mixture. The term "Lewis acid" is used herein to refer to a substance which can accept an unshared electron pair from another molecule. Lewis acids which can. be used in the practice of this invention include, for example, aluminum trichlo ' ride, aluminum tribromide, antimony pentac ' hloride, antimony pentafluoride, indium trichloride, gallium trichloride, boron trichloride, boron trifluoride, zinc chloride, ferric chloride, stannic chloride, titanium tetrachloride, and molybdenum pentachloride. The use of 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 polymerization (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 m.onomers and the reaction conditions in a manner as set forth below. Further, if a comonomer containing other basic species, such as sulfone groups, is used, additional Lewis acid may be required. As indicated above, the Friedel-Crafts polymeriza¬ tion reaction is controlled by the addition of a controlling agent or by varying the reaction conditions, including varyi " ng the amount of Lewis acid to achieve the desired melt-prσcessable, high molecular weight, substantially linear poly(arylene ether ketones). In a preferred embodiment of the invention, the polymeri¬ zation reaction is controlled by the addition of a controlling agent which, inter alia, suppresses undesirable side reactions, particularly ortho substitution of activated aryloxy groups. Suppression of side reactions results in a polymer that is thermally stable, that is it does not degrade or cross-link when subjected to elevated temperatures, e.g. temperatures above t-he melting point of the polymer, for a period of time. 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. Typically 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. Preferred controlling agents for the polymerization are Lewis bases. The term "Lewis base" is used herein to refer tσ a substance capable of donating an unshared electron pair to a Lewis acid. Thus, the Lewis base forms a complex with the Lewis acid used in the reaction medium. It has been found that Lewis bases whrch form a 1:1 complex having a heat of association at least about that of diphenyl ether with the Lewis acid are preferred. For example, where aluminum trichloride is the Lewis acid the Lewis base used should form a 1:1 complex having a heat of association of at least about 15 kcal/mole, 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 0. Chem Soc. (A), 1971, pages 3132-3135 (D.E.H. 3ones et al) 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 controlling 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 polymerization. When a Lewis base is used as a controlling agent, an addition amount of Lewis acid generally about one equivalent per equivalent of Lewis base. When aluminum chloride is used as the Lewis acid one equivalent is considered to be AlCl,. Typical Lewis bases which can be employed include,, for example, amides, amines, esters, ethers, ketones, nitriles, πitro 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, cyclohexanoπe, methyl acetate, ethylene carbonate, N-methyl- formamide, aceta ide, N r N-dimethylacetamide, N-methylpyrrolidone, urea, tetramεthylurea, N-acεtylmorpholine, dimethyl sulfoxide, N, N-dimethylformamide, diphenyl sulfone, N, N-dimethylmethane- sulfonamide, phosphor.yl chloride, phenylphosphonyl chloride, pyridine-N-αxide, triphenylphosphine oxide, trioctylphosphine oxide, nitropropane, nitrobenzene, benzonitrile, n-butyronitrile, methyl ether, tetrahydrofuran, dimethyl sulfide, trimethylamine, N, N, N' ,N'-tεtramethylethylenediamine, N, -dimethyldodecylamiπe, imidazole, pyridine, quinoline, isoquinoline, beπzimidazole, 2, 2'-bipyridine, o-phenanthroline, 4-dimethylaminopyridine, and the -like. In addition to covalent organic compounds, suitable Lewis bases include inorganic salts which can form complexes with Lewis acids, for example, chlorides, such as trimethylammonium chloride, tetramethylammonium chloride, - sodium chloride or lithium chloride, perchlorates, trifluoro- ethanesul onates and the like. Preferred Lewis bases for the reaction medium of this invention are N-methylformamide, N, -dimethyl- formamide, N, N-dimethylacetamide, 1 -meth.yl-2-pyrrolidone , tetramethylene sulfone (also known as sulfolane), n-butyroni¬ trile, " dimethyl sulfide, i idazole, acetone, benzophenone, trimethylamine, trimethyla ine hydrochloride, tetra ethyl- ammonium chloride, pyridine-N-oxide, 1 -εthylpyridinium chloride, lithium chloride, lithium bromide, sodium chloride, sodium bromide, potassium chloride, potassium bromide and mixtures thereof. 'The amount of Lewis base present should be from 0 to about 4 equivalents per equivalent of acid halide groups present in the monomer system. Amounts greater than 4 equivalents could be employed, if desired. However, no additional controlling effect is usually achieved by adding larger amounts. Thus, it is preferred to use no more than about 4 equivalents and generally about 2 equivalents. When a Lewis base is added to control the reaction at least- about .01, 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. The particular amount of Lewis base. added, depends to a certain extent on the nature of the monomers present. When a Lewis base is used to control the reaction the temperature at which the reaction is conducted can be from about '-50°C to about -+150°C. It is preferred to start the reaction at lower temperatures, for example at about -50 to about -10°C particularly if the monomer system contains highly reactive monomers. After polymerization has commenced, the temperature can be raised if desired, for example, to increase the rate of reaction. It is generally preferred to carry out the reaction at tempεratures in the range of between about -30 C C and +25°C (room temperature). f OMPI While it is not understood exactly how the 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 act as a solvent for the polymer-Le is acid complex formed during the reaction, thereby maintaining the polymer in solution or in a reactive gel state. Further, the reaction mixture is more tractable, making work up of the polymer easier and ensuring effective removal of catalyst residues during purification. The solubilization property of the Lewis acid/Lewis base complex is particularly significant in the preparation of para-linked poly(arylene ether ketones) . - As mentioned above these polymers are more highly crystalline than ' other members of this polymer family and their complexes with the Lewis acid tend to precipitate from the reaction medium in low molecular weight form and/or in .a particularly intractable mass difficult to recover and purify. When such polymers are made in accordance with this embodiment of the invention, it is advantageous to select a Lewis acid and Lewis base . combination which form a complex which, in addition to the above specified characteristics, also dissolve the desired poylmer. This can readily be determined by preparing a complex, optionally adding a diluent, and then adding the polymer to see if it dissolves. If a diluent such as methylene chloride or dichloroethaoε is used, it is believed that the Lewis acid/Lewis base complex rεducεs thε tendency of the diluent to act as an alkylating agent by competing with the diluent for available Lewis ac-id 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. It is believed that the aromatic rings which are particularly susceptible to ortho substitution are active arylαxy groups. Such groups are referred to herein as undeactivated aryloxy groups. By "undeactivated aryloxy group" " is meant an aryloxy group which is in a molecule in which there are no deactivating groups or is located at least two aromatic moieties (i.e. Ar as defined above) away from a deactivating group such as a carbonyl. Conversely a "deactivated aryloxy group" is an aryloxy group separated from a deactivating group, usually carbonyl, by an aromatic group containing one aromatic ring, fused aromatic rings or aromatic rings linked by direct bonds. A non-protic diluent can also be employed, if desired. Advantageously, the diluent should dissolve the Lewis acid/ Lewis base complex and the resulting polymer/Le is acid complex. It should also be relatively inert toward Friedel- Crafts reactions. The diluent is preferably somewhat polar as measured by its dielectric constant and solubility . parameter. Preferably the dielectric constant of the diluent is at least about 2.5 at 24°C, and preferably in the range of from about 4.0 to about 