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Unite States, Patented Dec 3,l4,7l Unite States, Patented Dec. 26, 1961 1 2 Company); sulfonated coal types, such as Zeo Karb 3,014,871 (Permutit Company); nuclear sulfonic types such as NEW COWDUNDS AND LUBRICANT COMPGSi Amberlite IR-120 (Rohm and Haas Company) and TIUNS CONTAINING SAME Dowex 50 (Nalcite HCR) (Dow Chemical Company); .l'ames M. Fulton, Verona, Pa, and William E. Brown, Dallas, Tern, assignors to Gulf Research & Develop: 5 carboxylic acid types such as Alkalex (Research Products ment Company, Pittsburgh, Pa., a corporation of Dela Corporation), Amberlite IRC-SO (Rohm and Haas Com ware pany), Duolite CS-lOO (Chemical Process Company), No Drawing. Filed Sept. 17, I956, Ser. No. 610,417 Permutit 216 (Permutit Company), and Wofatit (I. G. 10 Claims. (Cl. 252-497) Farben Industrie—A.G.). Of these the alumino-silicate 10 ions are preferred. This invention relates to new compounds and to new Among the alumino-silicates which can be employed compositions of matter containing the same such as in preparing the above compounds can be mentioned clay lubricants, particularly greases. minerals of the montmorillonite group, such as montmor The new compounds of this invention can be de?ned illonite, saponite, nontronite, hectorite, and sauconite; as compounds whose anionic portion comprises a poly 15 the kaolin group such as kaolinite, nacrite, dickite, and meric anion having a base exchange capacity of at least halloysite; the hydrous mica group such as hydrobiotite, about 5 milliequivalents per 100 grams and whose cationic glauconite, illite, and bramallite; the chlorite group such portion comprises an onium precursor substituted onium as chlorite and chamosite; clay minerals not belonging to cation. the above groups such as vermiculite, attapulgite, and In preparing the new compounds any polymeric com 20 sepiolite; and mixed-layer varieties of the above minerals pound having a cationic base exchange capacity of at least and groups. about 5 and preferably about 20 to about 1000 milli The clay minerals de?ned above occur as minute, plate equivalents per 100 grams of polymeric compound can like, tube-like and/or ?ber-like particles having an ex be used. By “polymeric compound” we mean to include tremely large surface area compared to that of an equival any compound having a repeating structural unit such 25 ent quantity of a granular material such as sand. This as the combination of small size and great surface area results in a high surface energy with attendant unusual surface properties and extreme a?nity for surface-active agents. The structure of some of these clays, as for instance mont 30 morillonite, can be pictured as a stack of sheet-like three layer lattice units which are weakly bonded to each other and which are expanded in the “c” crystallographic direc tion by water or other substances which can penetrate be unit in sulfonated polystyrene cr0ss~linked with divinyl tween the sheets and separate them. 35 All clay minerals have ion-exchange properties. Thus, for example, montmorillonite has a cation-exchange cap pacity of from 90 to 130 milliequivalents per 100 grams of clay, illite from about 20 to 40 milliequivalents and kaolinite from about 5 to 15 milliequivalents. The proper ties of the clays vary widely with the cations occupying the base exchange positions or sites. A “base-exchange position or site” can be de?ned as an area, in this instance on a clay crystal, which has associated with it an ex changeable cation. Among the cations which are general 45 ly found on the base-exchange position or site can be mentioned sodium, potassium, calcium, manganese, iron, hydrogen, etc. The ions are believed to be held to the clay surface by ionic forces. Of the alumino silicates which are particularly effective in obtaining the new compounds of this invention are montmorillonite and illite. In preparing the compounds of this invention an acid or a salt of the polymeric anion de?ned above, preferably ' an acid or a salt of an alumino-silicate, is preferably re unit in a sulfonated phenol-formaldehyde resin, 55 acted with an onium precursor substituted onium com "SiaA14O1s(HzO) l2—x0x(_) pound by the substitution for the polymeric compound cation of the cation of the onium precursor substituted where x is a number between one and 12, as in mont onium compound. Another method for preparing the morillonite, Si4Al4Om(OH)8_xOXX<~), where x is a num new compounds involves mixing with the acids of the ber between one and 8, as in kaolinite or halloysite, etc. 60 mentioned polymeric anion the onium precursor of the Included among the anions which can constitute the onium-precursor substituted onium compound. anionic portion of the new compounds of our invention By “onium ion” we mean to include such ions as de are the alumino-silicate ions, natural and synthetic, ?ned in Hackh’s