Патент USA US2408697код для вставки
Patented Oct. 1, 1946 _ 2,408,696‘ UNITED STATE-S PATENT OFFICE TREATMENT OF CARBON BLACK Hugh M. Smallwood, Nutley, N. 1., assignor to ' United States Rubber Company, New York, N. Y.,~a corporation of New Jersey _ No Drawing. Application July 13, 1940, Serial No. 345,429 ' 8 Claims. (Cl. 106-307) . '2 . treatment proceeds, this warm ‘zone passes ' The present invention relates to the treatment throughout the entire body of the black. When chlorine -is passed rapidly into large bodies of carbon black, in which the heat developed in the ‘ flcation of certain carbon blacks which has the property of yielding rubber mixes having abnor 5 reaction cannot be rapidly dissipated, mild ex plosions may take place. mally low viscosities and electrical conductivities, The rate of passing chlorine through the‘car together with exceptionally low hysteresis in the bon black is, therefore, determined by, the size 4' vulcanized condition. Other objects will be ap and shape of the container used to confine the parent from the following description. ' This invention comprises treating hydrogen 10 carbon black. The rate may vary through a wide containing carbon black with gaseous chlorine ; range without appreciably affecting the properties of the ‘product. , The treatment is preferably con-' under such conditions as will leave more than of carbon black. ‘ ' An object of the invention is to obtain a modi- ' tinued until chlorine issues freely from the out about 1% hydrogen chloride adsorbed on the - let, i. e., until the reaction has been completed. ‘ lblack. Any carbon black prepared from natural As noted above, considerable quantities of‘ hy gas or from aromatic hydrocarbons can be used 15 drogen chloride are formed in the course of the in the practice of this invention. - The treatment treatment of the carbon black with chlorine. Part of the black is spoken of as a treatment with chlorine. Bromine, however, ‘can be successfully of this hydrogen chloride is evolved as such, and substituted for chlorine, but the latter is prefer part is retained in the adsorbed state on the car- , . able because it is cheaper. ~ - Carbon black treated according to the presen invention gives a product which possesses the fol 20 bon black. The relative amounts of hydrogen chloride evolved or retained on the black will depend primarily on the temperature at which ‘ the treatment is carried out. The higher the J temperature of treatment the'greater the propor ‘such low viscosity that much higher loadings of 25 tion of hydrogen chloride evolved, and the smaller lowing advantages: - ‘ (1) When mixed into rubber the product, has 1 the treated carbon black can' be used than of un the proportion of adsorbed hydrogen chloride re maining on the black. ' 7 treated black. Substantially all of the hydrogen chloride (2) The mixture with rubber has an abnor - formed in the process can be removed from the -mally low electrical conductivity, and, when vul canized, an abnormally low hysteresis. 80 carbon black by heating it in a stream of nitro gen at temperatures in the neighborhood of 400° The process consists in passing gaseous chlorine C., or by washing the chlorinated black with hot over the carbon black at any temperature ‘in the ' range from room temperature to 500° C. water. Experiments have shown that the at-_ tainment of desirable properties in the rubber mix Throughout ‘this entire range a reaction takes place between the chlorine and the carbon black. is dependent upon retaining as much adsorbed The main features of this reaction will now be hydrogen chloride on the black as is possible. The described. preferred treatment, therefore, consists in treat - Carbon black of the present invention contains ' several tenths of a per cent of hydrogen in a state other than as loosely absorbed water. It ‘is ?rmly attached to the carbon, since this hy drogen is only slowly driven off from the carbon on heating in a current of nitrogen at 1000° C. ‘ ment of the carbon-black with chlorine at tem peratures as ‘close to room temperature as pos sible. ' ' v , , Treatment of carbon black with hydrogen chlo ride under conditions which leave appreciable amounts of hydrogen chloride adsorbed on the When chlorine is passed through carbon black at temperatures in the range given above, hydro ' 45 black are not equivalent: to the chlorine treat‘ ment, since the desirable properties are not ob gen chloride is formed. In the lower part of the tained in full measure. , temperature range evidence of a vigorous reac Typical treatments of black are ‘given in Table tion is found in the factthat appreciable wann L‘blacks A, B, C and .13 being examples of 'my _ ing of the carbon black occurs at the point where the ‘chlorine ?rst encounters ‘the black. As the 50 invention. - “cases Table I A Black treated with B 01' Oi! O ,D Oi! - 1! Hm Brl. Temp. 0! treatment _______________ -_ 340-4709 0... 161-173‘ 0--. Room Room 110-18)‘ 0. Time of treatment, min ........... __ 12o Weight of black, . 11) an 10m 1900 120. 