25 at 24°C. The Hildebrand solubility parameter of the diluent is preferably at least about 7.2 [cal/cm 3]1/2 and is preferably in the range of from about 9.2 to about 15 [cal/cm 3]1/2. Preferred diluents include, for example, methylene chloride, carbon disulfide, o-dichlorobenzene, 1 ,2, 4-trichlorobenzene, o-difluorobenzene, 1 , 2-dichloroethane, 1 , 1 , 2, 2-tetrachloro- εthan ' e and mixtures thereof. The diluent is used in an amount from 0 to about 935_ by weight, based on the weight of the total reaction mixture. As is known in polymerizations of this type, 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. As discussed in more detail below, it has been found that the monomer to diluent molar ratio can contribute to control of the polymerization reaction to yield the desired product. Typically the diluent is used in an amount of at least about 1QS_, prefer¬ ably at least about 20S. by weight based on the weight of the reaction mixtures. Use of an alkylating or acylating diluent can lead to undesired side reactions as mentioned above. When such solvents are employed control of the polymerization by techniques taught in this specification suppresses such alkylation or arylation. The result is a thermally stable, melt processable, essentially linear polymer. The polymerization reaction can also be controlled by us'e of the appropriate reaction conditions without the addition of a Lewis base. The term substantial absence of Lewis base is used herein to refer to reaction mixtures to which no Lewis base is added as a controlling agent. Minor amounts of Lewis base may be generated in situ during the polymerization reaction, but such amounts are inadequate to control the reaction. The reaction conditions required depend on the reactivity of the monomers used. Two general classes of monomers need to be considered - those containing undeactivated aryloxy groups as defined above and those which do not. If any monomer in the monomer system contains an undeactivated aryloxy group, the amount of Lewis acid used generally should not exceed a certain amount. Monomer systems which can be used in the practice of this invention have been defined above with consideration cf the reactivity of the aryloxy groups present. The conditions under which the polymerization will be controlled to produce the desired product can then be set forth, with further requirements provided where the relative activity of the acid halide groups make this necessary. . Briefly, the monomer systems are: I) (i) phosgene or an aromatic diacid dihalide together with (ii) a polynuclear aromatic comonomer comprising: (a) H-Ar-0-Ar-H " (b) H-(Ar-0) n -Ar-H wherein π is 2 or 3 (c) H-Ar-O-Ar-(CO-Ar-O-Ar)m-H wherein m is 1 , 2 or 3 or (d) H-(Ar-O)n-Ar-CO-Ar-(O-Ar)m-H wherein is 1, ' 2 or 3, and n is 2 or 3 or II) an acid halide of the formula: H-Ar-0-[(Ar-C0)p-(Ar-0)q-(AΓ-C0)r],k-AΓ-C0-Z. wherein Z is halogen, k is 0, 1 or 2, p is 1 or 2, q is 0, 1 or-2 and r is 0, 1 or 2; or I I I ) an acid halid e o f the formul a : H- C AΓ - 0 ) n - AΓ - Y wherein n is 2 or 3 and Y CO-Z or CO-Ar-CO-Z wherein Z is halogen; wherein each Ar is independently selected from substituted or unsubstituted phenylene, and substituted and unsubstituted polynuclear aromatic moieties free of ketone carbonyl and ether oxygen groups. Monomer systems that contain undeactivated aryloxy groups are I wherein the comonomer is as defined in I(ii)(a), I(ii)(b), I(ii)(d) and III. In general, ' when monomers of this type are used the amount of Lewis acid present in addition to the above noted one equivalent per equivalent of carbonyl groups present plus an amount effective to act as a catalyst for the polymerization, should be less than 0.8 equivalents per equivalent of undeactivated aryloxy groups. Preferably even less than that should be used, for example less than about 0.6 equivalents and most preferably less than about 0.4 equivalents per equivalent of undeactivated aryloxy groups present. However, because of the reactivity of certain polynuclear diacid dihalides such as diphenyl ether dicarbonyl dichloride, it has been found desirable to employ a different amount of Lewis acid when such diacid dihalides are used in the monomer system. When such poly¬ nuclear diacid dihalides are used in monomer system I with a comonomer defined in I(ii)(a), I(ii)(b) and I(II)(d) it is often desirablε to add further Lewis acid up to about 0.5 equivalents per equivalent of acid halide groups. Preferably the further amount added is between about 0.03 and 0.5 equivalεπts per equivalent of acid halide groups. ' We have found that meta-benzεnε dicarbonyl dichloride is sufficien-tly reactivε and thε product sufficiεntly soluble in the reaction fa " 'J —- ~ mεdium that it is not necessary to limit the maximum excess of Lewis acid to obtain high molecular weight polymer. However, to prepare polymers which are at least, partly crystalline from mo.nomer systems including substantial amounts of the less reactive para benzεne dicarbonyl di- chlorides, it is very beneficial to use an amount of Lewis acid in excess of that defined in A) above by- an amount of up to about 0.8 equivalents per equivalent of undeactivatεd aryloxy groups in thε monomers. Crystallinity of the polymers may be measured by standard techniques such as differential scanning calorimetry or X-ray diffraction. It has also been found to be necessary when the monomer system used is I with the comonomer being that defined in I(ii)(a), I(ii)(b) or I(ii)(d) that the concentration of monomers in the reaction mixture be at least about 7S_, preferably at least about 10Λ, and most preferably at least about 15Λ, by weight based on the total weight of the reaction mixture. When the monomer system employed is III, it is also desirable to conduct the reaction at similar monomer concentrations. The second genεral class of monomers are monomer systems which contain no undeactivated aryloxy groups. ■ Monomers of this type are sεt forth in monomer system I wherein the comonomer is as defined in I(ii)(c) and II. With " this class of polymers it is preferred to use a large excess of Lewis acid, the excess depending on the particular monomer to diluent molar ratio (D). Generally, it is preferred .to have a relatively high monomer to diluent ratio and a relatively large excess of Lewis acid. The amount of excess Lewis acid (in addition to the above noted equivalent per equivalent of carbonyl groups plus a catalytic amount) is at least about 0.6 + (0.25 X tanh [50(0.1-D)]) equivalents per equivalent of acid halide groups. The amount of excess Lewis acid is prefeably at least about 0..8 + (0.25 X tanh [50(0.1-D)]) and most preferably is at least about 1.0 + (0.25 X ' tanh [50(0.1-D)]) equivalents per equivalent of acid halide groups. When the monomer to diluent molar ratio is greater than about 0.15, the amount of Lewis acid in excess of the standard amount is at least about 0.3 equivalents per equivalent of acid halide groups. In general, it is preferred to add Lewis acid in a substantial excεss of thε minimum amounts spεcified. Generally, at least about 0.5 equivalent and preferably at least about 1.0 equivalents of additional Lewis acid, per equivalent of acid halide groups are used. The reaction conditions found to be necessary to prepare melt-processable, high molεcular weight, substantially linear poly(arylene εther ketones) are not taught or .suggested by the prior art and in fact are contrary to the generally held beliefs of Friedεl-Crafts chεmistry. Convεntionally, a moderate excess of Lewis acid usually about 0.4 equivalents per equivalent of carbonyl groups in the monomer system is used in Friedel-Crafts reactions. Applicant has found that when all aryloxy groups presεnt in thε monomer system are deactivated by carbonyl groups as defined above, a large excess of Lewis acid must be used. This is illustrated in Figure 1, by a graph showing the relationship betwεen the amount of Lewis acid used and the molecular weight of the polymer -as measurεd by inhεrent viscosity as describεd bεlow. Prior art Friedel-Crafts polymerization reactions of this type were conducted using a Lewis acid to monomer ratio well below that neεdεd for thε production of poly εr having the desired inherεnt viscosity or usεd monomer to diluent molar ratios bεlow that rεquired. This is illustrated in Figurε 1, where it is shown that at least 2 equivalents of aluminum chloride per equivalent of monomer are required when preparing poly(carboπyl-p-phenylenβroxy-p-phenylene) . Prior