Document zzBNoE3vO8MB93kexRYRBm6ym

/ Inventor: Frank M. Clark, 0632561 ' HARTOLDMON0005054 Patented Apr. 2& 1949 2,468,544 UNITED STATES PATENT OFFICE . f "J- - *. 2,483,544 . . STABILIZED HALOGENATED COMPOSITIONS (v , . . AND ELECTRICAL DEVICES - v - . - FrankM.Clark,Pittsfield,Ma--,,assignortoOenml Electric Company, a corporation of New York ' Application November 10,1945, Serial No. 627,834 10 Claims. (CL 175--41) 12 The present application is a continuation-in" MR* may Include compounds In which R rep part of my prior application Serial No. 468,834, resents only aliphatic, aromatic or allcycllc Sled Auguri 10,1643, now abandoned. The In groups. It also Includes compounds In which R vention thereof comprise* compositions of halo represents combinations of the aliphatic, aromat genated hydrocarbons, and In particular, liquid 5 ic, and allcycllo groups and Includes compounds chlorinated hydrocarbons. In accordance with In which such groups contain substituents, such my Invention such compositions are associated as chlorine or other halogen or hydroxyl or amine with a minor amount, which may be less than one radicals. For example the formula MR* may In per cent, of organo-metalllc compound, whereby clude a metal combined directly with an aliphatic the deleterious effect of halogen decomposition 10 group or groups and also one or more aromatic product Is inhibited. or allcycllc groups. An example of an organo- Halogenated aryl hydrocarbons are relatively metalllc compound containing such a multiplicity stable compounds. Halogenated alkyl compounds of unlike groups Is dibutyl diphenyl tin. are less stable, being dissociated but slightly even Other examples of an organo-metalllc com on standing. Decomposition of a halogenated is pound capable of use as an inhibitor In accord aryl compound, however, may occur when such ance with my Invention are compounds having compound is brought into contact with an elec the formula MR*Y In which R represents organic tric arc.' Some decomposition may even occur groups or combinations thereof as previously stat when such oompound is subjected for long pe ed and Y represents inorganic substituent radical, riods to voltage stress (as in capacitors), eape- so such as halogen or hydroxyl, which are attached dally at elevated temperatures. directly to the metal. Examples of compounds Liquid halogenated compounds of benzene, di having the formula MR*Y are triphenyl tin chlo phenyl. and the like, are used In various electric ride, triphenyl tin hydroxide, diphenyl tin di devices as dielectric, Insulating or cooling agents. chloride, and monophenyl tin trichloride. All The presence of even very small amounts of hy- *5 such organo-metalllc compounds will effectively drogen halide, or other eorroelve decomposition combine with hydrogen halide In a liquid halo product, such as may be produced by an arc In genated composition when liberated by any cause contact with a halogenated compound, may dam In such composition. age such apparatus. For example, paper insu In the accompanying drawing, Fig. 1 Is a side lation in eloctrio transformers Is seriously depre- so elevation of a transformer as illustrative of one elated by the premnee of hydrogen chloride, es form of electrical device containing a composition pecially when some moisture is present. Manila embodying my Invention; Fig. 2 Is a graph show or kraft paper after even one day of exposure at 76* C. to a liquid ohlorinated hydrocarbon con ing the extent of protection afforded paper by tin tetraphenyl In a liquid halogenated compo taining hydrogen chloride will lose 70 to 80 per 35 sition which Is exposed to hydrogen chloride gas; cent of Its UnsEe strength. Fig. 3 is a graph showing power factor values I have discovered that halogen decomposition over a range of temperatures in capacitors con products can be rendered substantially Innocuous taining a dielectric material embodying my in if, In accordance with my present Invention, a vention. halogenated! composition, which Is In contact 40 Referring to Fig. 1, the transformer Illustrated with Insulating or other material to be protected. comprises as usual a tank I containing trans Is associated with organo-metalllc compound. former elements comprising essentially a cor* 2, Such compounds, which have a molecular carbon- electrical windings 3. and a quantity of liquid to-metal linkage, are described in Organic Chem cooling and insulating liquid I. The tank cover istry by Oilman, vol. X, pages 491 and 493. This 45 I may be tightly sealed, a frangible window (not book was published In 1943 by John Wiley ft Sons, shown) being provided for the emergency reiease New York. of excessive gas pressure. An externa] bushing An organo-metalllc compound, for example, 8 of the transformer having no relevance to the may have the formula MR*. In this formula M present invention has been shown in part broken represent* a metal chosen from the group con- 60 away. sifting of tin, lead, and mercury; R represents The liquid filling 4 Is liquid halogenated hydro a plurality of aliphatic, altcycllc, or aromatic carbon and may consist of a mixture of chlorinat groups; and x represents an Integer correspond ed diphenyl and chlorinated benzene in which the ing to the valency of the metal In the compound chlorinated diphenyl content may vary widely, and numerically is within the limits of 3 to 4. 