822. in 2.6- Per cent HI retaiilinnd - 944 - 827 12 3.8. . ’ 4.0. ‘large quantities of carbon black, to drop the black In these experiments a typical channelblack -'of the type used for manufacture ‘of tire treads was Lused throughout. This black contained ap slowly through an atmosphere of chlorine. _ The blacks prepared as above were compound ‘ed in rubber according to the following formula proximately .2% . hydrogen‘ as determined by (parts are by weight): chemical analysis. The‘black was, in all cases, 15 con?ned in aé'glass container equipped with an. ' inlet for chlorine at one end and with an outlet - I Parts Smoked sheet Treated black at the other end for removal of evolved gaseous Pine tar products and excess chlorine. In‘those cases in which experiments were made 20 Stearic acid at elevated temperatures, theglass container was .I ’ 100 50 2 > 4.5 - Fast curing zinc oxide_-___. ______ ___s _____ __ ' ' ' 2 Acetone-diphenylamine reaction product___ 1.7 heated externally by means of an electrical re After the treatment, the N,N'-diphenyl' p-phenylene diamine _____ -_ ‘0.3 amount of adsorbed, hydrogen chloride was de-' Thiazole accelerator ____________________ __ ‘1.12 Sulfur ' 2.62 sistance furnace. termined by the following procedure: , Five-gram samples of carbon black were re The compounds of rubber and chlorinated ‘ ?uxed for thirty minutes with 150 cc. distilled blacks were mixed as follows. Rubber was broken down in the customary manner on a 12."~ water. The samples were then ?ltered while hot, and washed six or seven times with 30 cc. por mill with rolls maintained at' 200-250av F. The tions of hot water. » The ?ltrate and washings 80 carbon black, treated or untreated ‘control. was were combined, allowed to cool, and titrated with then added in the customary manner, and mill ing continued‘ with cutting until 'an intimate mixture had been obtained. The remaining com the washing failed to remove any further acid pounding ingredients were then added in the 35 order given above. Experience indicates that the from the black. A detailed description of the preparation of usual methods of- preparing mixes, common to the art, are adequate to enable observation of chlorinated carbonblack C will now be given. ‘ standardized ‘sodium hydroxide solution. ‘Pre liminary experiments showed that prolonging _ ~302 grams of a standard rubber channel black ._ the unique properties of chlorinated black. The mixes were’ cured as usualin a steam . was placed in a glass tube,'approximately 4 cm. inside diameter and 75 cm long. The bottom of 40 heated platen press for 40 min. at 143‘0. ' Table 11 . ‘ r _' o' ‘ I n v I ' - r 1 Above basemix containing ............... -_ Untreated control--- A. 'r-so -11.4... o.n ' s. 4.5.... $2.: ............ .- -4.s.--_ -4.e. Electrical resistivity (ohm-cm.) ........... .. 2.5)(10' ............ .. 2X10‘-.. reaterthan10"-_ 1X1 ... 6X10‘. Torsional hysteresis at can? I‘ .... .7; ...... .. .157 ............... -. .l48...-. .103 ............ -1. .l4_4....- .134. the tube was constricted and ‘closed witha loose ‘so plug of asbestos. At this point an 8 mm. glass ' tube had been sealed to the large tube. Com mercial chlorine from a cylinder was introduced The torsional hysteresis testis described in Gerke et' al., U. B. P. 2,118,001. The electrical resistivity was measured according to the tech nique described in the Gerke et al. patent. at the smaller tube attached to the large tube. ‘ _ In Table II note that the halogenated blacks. (Formulas G. H and vJ) give higher electrical resistivity and lower torsional hysteresis than the control (li'orrnula'li')v containing untreated leading to a hood for removal of waste gases. - black. Further. the black ‘treated with hydro; Chlorine was passed through the column of car gen. chloride (D, Formula I) gave very little low-1 bon black at a rate of approximately 50 to. per ering of hysteresis and only a. four-fold chi-n86 minute for a period of 2 hours. A slight warm in resistivity, even though it‘ contained'more ad-. ing of'the blackwas ‘noticed during the course sorbed hydrochloride than black A. ' of the-treatment, but apart from this, the tem It will be noted from the foregoing data that perature remained at room temperature. The the chlorinated carbon black exerts a strong res black so obtained was found to contain 4.0% ad tarding action upon the vulcanization reac-_ sorbed hydrogen chloride by means of the an tion, as judged by T-BO. This is due to the well alytical procedure described above. . 'known retardation of vulcanization by strong Experience with this process indicates that shape of container used for the black. and the‘ acids. This eifect can be overcome by adding to the mix, along with the customary curing in rate of streaming chlorine through the black, are _' relatively unimportant. Temperature is of im gredients, su?lcient basic material to neutralize portance only insofar as vit controls the amount , the hydrogen‘ chloride contained on the black. The basesusedinthisoperationmustbesuill of hydrogen chloride remaining on the black. ciently strong to form salts with hydrochloric Various means of bringing the carbon into con- . acid which do not retard vulcanization. Zinc tact with the ‘chlorine could be used without de ' parting from the-spirit of this invention. For 7| oxide is not a sufliciently strong base for this - The upper end of the large tube was connected. by means of- a ground joint,'to a smaller tube example, 'it might be advisable. when treating purpose. Sodium hydroxide is sumeiently basic, 2,408,090 (y . 