art processes used aluminum chloride to monomer ratio shown to produce polymer of lower inherent viscosity, as shown on the graph, or where there are undeactivated aryloxy groups present in the monomer system, it has been found to be necessary to add a smaller excess of Lewis acid than taught in .the prior art but to maintain a relatively high monomer concentration in the reaction mixture. As mentioned above, this results in suppression of side reactions, particularly in the- ortho position of para-linked aromatic rings in the polymer chain. Traditional Friedel-Crafts chemistry suggests the use of a moderate excess of Lewis acid and a more dilute reaction mixture to achieve these results. Applicants have found the opposite to be necessary in the preparation of poly(arylene ether ketones). As mentioned above, one of the important features of this invention is that poly(arylene kεtonεs) of high molεcular weight can be obtained. By "high molecular weight" is meant polymer having an inherent viscosity greatεr than about 0.6. Prεfεrably the polymer prepared by the process of this invention has an inherent viscosity in the range of about 0.6 to about 2.0. Polymers having an inherεnt viscosity below about 0.6 are generally not useful because they have poor mechanical properties, such as tensile strength and elongation. Thεy also tend to be brittle while polymers having an inherent viscosity above about 2.0 are very difficult to melt process. Throughout this application, inherεnt viscosity refers to the mean inherent viscosity determined according to the method of Sorεnson et al, "Preparative Methods of Polymer Chemistry" Intersciencε (1968), at pagε 44 [0.1g polymεr dissolved in 100 ml of concentratεd sulfuric acid at 25°C]. If desirεd, the molecular weight of the polymer, the degree of branching and amount of gelation can be controlled by the use of, for examplε, c.apping agents as describεd in U.S. Patεnt No. 4,247,682 to Dahl, the disclosure of which is incorporated herεin by reference. The molecular weight of the polymer can also be controlled by a polymeriza¬ tion reaction utilizing a two-monomer system as describεd abovε, by ε ploying a slight excess of one of the monomers. Capping agents, when employεd, are addεd to the polymerization reaction medium to cap the polymεr on at least- one end of the polymεr-chain. This tsr inatεs continuεd growth of that chain and controls thε 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 incrεasεs mεlt stability. Both nuclεophilic and εlεctrophilic capping agents are- used to cap the polymer at each end of thε chain. Prεferred nuclεophlic capping agεnts arε 4-chlorobiphεnyl, 4-phεnox bεnzoph8non8, 4-(4-phεnoxyphenoxy)bεnzophεnonε, biphεnyl 4-bεnzεnesulfonylphenyl phεnyl ether, and the like. Typical elεctrophilic capping agεnts arε compounds of thε formula 0 0 11 ι» Ar " C-E o r Ar "- S -E |l 0 ^ OM.EPI wherein Ar" is phenyl, 3-chlorophenyl, 4-chlorophεnyl , 4-cyanophεnyl, 4-mεthylphenyl 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, benzεnεsulfonyl chloridε and thε likε. As mεntioned above, a key aspect of this invention is that the Lewis acid/Lewis base complex solubilizes or solvatεs the polymer so that it remains in the reaction medium in a form capable of sustaining continued polymeriza¬ tion -so that the desired high molecular weight is obtained in a controlled and reproducible fashion. ' Lewis acid is also present in the reaction medium as the catalyst for the Friedel-Crafts polymerization reaction. The resulting polymer contains Lewis acid complexed to the carbonyl groups of the polymer. For many polymerizations, the Lewis acid is complexed to substantially all. the carbonyl groups in the polymer. As is well known with polymers of this type,- the catalysit residue must be removed, i.e. the Lewis acid must be dεco plεxεd from thε polymer and removed. A method for removing the catalyst residuε is described in U.S. Patent No. 4,237,884 to Dahl, the. disclosure of which is incorporated herεin by reference. Decomplεxation can bε accomplished by treating the polymerization reaction mixture with a deco plexing 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 decomple ation should be effected before isolation of the polymer from the reaction mixture. The amount of decomplεxing base used should be in excεss of thε 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 decomplexing bases w ' hich can be used include water, dilute aqueous hydrochloric acid, methanol, ethanol, acetone, N,N-dimethyl- formamide, N, N-dimethylacetamide, pyridine, dimethyl ether, diethyl ether, tetrahydrofuran, trimethylamine, trimethylamine hydrochloride, dimethyl sulfide, tεtramεthylεnεsulfonε, bεnzophεnonε, tetramεthylam onium chloridε, isopropanol and thε likε. Thε decomplexed polymεr can thεn bε rεmovεd by convεntional tεchniquεs such as adding a nonsolvεπt for thε pαlymεr which is a solvεnt for or miscible with thε Lεwis 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 from the reaction medium and then washing with an ' appropriate solvent to rεmove any remaining base/catalyst complex and diluent from the polymer. In recovery of the polymer from the reaction mixture, the reaction mixture can be liquified, if desirεd by the method described in application Serial No. (atty's docket no. ) of R. Reamey, thε disclosurε of which is incorporatεd hεrεin by reference. The following examplεs illustratε thε procεss of this invεntion using a variety of Lewis acids, Lewis bases, inert " diluents and monomers. It is to be understood that other reactants and reaction media within thε scopε of thε teaching of this invention can be employεd, if desired. Ex am pl ε 1 A 500 ml 3 nεck round bottom flask equipped with a stirrer, thermometer, and nitrogen inlet was charged with 1 ,4-diphenoxybenzene (13.2198 g, 0.0504 mole), tεrephthaloyl chloride (10.1515 g, 0.0500 mole), benzoyl chloride (0.1.124 g, 0.0008 mole), sulfolane (27.04 g, 0.225 mole), and anhydrous methylene chloride (150 illiliters, ml). The atmospherε insidε thε flask was purgsd with and kept under nitrogen. The flask and its contents were cooled to -40°C with a dry ice-acetonε bath. Anhydrous aluminum chloride (49.7 g, 0.373 mole) was added over a 12 minute period, with continued cooling. Thε stirrεd reaction 'mixture was allowed to warm up to about 15" C over a period of 1.5-2 hours.. The rεd, highly viscous mixture was then transferred to a glass tray under nitrogen, allowed to warm up to 20°C, and added portionwise to rapidly stirred methanol (Waring blender). The resulting fibrous polymer was collected, washed with methanol, and soaked over night in more methanol. Following a second overnight soaking, this time in water, another methanol wash, and vacuum drying ( 120-160°C)', therε was obtained a colorless fibrous polymer (18.9 g, 96.3% yield) . Its inherent viscosity was 1.09 (.15. solution in cone, sulfuric acid). Compression molding at 400°C for 3 . in gave nearly colorless flεxible slabs of essentially unchanged inherent viscosity (1.10). Stress/strain analysis of the slabs gave a Young's modulus of 216,700 psi, elongation at break of 805., and tensile strength of 9,130 psi, as measured by ASTM D-638-80. Material extruded at 400°C also exhibited no change in inherεnt viscosity (1.10). OMFI Ex a ple 2 To a 250 ml threε nεck round b.ottom flask equipped with a mechanical stirrer, a πitrogεn inlεt, and a thermometer well ' fitted with a 0-type thermocouple was added methylenε chloride (30 ml, freshly distilled from phosphorus pentoxide). The flask and its * contents were purged with and kept under nitrogen and cooled to -27°C with a dry ice-acεtone bath. Anhydrous aluminum chloride (17.68 g, 132.6 mmole) was thεn added via Gooch tubing.. To thε resulting cold solution, N, -dimεthylformamidε (DMF,5.54 g, 75.8 mmole, freshly vacuum distilled from calcium hydride) in methylεnε chloridε (15 ml) was added slowly (to control the vigorous exothεrm) . Wi-th continued cooling, a solution of 1 , 4-diphenoxybenzeπe (6.6811 g, 25.5 mmolε) , terephthaloyl chloridε (5.1302 g, 25.3 mmole), and benzoyl chloride (0.571 g, 0.40 mmole) in methylene chloride (25 ml) was added. The transferring flask was rinsed with an additional volume of methylenε chloride (10 ml) to ensure completε transfer. The stirred reaction mixture was allowed to warm up to room tempεraturε over a 6.3 hour period, during which time it becamε a viscous orange-red suspension. It was next cooled down to 5-6 β C with an ice