Chemical Dictionary, third edition, page such as montmorillonite and Permutit, Decalso and Zeo 594: “A group of organic compounds [ions] of the Dur (Permutit Company), and organic resinous anionic 65 matrices such as phenolic methylene sulfonic acid types type RXl-Iy, which are isologs of ammonium and con tain the element X in its highest positive valence, as which go under such trade names as Amberlite IR~100, Amberlite lR-lOS (Rohm and Haas Company, Dowex 30 X is pentavalent: (Nalcite MX) (Dow Chemical Company), Duolite C~3 Ammonium, --NH4 (Chemical Process Company), lonac C—2OO (American 70 Phosphonium, R.PH4 Cyanamid Company), Wofatit P, Wofatit K, Wofatit KS Arsonium, >R.AsH4 (1. G. Farben Industrie—A.G.), Zeo Rex (Permutit Stibonium, R.SbH¢ 3,014,871 3 X is tetravalent: monohydrochloride. The monohydrochloride can then Oxonium, ROI-I3 be reacted in aqueous solution wtih montmorillonite to Sulfonium, R.SH3 give aminoethylammonium montmorillonite. Selenonium, RSeI-Is The preparation of compounds embraced by the pres Stannonium, R.SnI-I3 ent invention can be illustrated by the following exam X is trivalent: ples. Iodonium, R.IH2 EXAMPLE I They may also be considered as addition compounds Crude Wyoming bentonite was dispersed in distilled [ions] cf. oxonium, carbonium, stibonium, -inium, -yli water at a concentration of 10 to 15 grams per liter and um.” By “onium compound” we mean to include the puri?ed by sedimentation for 15 hours. The material combination of an onium ion with a cation such as chlo remaining in suspension (equivalent spherical diameter ride, bromide, sulfate, etc. Byv “onium precursor” we less than 2.6”.) was siphoned ed and used to prepare the mean a compound from which an onium ion would be reaction product described below. The monohydrochlo formed by the addition thereto of at least one proton, ride salt of “Duomeen-T” (Armour Chemical Company, as for example from ammonia would be formed am 15 R—NH—CH2—CH2~CH2—NH2, where R is a mixture monium by the addition of a proton. of straight chain hydrocarbons of average molecular Any onium precursor substituted onium compound can weight of 247 derived from tallow) was prepared by add be reacted with the de?ned polymeric compound to form ing sufficient hydrochloric acid to reach the ?rst equiv the desired new compounds of this invention. For best alence point of the titration (pl-1:35) which corre results, however, we prefer to employ onium precursor sponds to neutralization of the secondary nitrogen. substituted onium compounds having no carbon atoms, Gravimetric analysis of the clay suspension showed that as in hydrazino, to as many as 100 carbon atoms in the the clay content was 13.8 grams per liter. A two-fold molecule. While R in the above formulae is preferably excess of “Duomeen T” monohydrochloride (on the basis an onium precursor substituted alkyl group having about of one gram of clay equals one milliequivalent base ex one to about 100 carbon atoms in the molecule, R can 25 change capacity) was added to 21 liters of clay suspen be aryl, alkaryl, aralkyl, cycloalkyl, cycloalkaryl, etc. sion. After mixing thoroughly on a shaker, the resultant having about one to about 100 carbon atoms. The num curdy precipitate was allowed to stand in contact with ber of onium precursors, the same or different, which can the supernatant solution for three days to ensure com be present on the onium compound is at least one and plete reaction. The precipitate was ?ltered off and is dependent, to an extent, by the length of the onium Washed with distilled water until a clear ?ltrate with a compound itself. Thus, when the onium compound is of negative chloride test (AgNO3) was obtained. This ma long length, many onium precursors can be accommo terial was dried to produce friable, off-white granules dated. In general, the number of onium precursors sub which were used to make a grease. stituted on the onium compound can be as much as ?fty EXAMPLE II or more. Among the compounds which can be employed 35 to form the anionic portion of the new compounds of A two-fold of hydrazine chloride is added to the this invention are Z-amino-ethylammonium montmoril clay suspension of Example I. After mixing thoroughly lonite, Z-aminoethylammonium Amberlite IR-lOO, sodi on a shaker, the resultant precipitate is allowed to stand um calcium 2-aminoethylammonium montmorillonite, in contact with the supernatant solution for three days to sodium calcium Z-aminoethylammonium Zeo Dur, 2 ensure complete reaction. The precipitate is ?ltered oil aminoethylarnmonium dodecylammonium bentonite, 2 and washed with distilled water until a clear ?ltrate with aminoethylammonium dodecylammonium Dowex 30, 3 a negative chloride test (AgNO3) is obtained, after which arnino-n-butylphosphonium illite, 3t-amino-n-butylphos the material is dried for subsequent use.
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