65 say from 1 to 99 per cent. Such a composition 06*2562 HARTOLDMON0005055 * 9,468,044 may consist oi a mixture of trichlorbenzene and capacitor dielectric media. Such compounds hexachlor or pentachlor diphenyL A preferred commonly are Introduced as an lmpregnant for liquid chlorinated aryl compoeltion consist* by capacitors in which the armatures are separated weight of 40 per cent trlchiorbeozene and 60 per by several sheets of thin paper. It is frequently cent hexachlordipheny). Compositions of this desired to operate such capacitors continuously character are described in my prior Patent 1,931, when the ambient temperature Is as high as 90* 466 of October 17,1933. Various other halogenat- C.. or higher. . ed compounds,may constitute a part of such com- .. As shown In Fig. 3 by graph 11, the power factor positions as w&L understood, including, for ex- expressed in per cent of a capacitor impregnated ample, halogenafad compounds of diphenyl oxide, 10 with ordinary pentachlor diphenyl tends to fall diphenyl ketone/ diphenyl methane, diphenyl somewhat as the ambient temperature is In ethane, naphthalene and nltro-diphenyl. creased from about 25* C. to about 80* C. The The insulation of the transformer windings or-. power factor rises with further increase in tem- dinarUy consists of manila or kraft paper about perature above 80* C. When the same type of .003 inch in thickness. Cotton and other fibrous 13 capacitor is Impregnated with pentachlor dl- insulatlon may be used. If the cooling and in- phenyl having associated therewith about one- sulatlng liquid consisting of chlorinated aryl quarter per cent of tin tetraphenyl. as shown compounds is subjected to conditions favoring de- by graph 11, lower power factor values ac- composition, hydrogen chloride is formed and the company operation over an elevated range of paper insulation in contact with the contamlnat- ^0 temperature. ed liquid becomes quickly deteriorated. Life teste have shown that capacitors contain- The curve of Fig. 2 shows the relation of loss lng an. organo-metalllc compound such, for ex in tensile strength of paper in per cent when lm- ample, as tin tetraphenyl. have a longer useful mersed in a series of chlorinated compositions life and a greater dielectric stability than exactly containing respectively by weight from 0.05 to 1.2 a* similar capacitors unprovided with such com- per cent of tin tetraphenyl In solution and ex- pound. Capacitors containing organo-metalllc posed to the conditions favorable to the forma- compound do not show the slow rise of power tlon of hydrogen chloride. As Indicated by the factor with time when operated in a high am- graph, paper immersed in chlorinated compound blent temperature which is characteristic of containing no additive ingredient, thus permit- so capacitors impregnated with chlorinated dielec- ting hydrogen chloride to remain in solution trie materials which are unassociated with An therein, loses about 75 per cent of its tensile organo-metalllc compound, strength in one day. On the other hand, paper The advantages accruing from my Invention immersed in the same kind of chlorinated com- are obtained In electric switches. When chlo- posltion containing in solution about .25 per cent 33 rlnated diphenyl or other suitable halogenated of tin tetraphenyl under the same conditions aryl compounds are employed in electric switches, loses only about 6 per cent of Its tensile strength the unavoidable arcing which accompanies make- in the same length of time. As indicated by the and-break of the switch terminals results in some graph, the loss of tensile strength of paper under decomposition. The hydrogen halide thus formed the same conditions resulting in decomposition 40 is rendered Innocuous by the presence of an of the chlorinated composition is reduced sub- organo-metalllc compound. Switches so pro- stastlally to zero if the content of tin tetraphenyl vlded are practically free from the rusting and therein is as high as about one per cent. Amounts corros.l.o..n...w...h..i.c..h....o..r..d..i.n..a..r..ily accompanies the use as low as .05 per cent of a metallo-hydrocarbon of switches filled with halogenated hydrocarbons. present in a cidorlnated aryl compound produce 45 Reference has been made herein to tin tetra an advantageous reduction in the harmful chem- phenyl and other examples of my Invention. leal effect of dissolved hydrogen chloride on Other organo-metalllc compounds which may be paper, cotton or other celluloslc material present associated with halogenated hydrocarbons for the therein. purposes of my invention, include among the Not only dees the presence of an organo- 50 tin compounds, the tetramethyl and the tetra metalllc compound in a halogenated liquid in the ethyl compounds. Mercury compounds, such as amount by weight of about 0.05 to one per cent the methyl and the ethyl, constitute other ex reduce the deleterious effect of such liquid on amples. Lead compounds, such as lead tetra organic insulation, it also greatly reduces ordl- methyl or lead tetraethyl, may be used as Inhlbl- nary rusting of various metals which would occur 55 tors. In general, tin tetraphenyl dlbutyl diphenyl when metal normally located below the surface of tin and lead