bath and the reaction was quεnchεd with DMF (50 ml). At this ti ε, thε polymεrizatioπ mixturε became a highly viscous white slurry. The polymer was isolated by filtration, transferred into a 1 qt. glass blendεr containing cold (0°C) DMF (100 ml), and blεndεd at high speed until room tempεrature was reached. This process was repeated. Thε poly εr was then diges'ted twice in DMF (250 ml,' 50°C, 24 hrs) , once in water (300 ml, room tempεra¬ ture, 24 hours), and once in hydrochloric acid (0.5 M, 500 ml, room tempεraturε., 24 hours). Aftεr washing with more water and vacuum drying, polymer (8.9g, 90S. yield) of inherent viscosity 1.2 (0.155 in sulfuric acid) was obtained. Its melt stability and processability were demonstrated by the fact that slabs pressed for 30 min at 400°C showed minimal change in inherent viscosity. OMPI Ex amp l ε 3 The procedure of Example 2 w-as repeated using terephthaloyl chloride (5.17 g, 25.2 mmole), 1 ,4-diphenoxybεn- zene (6.56 g. 25.0 mmole) and 4-(4-phenoxyphenoxy) bεπzophεnonε (0.1466 g, 0.4 mmolε) . The resultant, polymer had an inherεnt viscosity of 1.25. Polymsr pressed for 30 minutes at 400°C gave slabs of inhεrent viscosity 1.34 (averagε of 2 samplεs) . Prεssing at 410 β C for 30 minutes gave slabs of inherent viscosity 1.71 (average of 3 samples), with a slight amount of gel. Example 4 The procedure of Example 2.was repeated using purified aluminum chloride. The initial temperature employed was -15°C and the reaction mixture was allowed to warm up to 8°C. The aluminum chloridε was purified prior to introduction into- the reaction medium by vacuum distillation from a mixture of 1500 g aluminum chloride, 100 g sodium chloride and 5 g aluminum powder followed by vacuum sublimation. The polymer thus obtained had an inherεnt viscosity of 1.17 (average of 2 samples). Slabs pressed at 400 or 410°C for 30 minutes had inherεπt viscosities of 1.15 .(average of 4 samples) and 1.18 (averagε of 4 samplεs), respectively. No gel was observed in any of the slabs. Example 5 A reaction flask equipped with a magnetic stirrer and purged with nitrogen and charged with methylene chloride (8 ml) was cooled in an ice bath. To it was added n-butyronitril (1.382 g, 0.020 mole) followed by aluminum chloride (6.56 g, 0.050 mole). The latter was added slowly becausε of the vigorous exothεrm gεnεratεd. Whεn this addition was completed, p-phenoxybεnzoyl chloridε (2.33 g, 0.010 molε) was addεd, also gradually. Polymεrization was allowsd to procεed overnight (about 16 hours) at room temperature. The polymer was recovered by transferring the polymerization mixture into methanol (about 100 ml), breaking it up in a blender at high speεd, filtεring, and washing gεnεrously with methanol. After digesting overnight in more mεthanol (about 100 ml) at room temperature, the polymer was washed with water and vacuum dried (120-160°C). The product was a white polymer of inherεnt viscosity 1.69. Whsn compression moldεd at 400 β C for 3 rnin, it formεd a transparent yellow, tough, flexiblε slab. Example 6 Ex ample 5 w as r epeated , but with thε Lewi s b-asεs ( 0.020 molε) givεn in Tab lε I in place o f the n-b ut yronitrile , _ ' : - " l " i Tablε I Inherent Lewis Base Color Viscosity Slab (3 min , 400°C) Dimethyl sulfide White 0.79 Tough , flexible , yellow 1— itropropane White 0.57 Tough , flexible , 1. tan Pyridine N-oxide L. pink 2.5** Tough , flexible, 1. tan Isoquinoline L. pink 0.84 Tough, flexible , 1. tan Methylamine White 0.40 Brittle, 1. tan ydrochloride 1-Ethylpyridinium L. pink 2.50** Tough , flexible, 1. pink bromide Triphenyl phosphine L. pink 0 0..5500 (( sscome*** Flexible , 1. tan oxidε ge ♦ Diethylamine 0.77 Tough, flexible hydrochloride ♦ Diethyl ether 0.80 Tough, flexible ♦ Imidazole 1 .79 Tough, flexible Acetonε White 0.73 Tough , flexible Mεthyl Acεtate White (some ge *"** Tough, flexible N, N-Dimethyl formamidε White 1 .82 Tough , flexible Tetra ethyl ammonium White 0.82 Tough , flexible chloride ♦ Run on the scale corresponding to 0.006 mole p-phenoxybenzoyl chloride. **The high inhεrεnt viscosity indicatεs production o f high molεcular weight polymer . Use of capping agents so described above would yield a polymer in the desired molecular weight range. ***The presence o f gel indicates cross-linking has occurred . The inherent viscosity measurεmεnt reflects the molecular weight of the uπcross-linked portion of thε poly εr product . Examplε 7 Examplε 5 was repeated, excεpt that o-dichlorobεnzεne was used in place of the methylene chloride. The ' rεsultant polymer was light yellow and had an inherent viscosity of 1.12. It could be pressed at 400°C into a tough, flexible, pale yellow slab. Example 8 Example 5 was repeated, except that DMF was substituted for n-butyronitrile and o-difluorobenzεπε for mεthylεne chloride. The resultant polymer was light yellow and had an inherεnt viscosity of 1.18. It could bε prεssεd into a tough, flεxible, pale yεllow slab. Examplε 9 Example 5- was repeated, except that DMF was substituted for n-butyronitrile and 1 , 2, 4-trichloroben∑εne for methylεnε chloridε. Thε rεsultant polymεr was whitε and had an inherent visco-sity of 1.50. It could be pressεd into a flexiblε light colored slab. Example 10 Diphenyl ether (1.7025 g, 0.010 mole) was pclymerizεd with tεrεphthaloyl chloridε (1.6242 g, 0.008 molε) and isophthaloyl chloridε (0.04058 g, 0.002 mole) in the presencε of methylene chloride (14 ml), trimethylaminε hydrochloridε (2.19 g, 0.023 mole), and aluminum chloride (6.0 g, 0.045 mole) by the procedurε dεscribεd in εxample 5. The resultant polymer had an inherent viscosity of 0.74. It could be pressed into a slab that was light colored and flexible. -$U_REΛ OMPI Ex amp l e 1 1 The N-succinimido derivativε of p-phenoxybenzoic acid (V.200 g, 0.004 mole) was polymerized in methylenε chloride (6 ml), trimethylamine hydrochloride (1.50 g, 0-.016 mole), and aluminum chloride (4.40 g, 0.033 mole) according to the procedure in εxample 5. The resulting polymer had an inherent viscosity of 0.95 and could be pressed into a flexible tan slab. Example 12 A suspension of lithium chloride (0.84 g, 0.0198 mole) and aluminum chloride (5.40 g, 0.0405 mole) in 1,2- dichloroethane (7.0 ml) was stirred under nitrogen in a se ' alεd reaction tube for 40 minutes. To the resulting solution was added p-phenoxybenzoyl chloride (2.20 g, . 0.00945 mole). Polymerization was permittεd to continue at room tεmperaturε for about 90 minutεs to yield a highly viscous solution. 1 , 2-dichloroethane (4 ml) was added to dilute the reaction mass. The polymer was recovered by decomplεxation of thε mixture with water in a Waring blender, washing with a water/methanol solution, soaking the product in water overnight, then washing with methanol and drying. The product was a colorless polymer having an inherent viscosity of 1.58. When compression molded at 400°C for ' 2 inut ' es, it formεd ε pale yellow, tough, flexible slab. OMPI Ex am p l ε 1 A 500 ml 3-nεck round bottom flask equipped with a stirrer, thermometεr and nitrogεn inlet was charged with N, N-dirπethylformamide (16.45g, 0.2250 mole) and anhydrous methylεnε chloride (150 ml). The atmosphere inside the flask was purged with nitrogen. The flask was cooled to -30°C with a dry ice-acetone bath. Anhydrous aluminum chloride (75.30 g, 0.5647 mole), followεd by 4,4*-diphenoxy- benzophεnone (18.3940 g, 0.05020 mole), terephthaloyl chloride (10.1510 g, 0.0500 molε) and benzoyl chloride (0.0493 g, 0.3500 mmole) were added with continued cooling. The transferring flasks were rinsed with anhydrous methylεnε chloridε (50 ml total) to ensure completε transfer. The stirred reaction mixture was allowed to warm up to Q α C in 15 minutes and to 21°C in 1.5 hours. Part of the viscous reaction mixture was added portionwise to rapidly stirrεd methanol (Waring blendεr) . Thε resulting fibrous polymer was collectεd, washεd with methanol and vacuum dried (120-160°C) Its inherεnt viscosity was 1.28 (0.15. in sulfuric acid). Thε remaining part of the viscous reaction mixture was added portionwise to rapidly stirred 1055 hydrochloric acid (Waring blender) . The fibrous polymer obtained was washed with water, then refluxed 15 minutes in N, N-dimethylacεtamide, washed with water and vacuum dried (120-160°C). Its inherεnt viscosity was 1.37. A compression molded slab pressεd at 400°C for 20 minutεs showεd an inhεrεnt viscosity of 1.40, indicating mεlt stability. Its processability was further demonstrated by extrusion at 400°C through a mini-εxtruder