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United States Patent Office 3,775,380 United States Patent Office Patented Nov.3,775,380 27, 1973 1. 2 3,775,380 fabricated by molding. There is a definite need in the art PoLYMERIZATION OF AROMATIC NITRILES therefore for a process to provide curable B-stage poly Gordon H. Miller, Richmond, Va., assignor to mers derived from aromatic polynitriles which can be No Drawi ESSESS 177,169 conveniently molded under, for example, heat and pres O rawing d I 756, I /io, o 0. 9 5 sure, to yield cured nitrile polymers containing triazine U.S. C. 260-78.4 N 13 Claims grOPS: BRIEF DESCRIPTION OF THE INVENTION ABSTRACT OF THE DISCLOSURE This invention relates to a process for preparing cur able polymeric compositions by heating an aromatic ni Aromatic nitriles having at least two -CN groups are 10 trile having at least two cyano groups in the presence polymerized by heating to a temperature of from about of a catalyst at a temperature of about 410 to about 410 to about 550° C. in the presence of a catalyst, such as 550° C. The polymeric compositions of this invention a metal chloride, to form curable polymeric compositions comprise recurring triazine rings linked together through which under the influence of heat and pressure can be con arylene groups joined to the carbon atoms of the said verted to high strength, thermally stable, insoluble, in- 15 triazine rings. In another aspect, this invention relates flusible, polymeric materials. to a method of curing the thus-obtained polymeric com positions at elevated temperatures and pressures to form BACKGROUND OF THE INVENTION insoluble, infusible polymeric materials. Field of the invention DETAILED DESCRIPTION OF THE INVENTION This invention relates to a process for polymerizing In the homopolymerization process of this invention aromatic nitriles having at least two cyano groups. More when Strating with an aromatic polynitrile, such as a particularly, the invention relates to a process for pre- dinitrile, the reaction is one of trimerization to form paring curable polymeric compositions by heating an triazine rings. When aromatic substituted 1,3,5-triazines aromatic polynitrile or an aromatic substituted 1,3,5-tri- 25 derived from polynitriles are employed as starting ma azine derived from a polynitrile in the presence of a terials, the resulting polymeric product has the same catalyst. In another aspect, this invention relates to cur- general polymeric structure as achieved by homopolym able B-stage resin compositions prepared from aromatic erization of the aromatic dinitrile starting materials. nitriles and to the cured products derived therefrom. The general polymeric structure of the polymeric Description of the prior art 30 compositions of this invention is shown below where R1, R2 and R3 may be the same or different arylene theKarguin preparation et al of in a U.S.variety Pat. of 3,164,555 polymeric haveproducts described from theradicals polymer. and where in represents the number of units of aliphatic dinitriles by heating, for example, perfluoro glutaronitrile, etc. at a pressure of at least 5,000 kg./sq. 35 -N N N cm. and at a temperature above 200 C. in the presence --R -o/ Y R of a catalytic amount of a nitrogeneous base or by heat- r -is-ul ing the same monomers in the presence of certain metal N. / halides, such as zinc chloride, etc. in a closed vessel at C (I) a temperature above 100° C. The perfluoronitrile poly- 40 mers formed are useful as antifriction drive train ele ments. Perfluoroether dinitriles have also been homo- M N polymerized or copolymerized with other perfluoroether YN dinitriles or perfluorodinitriles having from 2 to 8 car bon atoms between the nitrile groups, such as perfluoro- 45 The triazine rings formed in the initial polymerization suberodinitrile, to give easily fabricable resins with high step can be linked together in a number of patterns. resistance to corrosive chemicals which are good electrical One possible pattern for the polymer prepared from insulators (see Fritz, U.S. Pat. 3,317,484). 1,4-dicyanobenzene is shown below as Formula II while Of the polymers described in the art, most of them one possible pattern for the polymer prepared from 1,3- are infusible hard resinous materials which cannot be 50 dicyanobenzene is shown below as Formula III. N 3.N N N s 3. (II) 3,775,380 (III) The physical properties of the polymeric materials in 0 3-hydroxy-1,2,4,5-tetracyanobenzene, this invention are believed to be determined by the rela 2-bromo-1,3,4,5-tetracyanobenzene, tive amounts of the various triazine polymers formed 3-nitro-1,2,4,5-tetracyanobenzene, during the polymerization reaction. 