3,065,205 United States Patent Office Patented Nov. 20, 1962 2 ride, 1,4-naphthoyl dichloride, 1,5-naphthoyl dichloride, 3,065,205 AROMATIC POLY KETGINES AND PREPARATEGN 1,6-naphthoyl dichloride, anthracene-1,5-diacid chloride THEREGF and anthracene-1,9-diacid chloride. As representative ali Williard Hallam Borner, Jr., Wilmington, Del, assignor phatic diacid chlorides useful herein there may be men to E. H. de Poat de Nera ours and Company, Wilming tioned phosgene, succinyl chloride, glutaryl chloride, toa, Dei., a corporation of Delaware adipyl chloride and sebacyl chloride. No Drawing. Fied Oct. 27, 1959, Ser. No. 848,933 The preferred Friedel-Crafts catalysts are aluminum 12 Claims. (C. 260-63) chloride, antimony pentachloride and ferric chloride. Other Friedel-Crafts catalysts, such as aluminum bro This invention relates to polyketones, and more particu O mide, boron trifluoride, zinc chloride, antimony trichlo larly to novel aromatic polyketones and to a process for ride, ferric bromide and stannic chloride, can also be used. their production. The preferred organic solvent for the acylation reac Aliphatic polyketones, such as those obtainable through tions of this invention is nitrobenzene, in that the catalyst, the copolymerization of ethylene and carbon monoxide Such as aluminum chloride, is soluble in it. The reaction have been known for some time. Other predominantly mixture remains homogeneous throughout. Other sol aliphatic polyketones have been obtained by copolymeriza vents, such as symmetrical tetrachloroethane, dichloro tion of fury vinyl ketones with acrylic acid esters as de benzene or carbon disulfide may be employed; use of scribed in U.S. Patent 2,309,727. Some aromatic poly carbon disulfide insures a lower reaction temperature ketones, wherein the ketone groups are appended to the with consequent reduction in the amount of insoluble by main polymer chain, have been described in U.S. Patent products that may be formed. 1,937,063. However, until now, no aromatic polyketone The reaction may be carried out over a range of tem with the carbonyl groups incorporated in the main poly peratures of from about 50 C. to about 125 C. In mer chain and having a substantial degree of polymeriza general, it is preferred to carry out the reaction at a tem tion have been available or described in the literature. perature in the range of 65-80 C. In some cases it is Self-condensation of phenyl acetyl chloride has been re 2 5 advantageous to carry out the reaction at temperatures ported (Schmitt et al., Bull. Soc. Chim. France, 1955, as low as 0° C. and as high as 200 C. 1033) but a polyketone of only 2 to 4 repeating units was The following specific examples will serve to further obtained. illustrate the principles and practice of this invention. An object of this invention, therefore, is to provide Percentages are by weight unless otherwise indicated. novel predominately aromatic polyketones. Another ob 30 ject is to provide essentially linear, predominately aro Example I matic, polyketones. Still another object is to provide a simple, economical process for preparing essentially lin In a three-neck 250 ml. flask equipped with a dropping funnel, mechanical stirrer, and a reflux condenser sur ear, predominately aromatic polyketones. The foregoing mounted by a drying tube, the whole of which was flame and related objects will more clearly appear hereinafter. dried under a current of dry nitrogen prior to use, there These objects are realized by the present invention was introduced under anhydrous conditions, 50 ml. of which, briefly stated, comprises reacting in an inert or nitrobenzene and 10 g. of aluminum chloride (0.075 ganic solvent under anhydrous conditions at least one mole). In the dropping funnel there was placed 4.25 g. aromatic compound from the group consisting of aryl of diphenyl ether (0.025 mole) and 5.07 g. isophthalyl ethers and polynuclear aromatic compounds, with a diacid 40 halide from the group consisting of aromatic hydro chloride (0.025 mole) dissolved in 25 ml. of nitroben carbon dicarbonyl halides in which the points of attach Zene. The contents of the dropping funnel were added ment of the carbonyl groups are separated by at least one dropwise to the stirred suspension of aluminum chloride carbon atom, and alkylene diacid halides, in the presence in the reaction flask which was maintained at a tempera of a Friedel-Crafts catalyst, and at a temperature within ture of 65° C. After further heating for 14 hours at this the range of from about 50 to about 125 C. whereby to temperature, the catalyst complex was decomposed by produce an essentially linear, predominately aromatic pouring the reaction mixture into 200 ml. of methanol polyketone wherein the carbonyl groups are incorporated contained in a Waring Blendor. as an integral part of the main polymer chain and are The white precipitate which formed was filtered, washed alternately separated by a