to give -a light tan, flexible and smooth strand o ' f extrudatε of 1.42 inhεrεnt viscosity. Ex ample 1 4 « A 50 ml 3 neck round bottom flask equipped with a stirrer, thεrmometer and nitrogεn inlet was charged with aluminum trichloride (6.29 g, 0.0472 mole) and lithium chloride (1.00 g, 0.0236 mole) in 1 , 2-dichloroethane (17- ml) was cooled to 0°C in an ice-acetone bath. Diphenyl ether (2.01 g, 0.0118 mole) and phosgene (2.80 g, 0.0283 mole) were then added. The bath was removed and the reaction mixture was permittεd to warm to room tεmpεrature (24°C). The mixture was stirrεd at 24°C for 23 hours. A clear deep red viscous mass formed. Additional diphenyl ether (0.060 g 6X10 -4 mole) was then added and the reaction mixture stirred for 2 hours. The reaction mass was added to cold methanol (Waring blender) , filtered and the prεcipitate was washed in methanol overnight then soaked in water. The mixture was filtered, rinsed with methanol and dried under vacuum at 120°C. The resulting polymer (2.15 g, 92% yield) was an off-white powder having an inherεnt viscosity of 0.60 (0.15S in concεntrated sulfuric acid). Compression molding at 400°C yielded a light colored, tough, flexiblε slab. Thε slab beca ε brittle on annealing. Example 15 The procedure of Example 15 was repeated using 4,4'-diphenoxybεnzophεnone (2.162 g, 0.0059 mole), phosgene (1.43 g, 0.0144 mole), lithium chloride (1.00 g, 0.0236 mole) and aluminum trichloridε (6.24 g, 0.0468 mole) in 1 , 2-dichloroethane (8 ml). The resulting product (2.2 g, 94S_ yield) was an off-white polymer having a relatively high gel content which formed a yellow flexible slab when pressed at 400°C. OMPI Ex amp l ε 1 6 Procedure A: N,N-Dimethylform,amide (DMF, 1.45 g, 0.020 mole) was added dropwise with cooling and stirring to anhydrous aluminum chloride (5.70 g, 0.043 mole). ' An exotherm ensued, leading to a hot, fluid melt with a few suspeπdεd aluminum chloridε particles. The fluid was kept at 100-110°C for 5-10 minutes under nitrogen. Upon cooling, a light colored liquid was obtained, apparently containing some still undissolved aluminum chloride. p_-Phenoxybenzoyl chloride (3.00 g, 0.013 mole) was added with stirring. The entire mixture was heatεd according to thε schedule in the accompanying table, cooled, and worked up by precipitating into methanol, washing with water and methanol, and drying. Procedure B: The reaction was carried out as above, but with the following amounts of chemicals: DMF (1.46 g, 0.02 mole), anhydrous aluminum chloride (5.32 g, 0.040 mole), and £-phenoxybεnzoyl chloride (1.60 g, 0.007 mole). The polymerization mixture was not heated, but was instead maintained at room temperature for the times indicated Results are given in the table below. Iπherεnt viscositiεs rεportεd arε thosε of thε poly εr as obtainsd, and not of thε slabs. Slabs, if notεd, were pressεd at 400°C for 3 minutεs. Table II Time/ Temp. Inh. Procedure Profile Vise. Comments B 62 hr/24°C 1.46 Flexible yellow-red slab B 17 hr/24°C 0.57 Light colored polymer A 15 min/24°C and 1.14 Pale yellow polymer; light 10 min/100-20° C colored, flexible slab 1 hr/24°C and 0.86 Colorless crystalline slab 15 min/100°C 5 min/24°C, 0.73 Light tan flexible slab 5 min/80-100°C, 5 min/150-70° C, and 2 min/170-80°C Ex ampl e 1 7 A stock solution was preparεd from _-phεnoxy- bεnzophεnonε (0.6165 g, 0.00225 mole), benzoyl chloridε (0.3032 g, 0.00215 moles), dichloroethane (63.6 g) , and _p_-phenoxybenzoyl chloride (116.2 g, 0.400 mole) and stored at room temperature in a flask stoppered with- an-air/no-air sεptu . This stock solution was sufficient for about twenty polymεrizations of the scale below. Polymer prepared from this stock solution is double-capped at 0.6 mole % (calculated from the ratio of p_-phenoxybeπzophenone, the limiting capping agent, to p_-phenoxybenzoyl chloridε). A reactor consisting of 200 mL resin kettle and a top with four openings to which were attached a mechanical stirrer with a PTFE paddle, a 50 mL addition funnel, a glass-clad thermocouple probe and an inert gas supply tube .was assemblεd. (Glass equipment was dried at 100°C until just prior to use.) All ground glass joints were sεalεd with PTFE seals, excεpt for thε stirrεr shaft which was sεaled with vacuum greasε. Thε assεmblεd reactor was dried with a hot air gun or Bunseπ burnεr while being flushed with nitrogen or argon. The inert gas atmosphere was maintained throughout thε operations except for momentary interruptions for the addition of reagents. The reactor was charged with, in order, anhydrous aluminum chloride (10.0 g, 0.075 molε, Witco #0099), lithium chloride (1.59 g, 0.0375 mole, ACS Reagεnt Grade), and 1 ,2-dichloroethane (10.0 g) . Thε white slurry was cooled to betweεn -15 and -25°C with a dry icε/acεtonε bath. Monomεr stock solution (9.04 g) was added dropwise over a 7 minutε pεriod with continued stirring and cooling. After the completion of this addition, the reaction mixture's . temperature was maintained at -15°C for one hour and then raised to 0°C and maintained therε for 23 hours. ' Approximately 2-3 hours after addition of the monomers, a notable increasε in viscosity occurred. At this point stirring became extremely difficult and was usually discontinued. The polymer could be isolated by one of two workup procedures: (A) The rεaction mixture was transferred into a 500 mL Waring blender containing DMF (100-200 L) chilled to -40°C. The blender was turned on and the dark orange gel transformed into a white, decomplexed polymer. The polymer was collected by filtration, washed with DMF (100 L) , digested in DMF (100 mL, 50°C, overnight) , filtered, and digested in water (2 X 150 mL, 60°C, 1 hr each) . After filtration, the polymer was dried overnight at 165°C in a vacuum oven. (8) The reaction mixture was transferred into a 500 mL Waring blender containing 2 % aqueous hydrochloric acid (200 mL) at room temperature. The blender was turned on and the dark orange gel transformed into white, decomplexed polymer. The polymer was collected by filtration, washed with 2 % aqueous hydrochloric acid (200 L) and digested successively in methanol (200 mL, overnight, 40°C) and in hot 2 % aqueous hydrochloric acid (2 X 200 mL, 1 hr each) . After filtration, the polymer was washed with deionized water (500 mL) and dried overnight at 165°C in a vacuum oven.. OMPI A white fluffy polymεr with iπhεrεnt viscosity 1.1-1.2 dl/g was obtained. The inherent viscosity did not change by more than 0.10 dl/g aftεr 30 min at 400°C. Examplε 18 This εxamplε dεmonstratεs thε suppression of undesirable side reactions by polymerization in the presence of a Lewis base (in this case, lithium chloride). Two polymerizations were performεd, employing the procedure of Example 17, workup B, with the following exceptions: (1) the capping level was 0.45 ole*, (2) the time-tεmpεraturε profile was 1 hr/0°C followed by room tεmpεraturε reaction, and (3) one of the reactions was run without lithium chloride Aliquots were taken out at the times indicated in the accompanying table and figure, worked up, and analyzed. While the reaction with lithium chloride responds as expected to capping and achievεs stabls molecular -weight after about fifteen hours, the one without lithium chloride does not respond to capping, but instead keεps increasing in molecular weight, indicating the occurrence of substantial side reactions. The polymer from the lithium chloride reaction was more melt stable. T ab l e I I I Polymer Inherεnt Viscosity After Time at 400°C ( in) Reaction Time (hrs) 30 60 With Lithium Chloride ' 6 1.08 1.08 1.24 1.19 8. 1.09 1.12 1.15 1.30 10 1.11 1.14 1.12 gel 13 1.20 1.35 26 1.32 1.24 1,.36 1.18 32 1.33 1.34 1.32 gel Without Lithium Chloride 6 0.93 0.94 ____ 1.09 8 1.02 1.00 0.97 gel 10 1.05 1.13 1.18 gel 13 1.15 1.12 1.12 gel 26 1.72 gel 32 2.15 gel " Ex amp l e 1 9 Thε procedure of Example 17, wgrkup A, was followed, with these excεptions: (1) p-phenoxybenzophenone (0.45 molε Λ) ' as thε only capping agent and (2) the amount of 1 ,2-dichloroethane was adjusted to achieve the indicated pεr cent loading. For the purposes of this sxample, "per cent loading" is defined as 100 times the ratio of the theoretical yield (in grams) of polymer to the sum (in grams) of monomer, capping agent, Lewis acid, Lewis base, and solvent in thε reaction mixture. The results are tabulated below ' showing the effεct of monomer concentration on inherent viscosity of the polymer. Table IV Per Cent Polymer Loadinq Inh. Vise. 5 0.51 10 0.80 12 1.00 14 1.11 16 1.15 18 1.18 20 0.90 Ex a p l e 20 £-Phenoxybenzαyl chloride was polymerized as described in Example 17, workup B, except that no lithium chloride was used and _p-phenoxy-benzophenoπe (0.45 mole % ) was the only capping agent used. The results are provided in the table below which- illustrate the effect of the amount of aluminum chloride on the inherent viscosity of the polymer . Table V Molar Ratio of Polymer Aluminum Chloride Inherent to Monomer Viscosity 1 , . 