TITLE: Polyenamines from aromatic diacetylenic diketones and diamines United States Patent 4774359 ABSTRACT: The synthesis and characterization of several polyenamine ketones are discussed wherein conjugated diacetylenic diketones and aromatic diamines are used as a route to the formation of high molecular weight polyenamine ketones which exhibit good mechanical properties and can be cast into creasible films. Typical polymerization conditions involved the reaction of stoichiometric amounts of 1,4- or 1,3-PPPO and a diamine at 60°-130° C. in m-cresol at (w/w) solids content of 8-26% for a specified period of time under a nitrogen atmosphere. Novel polyenamine ketones were prepared with inherent viscosities as high as 1.99 dl/g and tough, clear amber films with tensile strengths of 12,400 psi and tensile moduli of 397,000 psi were cast from solutions of the polymers in chloroform. The polymers exhibited T[g] s as high as 235° C. and weight losses of 14% after aging at 232° C. in circulating air for sixty hours. The specific conditions for the preparation of the various polyenamine ketones are presented in Table I. In most cases, the elemental analyses for the polynamine ketones, shown in Table II, agree within ±0.3% of the theoretical values. INVENTORS: Hergenrother, Paul M. (Yorktown, VA) Bass, Robert G. (Richmond, VA) Sinsky, Mark S. (Richmond, VA) Connell, John W. (Richmond, VA) APPLICATION NUMBER: 07/000692 PUBLICATION DATE: 09/27/1988 FILING DATE: 01/05/1987 ASSIGNEE: The United States of America as represented by the Administrator of the (Washington, DC) PRIMARY CLASS: 564/396 OTHER CLASSES: 528/229, 546/262, 546/264, 564/315, 564/323, 564/330, 564/342, 564/344, 564/430 INTERNATIONAL CLASSES: C08G73/00; C08G73/00; (IPC1-7): C07C87/20; C08G12/00 FIELD OF SEARCH: 564/330, 564/396, 564/430, 564/315, 564/323, 564/342, 564/344, 546/262, 546/264, 528/229 US PATENT REFERENCES: 3242215 Bis-(2-chloroacryloyl) aryl compounds March, 1966 Heitmiller 528/229 OTHER REFERENCES: Ueda, M. et al., Journal of Polymer Science, vol. 14, pp. 931-938 (1976). Ueda, M. et al., Journal of Polymer Science, vol. 16, pp. 2809-2815 (1978). Paulisko, J. A. et al., Journal of Polymer Science, Polymer Chemistry Edition, vol. 20, No. 11, pp. 3079-3094 (1982). PRIMARY EXAMINER: Hollrah, Glennon H. ASSISTANT EXAMINER: Sopp, John A. Attorney, Agent or Firm: Helfrich, George F. Manning, John R. Glenn, Charles E. B. Parent Case Data: This is a division of application Ser. No. 734,366, filed May 15, 1985, now U.S. Pat. No. 4,663,483. CLAIMS: What is claimed as new and desired to be secured by Letters Patent of the United States is: 1. A high molecular weight polyenamine ketone having the general formula of: ##STR6## wherein n=10-500; R is selected from the group consisting of H and C[6] H[5] ; Ar is selected from the aromatic group consisting of ##STR7## and, X is selected from the aromatic group consisting of ##STR8## and the aliphatic group consisting of --C[4] H[8] --, --C[5] H --, --C[6] H --. 2. A high molecular weight polyenamine ketone having improved mechanical properties and formed as the reaction product of: (a) ##STR9## and (b) H[2] N--X--NH[2] where R is selected from the group consisting of H and C[6] H[5] ; Ar is selected from the aromatic group consisting of ##STR10## and, X is selected from the aromatic group consisting of ##STR11## and the aliphatic group consisting of --C[4] H[8] --, --C[5] H --, --C[6] H --. DESCRIPTION: FIELD OF INVENTION This invention relates to novel polyenamine ketones and a process for preparing same to yield polymers having different chemical structures and improved physical properties over those previously prepared. BACKGROUND OF THE INVENTION As part of an effort on high performance/high temperature polymers for functional and aerospace structural applications, the reaction of aromatic diacetylenic diketones with various monomers is under investigation. There are several reports in the literature on the preparation of polyenamine ketones. Ueda and co workers prepared polyenamine ketones from the reaction of diamines with 1,6-diethoxy-1,5-hexadiene-3,4-dione [M. Ueda, K. Otaira and Y. Imai, J. Polym. Sci. Polym. Chem. Ed. 16, 2809 (1978)]and 2,2'-disubstituted bis(4-ethoxymethylene-5-oxazolone [M. Ueda, K. Kino, T. Hirono and Y. Imai, J. Polym. Sci. Polym. Chem. Ed. 14, 931 (1976)]. These low molecular weight polyenamine ketones exhibited initial onset of weight loss by thermogravimetric analysis (TGA) in a nitrogen atmosphere at 200°-300° C. Pavlisko and co workers reported the preparation of polyenamine ketones for the reaction of bis(1,3-diones) and diamines [J. A. Pavlisko, S. J. Huang, and B. C. Benicewicz, J. Polym. Sci. Polym. Chem. Ed. 20, 3079 (1982)]. These polymers were prepared in