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. phonium Duolite C-3, arsinomethylethylenediarsonium EXAMPLE III montmorillonite arsinomethylethylenediarsonium Wofatit 45 P, 3-(aminoethoxy) propylstibonium zeolite, 3-(amino A ten-fold excess of a 10 percent aqueous solution ethoxy) propylstibonium Alkatex, 5-stibino-n-amylsti of Z-aminopyridinium bromide is recirculated, at a rate bonium saponite, S-stibino-n-amylstibonium Amberlite of 5 gallons per square foot per minute, ten times through IRS-50, ethylenediammonium chloride montmorillonite, one kilogram of a dry nuclear sulfonic cationic exchange ethylenediammonium chloride Duolite CS—100, 5-stibino resin manufactured by Dow Chemical Company and hav 3-keto-n-amylstibonium montmorillonite, 5-stibino-3-keto ing the trade name “Dowex-SO.” Bauman, Skidmore and n-amylstibonium Wofatit K, 1-methoxy-2-amino-3-thia-4 Osmun (Industrial and Engineering Chemistry 40, page chlorohexylammonium saponite, 1,4-diethylene diamine 1350 (1948), de?ne “Dower-50” as a “cationic exchange monosaponite, B-aminoanilinium bentonite, 3-arsino-5 resin . . . with a crosslinked aromatic hydrocarbon chain stibinophenyl phosphonium bentonite, Z-aminopyrrolini containing nuclear sulfonic acid groups as the sole cation. um zeolite, 2-aminoethylammonium 6-amino-2-ethoxy-l0 active group.” At the end of the contact period the re methylacridinium nontronite, orthopyrroloammonium circulating liquid is removed and a solid reaction product zeolite, 3-amino-l-naphthalenediazonium zeolite, (2 is obtained. aminovinyl) isopropyloxonium bentonite, 2,4,6-triarsino It is apparent that the above examples have been pre pyrylium montmorillonite (2-stibinovinyl) isopropylselen sented merely as illustrative of our invention and that we onium saponite, (2-aminovinyl) isopropylteluronium sa do not intend to be limited thereby. For example, each ponite and 3-ethylamino-7-dimethylaminophenazathioni of the speci?c polymeric compounds and onium precursor um spent cracking catalyst. substituted onium compounds de?ned above can be sub While any convenient method for preparing the new stituted for their corresponding compound in the examples compounds of this invention can be employed, we prefer 65 above and the new compounds of this invention are ob to prepare the same by reacting a fractional salt of the tained. onium precursor substituted onium compound with the The new compounds of this invention are very eifective de?ned polymeric compound. By "fractional salt” we in the preparation of lubricants, particularly greases, hav ing a high resistance to leaching by water. mean a compound in which the functional onium portion 70 In preparing the improved lubricants of this invention is neutralized but at least one of the onium precursor we can employ any of the oils of lubricating grade, natural substituents remains free. For example, ethylene diamine as Well as synthetic such as silicone oils, ?uorocarbon oils, can be reacted with hydrochloric acid (or other fairly etc., customarily used in compounding greases. Thus the low molecular weight acid, such as sulfuric acid or acetic oil can be a re?ned or semi-re?ned paraf?nie or naph acid) in a 2 to one mol ratio to obtain ethylene diamine 75 thenic-, or asphaltic-base oil having a viscosity of about 93,014,871 6 50 to 4000 SUS at 100° F. If desired, a blend of oils grams of grease in a ballbearing and thereafter revolving of suitable viscosity can be employed instead of ‘a single the bearing at 1800 r.p.m. for 30 minutes at selected tem oil, by means of which any desired viscosity within the peratures. At the end of 30 minutes the amount of range of 50 to 4000 SUS at 100° F. can be obtained. grease leaking from the bearing is weighed and the grease The viscosity of the oil has little effect on the dropping retention determined. The results were as follows: 'point of the compositions but more viscous oils produce compositions having greater stickiness and adhesive prop Grease Re ertim than do the lighter oils. The oil content of the tained in Ternperature, ° F. Bearings, Per compositions prepared according to this invention can cent by Weight comprise about 70 to about 95 percent or more by weight 10 of the total composition. The particular oil as well as RR 99. 4.» the exact amount of oil employed depends upon the char 150 99. 4 220 ______. 98. 0 acteristics desired in the ?nal composition. 260 98. 