20 0.50 ' 1 , . 50 0.98 1 , . 80 1.13 2. , 00 1.17 3 . . 00 1.15 A comparison polymerization run with aluminum chloride: lithium chloride: _-phεnoxybεnzoyl chloride molar ratio of 3.0:1.5:1.0 αave an inherent viscosity of 1.15. OMPI Ex a p l ε 21 A rεaction flask squipped with- a magnetic stirrer and a nitrogen inlet was charged with methylεne chloride (8 mL) and ,N-dimethyl formamide (1.45 g, 20 mmol). Anhydrous aluminum bromide (13.33 g, 50 mmol) was added gradually, with- cooling (exotherm ensues) , followed by _p_-phenoxyben∑oyl chloride (2.33 g, 10 mmol). Polymerization was allowed to proceed overnight at room tempεrature. The polymer -was isolated by precipitating it into methanol and washing overnight at room temperature consecutively with methanol and water. The polymer was a white powder with inherent viscosity 1.03. A slab pressed at 400°C for 5 minutes was transparent and flexible. Example 22 £-Phεnoxybenzoyl chloride was polymerized as in Example 17, workup A, except that (1) £-phenox benzophεnone (0.45 molε % ) was thε only capping agεnt, (2) the "per cent loading" was adjusted to the levεls givεn bεlow by varying thε amount of 1 , 2-dichloroethane used, and (3) no Lewis base was added. For the purposes of this example "per cent loading" is defined as 100 times the ratio of the theorεtical yield (in grams) of polymer to the sum (in grams) of monomer, capping agent, Lewis acid, and solvent. The results are provided in the table below. T ab l e V I Per Cent Inherent Loading ( % ) Vise, (dl/g) 5 0.65-0.75 10 0.84-1.01 16 1.10-1.20 Example 23 Diphenyl ether 4,4'-dicarbonyl 'dichloride was polymerized with diphenyl ethεr according to the procedure of Example 17, workup B, except that (1) the monomers werε added directly to the reactor, instead of from a stock - solution, (2) the equivalent ratio of aluminum chloride to acid halide groups was 2.0, (3) no lithium chloride was used, and (4) no capping agents were used. The polymer obtained an inherent viscosity of 1.03 Example 24 Diphenyl ether 4,4'-dicarbonyl dichloride was polymerized with 1 , 4-diphenoxybenzene according to the procedure of Example 17, workup B, except that (1) the monomers were addεd directly to- the reactor, instead of from a stock -solution, (2) the equivalent ratio of aluminum chloride to acid halidε groups was 2.0, (3) no lithium chloride was used, and (4) no capping agents were used. The polymer obtained had an inherεnt viscosity of 0.93. OMP Examplε 25 4,4' -Diphεnoxybεnzophenone .was polymεrizεd with tεrεphthaloyl chloridε, with and without addεd lithium chloridε, according to thε procεdurε of Examplε 17, workup A, with thεse exceptions: (1) the reactions were not capped: (2) aluminum chloride was added to a suspension of thε monomers in 1, 2-dichloroεthanε, instεad of vice-versa; (3) where lithium chloride was used, it was used in the amount of 2.0 equivalεnts per εquivalent of carbonyl groups in the reaction mixture; and (4) aluminum chloride was used in a.10 equivalent % excεss over the total εquivalεnts of carbonyl groups and lithium chloridε. Thε reaction with lithium chloride gave polymer with inherent viscosity 5.2 and the one without, 4.2. Both samples contained some gel. Example 26 This examplε demonstrates the necessity for controlling the εxcess of aluminum chloride where the monomers used are terεphthaloyl chloridε and a comonomεr as dεfined in I(ii)(a), I(ii)(b), or I(i)(d) and whεrε thε polymerization is conductεd in thε substantial absence of Lewis base. Terephthaloyl chloride was polymerized with 1 ,4-diphenoxybenzenε by thε procedure of Example 17, workup A, with these exceptions: (1) no capping agents werε employed, (2) the "per cent loading," as defined hereinbεfore , was about 12S5 (Example 17 calculates to about 16), (3) no lithium chloride was added, and (4) the equivalεnt % excess of aluminum chloride was either 10 or 100, relative to the total equivalεnts of acid chloridε groups present. The reaction with only 10 equivalent % excess aluminum chloride gave polymer with inherent viscosity 1.59. The reaction with 100 equivalεnt % excess aluminum chloride gave polymer with inherεnt viscosity 0.18. Examplε 27 This example demonstrates the benefits of poly¬ merizing terephthaloyl chloride with a comonomer as defined in I(.ii)(a), I(ii)(b), or I(ii)(c) in the presence of a Lewis base. Terephthaloyl chloride was polymerized with 1 ,4-diphenoxybεnzεne with and without lithium chloride added, according to the procedure of Example 17, workup A, with excεptions as noted: (1) the "percent loading," as defined hereinbefore, was about 12Λ, (2) the polymerizations were capped by employing 0.8 mole S. excess of 1 , -diphenoxy- benzene and 0.16 mole % of benzoyl chloride, (3) where lithium chloride was added, it was in the amount 'of 1 equivalent per equivalent of acid halide groups, and (4) the equivalent % excess of aluminum chloride over the sum of acid halide and lithium chloride equivalents was 1U°_. The reaction with lithium chloride was homogeneous and gave polymer with inherεnt viscosity 0.91, whilε onε without lithium chloridε was heterogeneous and gave polymer of inherent viscosity 0.60. OMPI Thε prεparation of aromatic polymεrs in accordance with this invention has been set forth above with reference to specific εmbodimεnts thereof. It is to be understood that the specific embodimεnts arε illustrativε in naturε and the iπv ' ention is not limitεd to such embodiments.- The invention in its broadest aspect is directed to an electro¬ philic polymerization reaction in which the reaction medium comprises free Lεwis acid and a complεx between a Lewis acid component and a Lewis base component " and, optionally, a non-protic diluent..

Claims: We Cl aim : 1. A method of producing a poly(arylene ether ketone) which comprises polymerizing (I) phosgenε or an aromatic diacid. dihalidε together with a polynuclear aromatic comonomer containing two active hydrogen atoms or (II) a polynuclear aromatic comonomer containing both an acid halide group and an active hydrogen atom, in the presence of a Lewis acid, optionally a controlling agent and optionally a non-protic diluent, the various components being presεnt in such proportions and the polymerization being conducted under such reaction conditions that a thermally stable, linear poly(arylene ethεr kεtone) substantially- free of pendant groups resulting from ortho substitution of para-linked aromatic rings in the polymer backbone is obtained. 2 , A method of producing a poly(arylene ether kεtonε) which cornprisεs polymerizing a monomer system comprising: I) (i) phosgenε or an aromatic diacid dihalide togεther with (ii) a polynuclear aromatic comonomer comprising: (a) H-Ar-0-Ar-H (b) H-(Ar-0) n -Ar-H wherεin n is 2 or 3 (c) H-Ar-O-Ar-(CO-Ar-O-Ar) -H wherein m is 1 , 2 or 3 or (d) H-(Ar-O) n -AΓ-CO-AΓ-(O-AΓ) m -H wherein m is 1 , 2 or 3, and n is 2 or 3 or II) an acid halide of the formula: H-AΓ-0-[(AΓ-C0) -(AΓ-0) -(AΓ-CO) ]. -AΓ-C0-Z P q r k wherεin Z is halogεn, k is 0, 1 or 2, p is 1 or 2, q is 0, 1 or 2 and r is 0, 1 or 2; or III) an acid halidε of thε formula: H-(Ar-O) n -Ar-Y whεrεin π is 2 or 3 and Y is CO-Z or CO-Ar-CO-Z where Z is halogen; wherein each Ar is independεntly sεlεctεd from s-ubstituted or unsubstituted phenylene, and substituted and unsubstitut polynuclear aromatic moieties freε of ketone carbonyl and ether oxygen groups; in a rεaction mεdium comprising A) a Lεwis acid in an amount of about onε equivalent per equivalent of carbonyl groups presεnt plus about one equivalent per equivalent of Lewis base, plus an amount effεctive to act as a catalyst for the polymerization; 8) a Lewis base in an amount from 0 to about 4 equivalεnts per equivalεnt of acid halidε groups prεsεnt in thε monomer system; and C) a non-protic diluent in an amount from 0 to about 93?. by weight, based on the weight of the total reaction mixture; with the proviso that in the substantial absence of Lewis base and : i) the monomer system includes a diacid dihalide and a