recurring group (I) selected successively with 10% hydrochloric acid in methanol and from the class consisting of diphenylene oxide and divalent with two-200 ml. portions of methanol, filtered, then dried polynuclear hydrocarbon groups, and a recurring group in vacuo at 65° C. The product weighed 7.0 g. (93% of theoretical). The material softened at 250 C., was solu (II) selected from the class consisting of phenylene and ble in m-cresol and tetrachloroethylene, indicating that an divalent aliphatic hydrocarbon groups, said polyketone essentially linear polymer had been produced. Heating of having an inherent viscosity of at least 0.15 when meas 5 5 the polymer gave a viscous melt from which long fibers ured at 0.5% solids in concentrated sulfuric acid at 30° C. could be drawn. An infrared spectrum showed a single In the practice of this invention various aromatic com carbonyl band at 1600 cm., characteristic of aryl-aryl pounds may be employed, the main criterion being that ketones. Inherent viscosity measured at 0.5% solids in the aromatic compound should contain at least two aro concentrated sulfuric acid at 30 C, was 0.18. matic rings and preferably these should be separated from 60 one another. Thus, aromatic compounds, such as di Elementary analysis.-Calculated for phenyl, dibenzyl, diphenyl methane, 2,2-diphenyl propane, diphenyl ether, dibenzofuran, carbazole, dibenzothio phene, naphthalene, anthracene, phenanthrene, perylene, -(c.H.0V cité-CH-A-M. fluorene, picene, chrysene, indene, and acridine are suit C, 80.0; H, 4.0. Found: C, 77.34; H, 4.10. able for purposes of this invention. Five grams of the aromatic polyketone described above, Either an aromatic diacid chloride or an aliphatic di was dissolved in a mixture of 20 ml. of concentrated acid chloride may be employed. In the case of the aro sulfuric acid and 2 ml. of fuming sulfuric acid. This matic diacid chlorides, it is essential that the points of mixture was held at a temperature between 35 C. and attachment of the two carbonyl functions be separated by 70 45 C. and there was added 2.1 grams of sodium azide at least one carbon atom. Suitable aromatic diacid over a period of 15 minutes while the reaction mixture chlorides include terephthalyl chloride, isophthalyl chlo was stirred. Stirring was continued for an additional 8,065,205 3 4. 2% hours, the reaction mixture was cooled to room tem Biphenyl and isophthalyl chloride with aluminum chloride perature, a stream of air was drawn through the reaction catalyst. mixture for two hours and the reaction mixture was then Biphenyl and isophthalyl chloride with aluminum chloride poured onto ice. The solid precipitate was washed free catalyst and with dichlorobenzene as the solvent in of sulfuric acid, filtered and dried. Inherent viscosity of place of nitrobenzene. the product was 0.18 as measured at 0.5% solids in Biphenyl and isophthalyl chloride with ferric chloride as concentrated sulfuric acid at 30° C. catalyst. A one square inch sample of the product was pressed Diphenyl ether and isophthalyl chloride with SbCls cata into a film by pressing at 30 tons pressure at 285-290 C. lyst. An infrared scan showed absorption bands at 3.1, 6.1 and 0 Diphenyl ether and isophthalyl chloride with aluminum 6.5 microns characteristic of N-Substituted primary chloride catalyst. amides. Diphenyl methane and isophthalyl chloride with alumi Example 2 num bromide catalyst, Example 1 was repeated, with an equivalent amount of Diphenyl methane and isophthalyl chloride with aluminum terephthalyl chloride substituted for isophthalyl chloride. 5 chloride catalyst. An 85% yield of polymer was obtained. The product Biphenyl and terephthalyl chloride with SbCls catalyst. had an inherent viscosity of 0.13 as measured at 0.5% The products were highly colored solids and had in solids in concentrated sulfuric acid at 30 C. herent viscosities ranging from 0.13 to 0.18 as measured at 0.5% solids in concentrated sulfuric acid at 30° C. Example 3 20 i claim: 1. A process for preparing essentially linear, substan Example 1 was repeated with an equivalent amount of tially aromatic polyketones which comprises reacting an sebacyl chloride substituted for isophthalyl chloride. A inert organic solvent under anhydrous conditions at least 91% yield of polymer was obtained. The polymer had one aromatic compound from the group consisting of aryl a melting point of 184'-185 C., an inherent viscosity at ethers and polynuclear aromatic hydrocarbons, with a di 0.5% solids in concentrated sulfuric acid at 30° C. of acid halide from the group consisting of aromatic hydro 0.15. Infrared analysis showed an absorption band at carbon dicarbonyl halides in which the points of attach 1678 cm., indicating an alkyl-aryl ketone. ment of the carbonyl groups are separated by at least one Calculated for carbon atom, and alkylene diacid halides, in the presence of a Friedel-Crafts catalyst, and at a temperature within -cilio C.H.