7 The amount of the new compoundof this invention used to prepare the improved lubricants, such as greases, 15 can vary over wide limits depending upon the particular In order to show the remarkable resistance to water oil with which the new compound is to be blended and leaching of the improved greases of this invention, another upon the properties desired in the ?nal lubricating corn~ grease was prepared exactly in accordance with the grease position. While as much as 30 percent by weight or" the prepared ‘in Example IV except that 14.3 percent by weight of montmorillonite - Duomeen - T - dihidrochloride .total composition can comprise the new compound, we 20 prefer to use smaller amounts, that is, on the order of was used in place of montmorillonite-Duomeen-T-mono about 5 to 15 percent by weight. it should be under hydrochloride. In other words, one had no free amine stood, however, that depending upon the consistency of groups present while the compound of Example IV had the composition desired, less than 5 percent or more than one free amine group on the chain. The greases were placed on a rotating rack and were sprayed with 500 milli 5 percent of the new compound can be employed. When 25 the composition contains less than 5 percent of the new liters of water per minute for 15 minutes at various tem compound very little gelling occurs. Compositions con peratures. The results are set forth below in Table I. taining less than 5 percent of the new compounds are Column 1 represents the percent by weight of grease re semi-?uid in nature and have penetrations on the order tained in the grease of Example IV, while column 2 repre sents the percent by weight of grease retained using the of 400. Compositions containing more than about 30 30 percent by weight of the new compounds are very stilt. grease prepared with montrnorillonite-Duomeen-T-dihy The consistencyétemperature relation of compositions con drochloride. taining as much as 30 percent of the new compoundsin~ Table I dicates that these compositions would be suitable for use Temperature, ° F. 1 2 where block greases are desired such as in open journal 35 bearings of paper mill driers and the trunnion bearings of rotary kilns. It is understood of course that when we 80. 84 i 56 100. 71 23 speak of one of our new compounds being employed in 120 49 5 ‘I40 ______18 0v 0 admixture with the mineral oil ingredient, one or more 160 6 of such compounds can be used. 40 180 0.0 In preparing ‘the new lubricants of this invention, we can employ one or more solvating agents to facilitate dis It can be seen from Table I that the greases prepared persion of the new compound in the oil. Suitable solvat~ in accordance with our invention have increased resistance ing agents are polar organic compounds such as organic to leaching by water. At 80° F., 84 percent by weight acids, esters, alcohols, ethers, ketones, and aldehydes, 45 of the grease was retained, whereas at the same tempera especially low molecular weight compounds of these ture almost half of the grease employing montmorillonite classes. Examples of suitable solvating agents are: ethyl Duomeen-T-dihydrochloride was lost. In fact, at 140° F. acetate, acetic acid, acetone, methyl alcohol, ethyl ‘alcohol, while none of the latter grease was retained, 18 percent, benzoyl chloride, butyl stearate, coconut oil, cyclohexa enough to give some lubricating protection, of the im none, ethylene dichloride, ethyl ether, furfural, isoamyl 50 proved grease was retained. Only when the temperature acetate, methyl ethyl ketone and nitrobenzene. In cases was raised to the extremely high temperature of 180° F. where the use of a solvating agent is desirable for effect was all of the improved grease leached as a result of ac ing more rapid and more comple dispersion of the com tion by water. While We do not wish to be bound thereby, pound in the oil, ordinarly only a relatively small amount we believe the unusual resistance to water leaching of of such agent may be necessary. However, as much as 55 the improved grease is due to the presence of the free about 50 percent by weight based on the amount of new amine group in the montmorillonite-Duomeen-T-mono compound can be used. 'In addition the new compounds hydrdrochloride used. of this invention can be incorporated in petroleum oils If desired, compounds employed for a particular pur by carrying out their synthesis in the oils. pose, such as an antioxidant, can be added to the lubri Example IV below shows the preparation of an im 60 cant prepared herein. Thus, in instances where the lubri proved grease in accordance with the present invention. cant compositions of this invention are to be subjected EXAMPLE IV to prolonged use under oxidizing conditions, we can ad 85.7 percent by weight of a 500/3 Texas Oil and 14.3 vantageously incorporate therein a small amount ofa percent by weight of the compound produced in Example diaryl amine oxidation inhibitor. As examples of some I, montmorillonite-Duomeen-T-monohydrochloride com 65 of the diaryl amines which can be used in the preparation of the lubricants can be mentioned diphenylamine, phenyl plex, were mixed at room temperature and then heated alpha naphthylamine, alpha alpha, alpha beta-, and beta . and stirred at a temperature of 230° to 240° F. for ap beta-dinaphthylamines and the like. The amount of the proximately one-half hour. This was followed by milling diaryl amine employed will depend to a large extent upon and rolling for one hour at 80 r.p.m. The grease pre 70 the severity of the conditions to which the grease is sub pared had a penetration, ASTM D-2l7-52T, unworked jected, as well as the particular diaryl amine used. Gen of 258 and Worked of 313 and exhibited excellent adhe erally, however, the amount of diaryl amine employed is sion to metal. The grease was