comonomer as defined in KiiXa) , I(ii)(b) or I(ii)(d) : (aa) the Lewis acid is present in excess of the minimum specified in A) above by an amount of up to about 0.8 equivalents per equivalent of undeactivated arylo y groups in the monomers, and, if the acid halide group are situated on separate non-fused aromatic rings, by an additional amount of up to about 0.5 equivalents per equivalεnt of acid halid groups; and (bb) the concentration of monomers in the reaction mixture is at at least about 75. by weight, based on the total weight of the reaction mixture; with the further proviso that when the monomer system includes a comonomer as definεd in I(ii)(a) and the diacid dihalide is benzenε dicarbonyl dichloride or diphenyl ether dicarbonyl dichloride, the polymer is at least partially crystalline; ϋ) the monomer system is III, the Lewis acid is presεnt in εxcess of the minimum specified in (A) above by an amount of up to about 0.8 equivalent per equivalent of undeactivated aryloxy groups -in the monomers; or iii) the monomer system is 1(c) or II, thε ' Lεwis acid is-prεsεnt in an amount in excess of the minimum specified in A) above by at least 0.6 +• [0.25 X tanh (50(0.1-D)] equivalεnts pεr' εquivalent of acid halidε groups where D is the molar ratio of monomer to diluent. 3 ' . A method in accαrdancε with Claim 2 whεrεin said monomεr systεm comprises p-phenoxybeπzoyl chloride. 4. A method " in accordance with Claim 2 wherein said monomer system comprises 1 ,4-diphenoxybenzεnε and terεp- hthaloyl chloride- 5. A method in accordance with Claim 2 whεrεin said monomer system comprises 4,4' -diphεnoxybenzophenone and phos ' genε or tεrεphthaloyl chloride. 6. A method in accordance with Claim 2 wherein said monomer system comprises diphenyl ether and phosgene. OMrl 7. A method in accordance with Claim 2 wherein said monomer system comprises 1 , 4-diphenox ybenzene and phosgene 8. A method of producing a poly(arylene ether ketone) which comprises- polymerizing a monomer system comprising: I (i) phosgenε or an aromatic diacid dihalidε togεthεr with (ii) a polynuclear aromatic comonomer containing two active hydrogen atoms or II a polynuclear monomer containing both a an acid halide group and an active hydrogen atom, in a reaction medium comprising a Lεwis acid, present in an amount of at least about one equivalent per equivalent of carbonyl groups present, plus about one equivalent per equivalent of Lewis base, plus an amount effective to act as a catalyst for the polymerization; and a Lewis base, in an amount of up to about 4 equivalents per equivalent of acid halide groups present in the monomer system. 9. A method in accordance with Claim 8 wherein said Lewis acid is selected from the group consisting of aluminum trichloride, boron trichloride, aluminum tribromide , titatanium tetrachloride, antimony pentachloride , ferric chloride, gallium, trichloride, and molybdenum pentachloride . OMPI 10. A method in accordance with Claim 9 wherein said Lewis acid is aluminum trichloride. 11. A method in accordance with Claim 9 wherεiπ said Lewis acid is aluminum tribromide. 12. A method in accordance with Claim 8 wherεin said Lεwis basε is sεlectεd from the group consisting of amides, amines, estεrs, ethers, thioethεrs, kεtonεs, nitriles, nitro compounds, phosphines, phosphine oxides, phosphoramidεs, sulfidεs, sulfonεs, sulfonamidεs, sulfoxidεs and halidε salts. 13. A msthod in accordance with claim 8 whεrεin said Lεwis basε is sεlεctεd from thε group consisting of acetone, benzophenone, cyclohexanonε, εthyl acεtatε, ethylene carbonate, N-methylformamidε, acεtamide, N, N-dimethyl- acetamide, N-methylpyrrαlidone, urea, tetramethylurea, N-acetylmorpholine, dimethyl sulfoxide, diphenyl sulfone, Nj-N-dimεthylmεthaπεsulfonamidε, phosphoryl chloridε, phεnyl- phosphonyl chloridε, pyridinε-N-oxidε, triphεπylphosphinε oxidε, trioctylphosphine oxide, nitropropane, nitrobenzene, benzonitrile, n-butyronitrile, methyl ether, tetrahydrofuran, dimethyl sulfide, trimethylaminε, N, , ' , ' -tetramethylethyl- enεd ' iaminε, N, N-dirnethyldodecylamine, imidazolε, pyridiπe, quinoline, isoquinolinε, bεnzimidazolε, 2,2' -bipyridine, O-phεnanthrolinε and 4-dimethyl aminopyridine . 14. A method in accordance with Claim 8 wherein said Lewis base is selected from the group consisting of N-methylformamide N,N-dimethylformamidε, N,N-dimεthylacεtamidε, 1-methyl-2- pyrrolidone, tetramethylene sulfone, n-butyronitrile, dimeth-ylsulfide, imidazole, acetonε, benzophenone, trimethylami trimethylamine hydrochloride, tetramethylamrnonium chloridε, pyridine-N-oxide, 1-ethylpyridimium chloride, lithium chloride, lithium bromide, sodium chloride, sodium bromide and mixtures thereof. 15 ' . A method in accordance with Claim 8 whεrein said Lεwis acid is aluminum trichloridε and said Le-wis basε is N,N- dimεthylformamidε, n-butyronitrilε, tetramεthylammonium chloridε or lithium chloridε. 1-6. A mεthod in accordance with Claim .15 wherein said Lewis base is N,N-dimethylformamide. 17. A method in accordance with Claim 8 wherein said polymerization is carriεd out in the presεncε of a non-protic diluent. 18. A method in accordance with Claim 17 wherein said diluent has a dielectric constant of at least about 2.5 at 2-4°C. 19. A method in accordance with Claim 18 wherein said diluent has a dielectric constant in the rangε of from about 4.0 to about 25 at 24°C. OMPI 20. A method in accordance with Claim 17 wherein said diluent is sεlectεd from thε group consisting of methylene chloride, carbon disulfide, o-dichlorobenzene, 1,2,4- trichlo obεnzεπε, o-difluorobεnzεnε, 1 ,2-dichloro- ethane-, 1 , 1 , 2,2-tεtrachloroethane and mixtures therεof. 21. A mεthod in accordance with Claim 8 wherεin said monomer system comprises p-phenoxybenzoyl chloridε. 22'. A mεthod in accordancε with Claim 8 whεrεin said monomer system comprises 1 ,4-diphenoxybenzene and terep¬ hthaloyl chloride. 23. A method in accordancε w'ith Claim 8 whεrεin said monomer system comprises 4,4' -diphenoxybenzophenonε and phosgene or terephthaloyl chloride. 24. A method in accordance with Claim 8 wherein said monomer system comprises diphenyl ethεr and phosgεnε. 25. A mεthod in accordaπcε with Claim 8 whεrεiπ said monomεr systεm comprisεs 1 ,4-diphεnoxybenzenε and phosgene, 26. A method in accordance with Claim 8 wherein a capping agent is added to the reaction medium. 27. A method in accordance with Claim 26 wherein both a nucleophilic and an electrophilic capping agent is added to the reaction medium. 28. A method in accordance with Claim 26 wherεin said nucleophlilic capping agent is selected from the group consisting of 4-chlorobiphenyl, 4-phenoxybeπzophεnonε, biphεnyl, 4-(4-phenoxyphenoxy)benzophεnone and 4-benzεne- sulfonylphenyl phenyl ethεr. 29. A method in accordance with Claim 2,8 wherein said electrophilic capping- agent is selected from the group consisting of benzoyl chloride and benzεnεsulfonyl chloride 3.0. A method of producing a poly(arylene ether ketone) which comprises polymerizing a monomer system comprising (i) phosgenε or an aromatic diacid dihalidε togεther with (ii) a polynuclear aromatic comonomer of the formula H-AΓ-0-AΓ-H wherein each Ar is indepεndεntly selectεd from substitutεd or unsubstituted phenylene, and substituted and unsubstituted polynuclear aromatic oietiεs frεε of kεtonε carbonyl and ether oxygen groups; in a reaction medium comprising: a non-protic diluent in an amount from Q to about 93% by weight, based on the weight of the total reaction mixture; and a Lewis acid in an amount of about one equivalent per εquivalent of carbonyl groups present plus an amount effective to act as' a catalyst for the polymerization, plus /^13 £ 0MPI an amount of up to about 0.8 εquivalεnts per equivalεnt of undeactivted aryloxy groups in the mononers, and if thε acid halidε group arε situated on separata non-fused aromatic rings, by an additional amount of up to about 0.5 equivalents per equivalent of acid halide groups; with the proviso that the concεntration of monomers in the reaction mixture is at least about 75. by weight, based on the total weight of the reaction mixture; with the further proviso that when thε diacid dihalidε is benzene dicarbonyl dichloride or diphenyl ethεr dicarbonyl dichloridε, the polymer is at least partially crystalline. 31. A method in accordance with Claim 30 whεrεin thε diacid dihalide is tεrεphthaloyl or isophthaloyl chloridε or mixtures therεof, and the polynuclear aromatic comonomer is diphenyl ether. 