N-methylpyrrolidone using an acid catalyst with inherent viscosities in the range of 0.25-0.36 dL/g. Polyenamine ketones are not at present commercially available. Poly(enamine-esters) comprise a second type of polymer containing the enaminocarbonyl system. The preparation and characterization of a number of such systems including some containing siloxane units has been reported by Moore and co-workers. [J. A. Moore and J. E. Kochanowski Macromolecules 8, 121 (2975); J. A. Moore and T. O. Mitchell J. Polym. Sci. Polym. Chem. Ed. 18, 3029 (1980) and 21, 1305 (1983)]. It is therefore an object of the present invention to provide novel polyenamine ketones having improved physical property characteristics. Another object of the present invention is to provide high molecular weight polyenamine ketones that can be solution cast to form films having improved mechanical properties. A further object of the present invention is a process for preparing high molecular weight polyenamine ketones. Another subject of the present invention is a process for preparing solution of polyenamine ketones that can be directly used to prepare prepregs, adhesive tapes, film and coatings. BRIEF DESCRIPTION OF THE INVENTION According to the present invention, the foregoing and additional objects are attained by employing a novel process to achieve novel soluble high molecular weight polyenamine ketones. These polyenamine ketones have glass transition temperatures and thermal stabilities much higher than those previously prepared. In addition, the polyenamine ketones of this invention can be solution cast to form films having high mechanical properties. No mechanical properties have been reported on previous polyenamine ketone films presumably due to the low molecular weights which prohibited film formation. Polyenamine ketones of this invention are readily prepared from the reaction of aromatic diacetylenic diketones and diamines as depicted in the following equation: ##STR1## where n=10-500 R=H or C[6] H[5] Ar=aromatic such as ##STR2## X=aromatic such as ##STR3## or aliphatic such as --C[4] H[8] --,--C[5] H --,--C[6] H[12] --, etc. The polymerization is generally conducted by reacting stoichiometric quantities of the two monomers in a stirred solution at 60°-130° C. for several hours. Although m-cresol is the solvent of choice, other solvents such as N,N-dimethylacetamide, dimethylsulfoxide, and chlorinated solvents such as sym-tetrachloroethane can be used. In some cases, the stoichiometry can be imbalanced, preferably by using a slight excess (1 to 3 mole %) of the aromatic diacetylenic diketone, to avoid extremely high molecular weight polymer. If the molecular weight of the polymer is too high the result is extremely viscous solutions and in some cases, gelation. The as-prepared solutions of polyenamine ketones can be used directly to prepare prepregs, adhesive tapes, films or coatings. The solvent is subsequently removed, generally by heating, to leave the polyenamine ketones on the substrate. Polyenamine ketones of a different chemical structure may be prepared by using different aromatic diacetylenic diketones as indicated on the following equation: ##STR4## where n, R, Ar and X are the same as discussed hereinbefore in reference to the first equation. The polymers in the latter equation have a major portion of the mer unit as pendent groups whereas those in the first equation have these groups within the polymer backbone. Also, substituted amines (secondary amines, RHN-X-NHR) can be used in place of the unsubstituted diamines (primary amines, H[2] N-X-NH[2]). The R group would be alkyl (e.g. CH[3], C[2] H[5], etc). The resulting polymers would have different properties than those in the first equation since the polymers from the substituted amines could not engage in hydrogen bonding to form a 6-membered ring. In addition, other nucleophiles may add across the activated acetylene to yield other classes of polymers, as example, synthesis of polymers from the reaction of aromatic diacetylenic diketones and dimercaptans (dithio compounds). A more complete appreciation of the invention and the specific process involved will be more clearly apparent from the following Tables and specific Examples illustrating the addition polymerization of two diacetylenic diketones, 1,1'(1,3-phenylene)bis(3-phenyl-2-propyn-1-one) (1,3-PPPO) and 1,1'-(1,4-phenylene)bis(3-phenyl-2-propyn-1-one) (1,4-PPPO), with various aromatic diamines as a facile route to novel polyenamine ketones. The synthesis and characterization of these polyenamine ketones is set forth in Table I. TABLE I _______________________________________________________________________ ___ Synthesis and Characterization of Polyenamine Ketones Monomer Reaction Conc., Reaction η[inh]^b, GPC Polymer