subjected to a BBC Test between about 0.1 and about 1.5 percent by weight based to determine the amount of grease retained in bearings at upon the weight of the ?nal lubricant composition. In various temperatures. This test involves placing 11/2 75 addition, the improved greases of this invention can be 3,014,871 7 8 used in combination with conventional greases, such as 4. A compound whose anionic portion comprises an sodium, lithium, silica, aluminum, calcium, strontium, alumino-silicate of the hydrous mica group having a barium, etc. base greases, to impart water stability thereto. base base exchange capacity of at least about 5 milli~ Our new compounds have uses in addition to their use equivalents per 100 grams and whose cationic portion as an ingredient in the preparation of the improved lubri comprises a substituted ammonium cation carrying two cants de?ned herein. Used in relatively small amounts in hydrocarbon radicals, at least one of said radicals carrying lubricants, the new compounds can be used to inhibit cor~ a free amine group. rosion of a metal surface in contact with the lubricant. 5. A compound whose anionic portion comprises an Added to waxes, the new compounds can improve the alumino-silicate of the chlorite group having a base ex coe?’icient of friction of the surface of the wax and in 10 change capacity of at least about 5 milliequivalents per crease the tensile and sealing strength thereof. The new 100 grams and whose cationic portion comprises a sub compounds would have valuable anti-stripping etfects in stituted ammonium cation carrying two hydrocarbon radi asphalts used in making aggregates and would raise the cals, at least one of said radicals carrying a free amine melting points of asphaltic compositions or pitch compo group. sitions in which they might be incorporated. Added to 6. A lubricant comprising a lubricating oil having dis— gasolines, the alumino-silicates, decomposed by combus persed therein the compound of claim 1 in an amount tion in the cylinderswould provide valuable abrasives for sui?cient to thicken said oil to the consistency of a securing the cylinder walls and keeping them free of harm grease. ' ful carbon deposits. 7. A lubricant comprising a lubricating oil having dis Obviously, many modi?cations and variations of the in 20 persed therein the compound of claim 2 in an amount vention, as hereinabove set forth, can be made without su?'icient to thicken said oil to the consistency of a departing from the spirit and scope thereof and, therefore, grease. only such limitations should be imposed as are indicated 8. A lubricant comprising a lubricating oil having dis in the appended claims. persed therein the compound of claim 3 in an amount We claim: su?icient to thicken said oil to the consistency of a 1. A compound whose anionic portion comprises an grease. alumino-silicate having a base exchange capacity of at 9. A lubricant comprising a lubricating oil having least about 5 milliequivalents per 100 grams and Whose dispersed therein the compound of claim 4 in an amount cationic portion comprises a substituted ammonium cat su?icient to thicken said oil to the consistency of a ion carrying two hydrocarbon radicals, at least one of grease. , said radicals carrying a free amine group. 10. A lubricant comprising a lubricating oil having 2. A compound whose anionic portion comprises an dispersed therein the compound of claim 5 in an amount alumino-silicate of the montmorillonite group having a su?icient to thicken said oil to the consistency of a grease. base exchange capacity of at least about 5 milliequiva lents per 100 grams and whose cationic portion com References Cited in the ?le of this patent prises a substituted ammonium cation carrying two by UNITED STATES PATENTS drocarbon radicals, at least one of said radicals carrying 2,283,236 Soday ______May 19, 1942 a free amine group. 2,421,082. Pier ______.._ May 27, 1947 3. A compound whose anionic portion comprises an 2,425,747 Lieber ______Aug. 19, 1947 40 alumino-silicate of the kaoline group having a base 2,569,400 Butler ______»_____ Sept. 25, 1951 exchange capacity of at least about 5 milliequivalents 2,668,145 Ronay ______Feb. 2, 1954 per 100 grams and whose cationic portion comprises a 2,767,177 Erickson ______Oct. 16, 1956 substituted ammonium cation carrying two hydrocarbon 2,767,189 Erickson ______Oct. 16, 1956 radicals, at least one of said radicals carrying a free amine group. ' UNITED STATES PATENT OFFICE

Patent No’.. CERTIFICATE‘OFTCORR'E-CTI-ON;-~~-~~~-~-v~3vo14q871 } > I December 269 1961. ‘

James Fulton et, el° T T It is hereby certified that error appears in gbhe above numbered pat , Hen‘brsquir‘ing correction and that the said Letters Patent should read as "corrected ‘below; Column 10 line 56? the formula should appear as shown below instead of as in the patent: -

. . x(—)

column Llv line 36‘, after "two-fold" insert -— excess ——;_ column 5W,“ llne 53V for "comple" read -- complete -——a Sirgwheo and sealeq this 8th clay of May 1962‘,

(SEAL) . I _ c. Attest: ERNEST W. SWIDER DAVID L. LADD ‘ AttestingDff-icer Commissioner of Patents