tetraphenyl are preferred examples the liquid chlorinated composition is exposed to of inhibitors embodying my invention, air. When a transformer containing such a chlo- Although the advantages of my Invention have rlnated liquid is drained, for example, for the been stated with reference to halogenated aryl carrying-out of repairs, exposure to air occurs of 00 compounds, it should not be considered as being surfaces coated with such liquid. Under such limited solely to such compounds. Halogenated conditions rusting occurs which is especially rapid alkyl compounds may be stabilized by the addt- In the presence of moisture. When, however, the tlon of organo-metalllc compounds, halogenated liquid In contact with surfaces con- What I claim as new and desire to secure by tained an organo-metalllc compound as herein 65 Letters Patent of the United States Is: described, then upon exposure to air rusting is re 1. A liquid dielectric and insulating composi stricted to the amount which normally occurs tion consisting essentially of halogenated aryl when clean ferrous metal is exposed to the at hydrocarbon and containing in solution by weight mosphere. about 0.05 to 1 per cent of an organo-metalllc A composition embodying my Invention advan compound chosen from the group consisting of tageously may be used as a liquid dielectric ma compounds having the formulae MR* and MR*Y terial in capacitors. As described in my prior in which Milt metal chosen from the group Patent No. 2,041,594* dated May 19. 1936, chlo consisting of tin. lead and mercury. R is an aro rinated aryl compounds, and particularly penta- matic radical, x Is an integer In the range of 2 chlor diphenyl, may be used advantageously as 75 to 4 and Y Is a halogen. 0632563 HARTOLDMON0005056 3 * 8.4M.M4 6 1 A Miaallr liquid dlalMtrlo tad buulttlng gano-uetallic compound containing carbon-to- eotnpodlloa oonltint MuntlaJIg of halogenttcd metal linkage of the type MR>, M being a metal 7l hydnoubon and containing in solution by chosen from the group consisting of tin, lead might about ona-fourth to one par cent of or- ' and mercury, R is an aromatic radical and x is gano-BMtallls oompound haring the formula ar Integer In the range of 2 to 4. IOU In which Id la a metal chosen from the group 6. A liquid composition suitable for dielectric consisting of tin, lead, and mercury; R Is an or purposes consisting of chlorinated aryl hydro ganic ruUoal ohosen from the group consisting carbon and In admixture therewith about .Ob to of aliphatic and aromatic radicals; combinations 1.2 per cent of tin tetraphenyl. of such radicals and radical containing substl- : i 7. A capacitor dielectric material consisting of tuenta; and a Is an Integer in the range of 3 pentachlor diphenyl having associated therewith to 4. a. A normally liquid dielectric and Insulating about one-quarter per cent of tin tetraphenyl. 8. Dielectric and insulating liquid compositions composition consisting essentially of halogenated consisting_ of chlorinated ar.yl hy. drocarbon and aryl hydrooarbon and containing In solution by ]g about .OS to .25 per cent of tin tetraphenyl. weight alsout one-fourth to one per cent of or 9. An electrical device provided with a dielectric gano-melalllo oompound having the formula and insulating element consisting of a halogen MIUT tn which M Is a metal chosen from the ated aryl hydrocarbon containing In solution group consisting of tin, lead, and mercury; R is therewith about .05 to 1.2 per cent of tin tetra- a radical ohosen from the group consisting of all- m phenyl. phatle and arouatlo radicals, combinations of 10. A liquid dielectric and Insulating composi such radicals, and such radical containing substi tion Including chlorinated diphenyl as an ingre tuents, * is an Integer tn the range of 2 to 4, and dient and containing in solution by weight about T Is an Inorganic substituent choeen from the 0.05 to 1 per cent of an organo-metalllc corn- group consisting of halogen and hydroxyl at- > pound of a metal selected from the group con tacted directly to the metal. slati--ng o#f *t*in", lead,-a-nJd-m---e-r-c-u--ry, the---m---e-t-al being 4. The method of rendering Innocuous hydro attached directly to a carbon atom of an aro gen haUdu formed in liquid halogenated aryl hy matic radical. drocarbon; when subjected to decomposing Influ TRANS M. CLARK. ence which oonslsts In causing such hydrogen to M combine chemically with an organo-metalllc com REFERENCES CITED pound choeen from the group consisting of com pounds having the formulae MR. and MR.Y in The following references are of record In the file of this patent: ' which M Is a metal choeen from the group con sisting of tin, lead and mercury. R Is an aromatic radical, ar Is an Integer In the range of 2 to 4, and 85 Number UNITED STATES PATENTS Name Date Y Is a halogen. 8. An electrical device comprising cooperating 1,668,022 MldgleyMay 1, 1926 1,657,761 McCabe et el..............May 10,1932 eleetrlo element# and a liquid chlorinated aryl hydrocarbon ooollng and Insulating medium 40 therefor, said medium containing In solution by weight about one-fourth to one per cent of or- 2,036,274 2,161,915 2,259,978 Roller.........................Apr. 7, 1936 Rosen.........................Deo. 6, 1939 McLean___________ Oct 21,1941 0632564 HARTOLDMON0005057