2-isopropyl-1,3,4,5-tetracyanobenzene, The process of this invention is applicable to the 3-n-pentyl-1,2,4,5-tetracyanobenzene, etc. polymerization of a wide variety of aromatic polynitriles 25 Mixtures of the above-mentioned aromatic polynitriles, including aromatic dinitriles, etc. as well as aromatic such as a mixture of about 66 percent by weight of iso substituted 1,3,5-triazines derived from aromatic poly phthalonitrile (i.e., 1,3-dicyanobenzene) and about 34 nitriles to form partially polymerized products as well as percent by Weight of terephthalonitrile (i.e., 1,4-dicyano fully cured, infusible, insoluble polymeric products. benzene) can be employed in this process, if desired. Usually, the aromatic polynitriles employed will have 30 Isophthalonitrile and terephthalonitrile are especially val not over 100 carbon atoms and, preferably, not over 35 luable starting materials for use of the process of this in carbon atoms. vention. In addition to the examples above, other substi Polynitriles useful as starting materials in the process tuted aromatic polynitriles can be employed. For exam of this invention include, for example, compounds of ple, those containing groups derived from a carboxyl the formula 35 group, such as carboxylic salts, amides and esters thereof, as well as nitrosulfone and sulfonic acid groups, Also, in the process of this invention aromatic sub R. stitutes 1,3,5-triazines prepared from any of the above listed aromatic polynitriles or mixtures thereof can be {} 40 employed as starting materials. Such aromatic substituted (CN) (I) 1,3,5-triazines can be prepared by the method set forth in Miller application entitled Process for Trimerization of Nitriles (Ser. No. 72,224) filed of even date herewith or where R is selected from the group consisting of hy by the process set forth by Toland in U.S. Pat. 3,060,179. drogen, alkyl of from 1 to 10 inclusive carbon atoms 45 Typical of the aromatic substituted 1,3,5-triazine prod as exemplified by methyl, ethyl, propyl, pentyl, heptyl, lucts formed by trimerizing an aromatic dinitrile is 2,4,6- octyl and isomers thereof, amino, nitro, hydroxyl, car tris(3-cyanophenyl)-1,3,5-triazine prepared from iso boxyl and halogen selected from the group consisting of phthalonitrile which has the formula: chlorine, fluorine, iodine and bromine, and n is an in teger of from 2 to 4 inclusive. 50 CN CN Among the nitriles which are suitable as starting ma terials in the method of this invention are -C C orthophthalonitrile, <>-i-KY isophthalonitrile, 55 S/ terephthalonitrile, 3-methyl-1,4-dicyanobenzene, 5-isopropyl-1,3-dicyanobenzene, 2,5-dimethyl-1,4-dicyanobenzene, CN 2-chloro-1,3-dicyanobenzene, 5-bromo-1,4-dicyanobenzene, 60. 5-amino-1,3-dicyanobenzene, Polymerization conditions 3-nitro-1,2-dicyanobenzene, 2-carboxyl-1,4-dicyanobenzene, The temperature at which the polymerization reaction 2-(dichloromethyl)-1,3-dicyanobenzene, of this invention is carried out can be varied widely al 2-ethyl-3-chloro-1,4-dicyanobenzene, 65 though generally the temperature utilized will be from 4-hydroxy-1,3-dicyanobenzene, about 410 to about 550 C. and, preferably, will be from 2-n-octyl-1,4-dicyanobenzene, about 420 to about 510 C. A wide variety of products re 3-nitro-1,2-dicyanobenzene, sult which are, in general, solids at room temperature but 1,3,5-tricyanobenzene, - at elevated temperatures range from highly fluid to viscous 2-chloro-1,3,5-tricyanobenzene, 70 and to rigid, infusible polymeric materials. Among the 3-fluoro-1,4,5-tricyanobenzene, products which can be made are partially cured thermo 6-nitro-1,3,5-tricyanobenzene, plastic compositions which, in this specification, are re 2-hydroxy-3,4,5-tricyanobenzene, ferred to as B-stage resins. Such compositions can be con 4-methyl-1,3,5-tricyanobenzene, 75 veniently cured under the influence of heat or heat and 1,2,4,5-tetracyanobenzene, pressure to yield rigid, infusible, insoluble compositions. 3,775,380 S. 6 The products formed in the early stages of this process The polymeric compositions of this invention can be are at elevated temperatures highly fluid, liquid polymers cured to form a variety of products ranging from materials and as the polymerization continues they become soft which are highly viscous liquids at elevated temperatures materials and finally rigid, infusible, insoluble polymeric to completely cured, hard, rigid, infusible solids. Such products result. The final products, i.e., the completely completely cured materials possess remarkable physical cured compositions, are presumably highly crosslinked ma properties. For example, the completely cured products terials. The products of this invention are extremely in after being heated for as long as 5 hours at 30° C. in air soluble materials which exhibit negligible solubility in or show a negligible weight loss and exhibit no oxidation ef ganic liquids, such as ethers, ketones and aromatic hydro fects. Likewise, these same polymeric materials can be carbons, such as ethyl n-propyl ether, methyl isobutyl O heated in the absence of air to 500 C.
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