32. A method in accordance with Claim 30 whεrεin thε Lewis acid is aluminum trichloride. 33. A method in accordance with Claim 30 wherein the concentration of the monomers in the reaction medium is at least about 10?_ by weight based on the total weight of the reaction mixture. 34. A method in accordance with Claim 30 wherein the concentration of the monomers in the reaction medium is at least about 155. by weight based on the total weight of the reaction mixture. 35. A method in accordance with Claim 30 wherein the polymerization is conducted at a temperature in the range of -30 β C to +25°C- 36. A method of producing a poly(arylene ether ketonε) which comprisεs polymεrizing a monomer system comprising ( i) phosgenε or an aromatic diacid dihalide together with (ii) a polynuclear aromatic comonomer of the formula H-(Ar-O) n-Ar-H wherein each Ar is independently selected from substituted or unsubstituted phenylene, and substituted and unsubstituted polynuclear aromatic moieties freε of kεtonε carbonyl- and εther oxygen groups and n is 2 or 3; in a reaction medium comprising a non-protic diluent in an amount from 0 to about 93 % by weight, based on the weight of the total reaction mixture; and a Lewis acid in an amount of about one equivalent per equivalent of carbonyl groups presεnt plus an amount effective to act as a catalyst for the polymerization, plus OMPI an amount of up to about 0.8 equivalεnts per equivalent of undeactivatεd aryloxy groups in thε monomers, and, if the acid halide group are situated on separatε non-fusεd aromatic rings, by an additional amount of up to about 0.5 equivalents per .equivalent of acid halide groups; with the proviso that the concentration of monomers in the reaction mixture is at least about 1 % by wεight, basεd on thε total wεight of the reaction mixtures. 37. A method in accordance with Claim 36 wherein the diacid halide is terεphthaloyl chloridε and thε polynuclear aromatic comonomer is bisphenoxybεnzeπe. 38. A mεthod in accordancε with Claim 36 whεrεin thε Lεwis acid is aluminum trichloride. 39. A method in accordance with Claim 36 wherein the concentration of the monomers in the reaction medium is at least about 10S. by weight based on the total weight of the reaction mixture. 40.. * A method in accordance with Claim 36 wherein the concentration of the monomers in thε rεaction εdium is at lεast about 15°ό by wεight based on the total weight of the reaction mixture. 41. A method in accordance with Claim 36 wherein the polymerization is conducted at a temperature in the rangε of -30°C to +25°C. 42. A method of producing a poly(arylene ether ketonε) which comprises polymerizing a monomer system comprising (_i) phosgene or an aromatic diacid dihalide together with (ii) a polynuclear aromatic comonomer of the formula H-Ar-0-Ar- (CO-Ar-0-Ar) -H wherein each Ar is indep rendently j selected from, substituted or unsubstituted phenylene, and substituted and unsubstituted polynuclear aromatic moieties free of ketone carbonyl or ether oxygen groups and is 1 , 2 or 3; in a reaction medium comprising: a non-protic diluent in an amount from 0 to about 935. by weight, based on the weight of the total reaction mixture; and a Lewis acid in an amount of about one equivalent per equivalent of carbon l groups present plus an amount effective to act as a catalyst for the polymerization, plus an amount of at least about 0.6 +[0.25 X tanh (50(0.1-0)] equivalents per equivalent of acid halide groups where D is the molar ratio of monomer to diluent. 43. A method in accordance with Claim 42 wherein the .diacid dihalide is terephthaloyl chloride and the polynuclear aromatic compound is bisphenoxybenzophenone . 44. A method in accordancε with Claim 42 wherein the Lewis acid is aluminum trichloride. 45. A method in accordance with Claim 42 wherein the polymerization is conducted at a tempεrature- in thε range of -30°C to +25°C. 46. A method of producing a poly(arylenε εthεr kεtonε) which comprisεs polymsrizing a monomεr systεm comprising (i) phosgene or an aromatic diacid dihalide 'together with (ii) a polynuclear aromatic. comonomer of the formula H-(Ar-Q)n-Ar-CO-Ar-(O-Ar) -H wherein each Ar is independently J selεctεd. from s-ubstitutεd or unsubstitutεd phεnylεnε, and substitutεd and unsubstitutεd polynuclεar aromatic moieties free of kεtonε carbonyl or ether oxygen groups, m is 1, 2 or 3 and n is 2 or 3; in a reaction medium comprising: a non-protic diluent in an amount from 0 to about 9350 by weight, based on the weight of the total reaction mixture; and a Lewis acid in an amount of about one equivalεnt pεr equivalent of carbonyl groups presεnt plus an amount εffective to act as a catalyst for thε polymerization, plus OMPI an amount of up to about 0.8 equivalents per equivalent of undeactivated aryloxy groups in the monomers, and, if the acid halide group are situated on separate non-fused aromatic rings, by an additional amount of up to about 0.5 equivalents per equivalent of the acid halide groups; with the provisio that the concentration of monomers in the reaction mixture is at least about 75. by weight, based on the total weight of the reaction mixture. 47. A method in accordance with Claim 46 wherein the monomer. system comprise phosgene and bis( pheno yphenoxy) benzophenone 4B. A method in accordance with Claim 46 wherein the Lewis acid is aluminum trichloridε. 49. A mεthod in accordance with Claim 46 wherein the concentration of the monomers in the reaction medium is at least about 105. by weight based on the total weight of the reaction mixture. 50. A method in accordance with Claim 46 wherein the concentration of the monomers in the reaction medium is at least about 155. by weight based on the total weight of- the reaction mixture. 51. A method in accordance with Claim 46 wherein the polymerization is conducted at a temperature in the range of -30°C -to +25 β C. 52. A method of producing a poly(arylene ether ketonε) which comprisεs polymεrizing a monomεr system comprising an acid halide of the formula: . H-Ar-0-[(Ar-C0)p-(AΓ-0q-(Ar-CO)r k-CO-Z wherein each Ar is indεpendeπtly selεcted from substituted or unsubstituted phenylene, and substituted and unsubstitu polynuclear aromatic oietiεs frεε of kεtonε carbonyl and ether oxygen groups; Z is halogen and k is 0, 1 or 2, p is 1 or 2 and q is 0, 1 or 2 and ' r is 0, 1 or 2; in a reaction medium comprising a non-protic diluent in an amount from 0 to about 935. by weight, based on the weight of the total reaction mixture, and a Lewis acid in an amount of about one equivalent per εquivalent of carbonyl groups present plus an amount effεctivε to act as a catalyst for thε polymεrization, plus an amount of at least about 0.6 +[0.25 X tanh(50(0.1-D) )] equivalents per equival ' επt of acid halidε groups where D is the molar ratio of monomer to diluent. 53. A method in accordance with Claim 52 wherein the monomer system comprises p-phenoxybenzoyl chloride. 54. A method in accordance with Claim 52 wherein the Lewis acid is aluminum trichloride. 55. A method in accordance with Claim 52 wherein the polymerization is conducted at a tεmperature in the range of -3 ' 0°C to +25 β C. 56. A method of producing a polyCarylene ether ketone) which comprises polymerizing a monomer system comprising an acid halide of the formula: wherein each Ar is indepεndεntly selected from sub¬ stituted or unsubstituted phenylene, and substituted and unsubstituted polynuclear aromatic moieties free of ethεr carbonyl and ether oxygen groups; Y is CO-Z or CO-Ar-CO-Z where Z is halogen; and n is 2 or 3; in a reaction medium comprising: a non-protic diluent in an amount from 0 to about 93 % by weight, based on the weight of the to.tal reaction medium; and a Lewis acid in an amount of about one equivalent per equivalent of carbonyl groups presεnt plus an amount εffεctivε to act as a catalyst for thε polymerization, plus an amount of up to about 0.8 equivalεnt per equivalent of undeactivatεd aryloxy groups in thε monomεrs. 57. A method in accordance with Claim 56 wherεin thε monomer system comprises p-phenoxy-p-phεnoxybεnzoyl chloridε. 58. A method in accordance with Claim 5 ' 6 wherεin thε Lewis acid is aluminum trichloride. 59. A method in accordance with Claim 56 wherεin thε pαlymεrizatioπ is conductεd at a tεmpεr ' aturε in thε rangε of -30°C to +25°C. -^JRE£ OMPI

Inventors: GORS HEINRICH CARL, JANSONS VIKTORS, GORS, HEINRICH, CARL, JANSONS, VIKTORS
Applicants: RAYCHEM CORP, RAYCHEM CORPORATION
Application year: 1984
Main classification: C08G67
IPC codes: C08G61, C08G67