5 , ' 6 a _. . The carbon black treated by the present inven- , tion is to be distinguished from activated char as are also the quaternary bases. Similarly, com pounds such as triethanola'mine can be used ad- ' - vantageously for this purpose. coal, which is not in the ?nely divided form such as channel black, but is in a granular porous The optimum amount of basic material is best determined by preliminary experiments in rub ber, rather than by calculation of the amount 01 basic equivalent to the acid adsorbed on the carbon black. It has been found that the op timum amountof base is rather'less than that.v ' equivalent to the acid content of the black. This 10 is probably due to the reaction of part of the hydrogen chloride with the rubber hydrocarbon. Alternatively, it may be that some of the hy drogen chloride is evolved during the mixing state. ‘ ' v ' ~ Having thus ‘described my invention, what I claim and desire to protect by Letters Patent is: 1. 'A process which comprises treating ?nely divided hydrogen-containing carbon black with gaseous halogen for a time and at a temperature su?lcient to leave more than about 1% hydrogen halide adsorbed on the black. _ 2. A process which comprises treating ?nely divided hydrogen-containing carbon black with 15 gaseous chlorine for a time and at a temperature operation. sufficient to leave more than. about 1% hydrogen chloride adsorbed on the black. 3. A process which comprises treating ?nely In any event, the chlorinated black may be mixed into rubber, and the excess acid may be ‘neutralized without any dis advantage to the re sultant vulcanizate. ' divided hydrogen-containing carbon black with - In these experiments the chlorinated black 20 gaseous chlorine at a temperature approximating ‘room temperature and for a vtime ,suilicient to wasladded to the rubber as described above. leave more than about 1% hydrogen chloride After the black was completely incorporated, the adsorbed on the black. ' ' base‘was added. The mix was then blended for " 5 min. 4. A processwhich comprises treating ?nely, The curing ingredients were then added. The following data were obtained. - 25 divided hydrogen-containing channel black ‘with ' Table In a K L M > N Bass mix as above with ........... -.' 4 Untreated black.-. Chlorinated black -' Chlorinated black Plum . 7 . (6.0% H01). _ a news bl'aOH iTo?‘tlg‘unolomiue. Chlorinated black‘ (6.0% HCl); ’ 8.28.. ~ ...-. (5.0% RC1). ‘10.3. ' OUBED W AT 143' C. v T-50-- _ _ > . > . \‘ -14.2- +135.--“ ..... ..-- -17.4 ........... .. Viscosity (Mooney).-. as 80 5B Electrical resistivity 2.5)(10' Greater than 101).‘. Greater than 10".- Greater than 10". ‘. Torsional hysteresisat 280° F ..... ._ .179 .275! ' - ' . ' —-7.8. --___--_--_- 65. .y.- - 1 .100. , l I This high value is due to the gross retardation of cure. Note that the mixes made from chlorinated black have yisoosities less than um 01 the control (rel-mun x). The low viscosity of the rubber mix, as a re gaseous chlorine for a time and at a temperature sult of chlorination oi the carbon black prior 45 sufficient to leave more than about v1% hydrogen’ chloride adsorbed on the black. to mixing with the rubber, was further demon 5. Carbon black derived from hydrogen con- ‘ strated by the preparation of a mix of 100 of rub tainlngcarbon black and containing more than 1% hydrogen chloride adsorbed on the black. 6. A process which comprises treating ?nely ber,v 90 parts of chlorinated black containing ' (‘4.8% adsorbed hydrogen chloride, 2 parts of pine‘ tar, 4.5 parts of stearic acid, and 14 partsot a 50 divided hydrogen-containing carbon black with 30% aqueous solution of‘ sodium hydroxide. This a gaseous halogen at a temperature and for a mix had a viscosity’oi 116. A parallelgmix con time su?lcientto produce about 4% of hydrogen taining untreated carbon black would be so hard halide adsorbed on the black. as to be substantially non-plastic. . 7. A‘ carbon black derlved'trom hydrogen-con By the present invention there may’ be pre pared a new type 01- carbon black which, when 55 taining carbon black and having about 4% hy drogen halide adsorbed on the black. '‘ compared to the conventional type of channel '8. A process which comprises submitting chan black, gives a mix with rubber of abnormally low viscosity and electrical conductivity. together ‘- nel black to the action of chlorine for a time and at a temperature su?icient to leave a _chlo-~ ’ with a vulcanlzate having abnormally low hysteresis. Carbon blacks or the color grades 60 rlne content of more than about 1% on the prepared according to thev present invention may I also be used to give inlrsand lacquers oi greater . ?uidity than do conventional carbon pigments. treated black. - ' - ' g HUGH 1d. EMAIL-WOOD.