Патент USA US2411840код для вставки
Nov. .26, 1946. v w. c. CALVERT COMPOUNDING RUBBER HYDROHALIDES, ETC. Original Filed March 26, 1957 2,41 1,840 ~~ 2,411,840’ Patented Nov. 26, 1946 7 UMrEojsTATEs ' PATENT tj'VjfO-FEI’CE ~ . ooMeoUNmNG ‘RUBBER Hypno - - @HALmEsE'ro. - ~ :William 0. Calvert, Gary, ‘Ind, assignor to Wingfoot Corporation, Wilmington, Del., and Akron, Ghio, a'corporation of Delaware Griginal application March 26, 1937, Serial No. 133,172. vDivided and this application August 2, 1946, Serial No. 587,897 4 Claims. ' ' 1 I (Cl. 260F738) 7 rubber hydrohalides', viz. rubber hydrochlorides, rubber hydrobromides' and rubber hydroiodides, and the treatment of resulting rubber hydrohalide compositions. The invention will be described more particularly as applied to the treatment of rubber hydrochlorides. ' 2 at the times and temperatures indicated as “time . 1n minutes”/“degrees Fahrenheit.” . 20/26‘0.__‘______> ____ _____,____.___; 10‘parts MgO " ' In milling and molding and otherwise treating rubber hydrohalides such as rubber hydrochloride . .20/260_.____,___p__‘ , . 20/260,____‘__(____ _ I gv__ 10 vparts CaO ___ 10 parts PbO . 29/260,____ _‘__._‘__\_________'____7_,20 parts CaO .'60/260 _________ __,__: _______ __' 20 parts QaO When the mechanical manipulation of the rubber hydrochloride is carried‘out at an elevated tem perature it has been found that in many oper . 20/260___,T______ ' __ 20 parts MgO ' g 20 partsMeo -.-__ 3.0 parts CaO - Bil/2th-.-. - ?ll/2'15"," ations the admixture of a basic material with the rubber'hydrochloride gives improved results. For example, in milling and then molding vrubber ' The following materials were milled into 100 parts of rubber hydrochloride and then molded This invention relates to the compounding of - sci/260-. 15 hydrochloride it has been found that the addi .__.- 30 parts 0.69 _ i ,- 30 parts'Mgo . 60/275 ____________________ __, 30 parts vlvlgo was foundthat these compositions could be milled under conditions of times and temperatures‘ It tion of inorganic basic materials such as lime and magnesia,etc. give improved products.’ Theuse which would cause evolution of hydrogen chlo of: bases ‘such as hex'amethylene tetramine ‘and diphenyl guanidine has likewise beeniound ad; ride rgfrom rubber hydrochloride containing no basic material. Other compositions satisfactorihr homogeneouslymilled together and then molded vantageous. > For certain operations it'has been found desirable to compound with the rubber hydrochloride and basic material a .plasticizing material such as rubber or other softener. Pig. 12. 60/220—11 parts vulcanizable rubber stock ments may be milled into the rubber hydrochlo~~ 25 13. 60/220..—11 parts vulcanizable rubber stoc ride where colored products are desired. plus 25 parts gas black > are: - This invention relates more particularly to the compounding ofv basic materials with rubber hy drohalides by milling and the molding and calen dering of compositions comprising rubber hydro 30 halides and basic materials." “But it is to’ beun derstood that it'is not essential to incorporate basic materials with.‘rubberihydrohalides for all such operations. For example, rubber hydrochlo ride may be satisfactorily milled perature in the absence of basic those instances where the use of rial is desirable the amount of i v 14. 60/220-1'1 parts vulcanizable rubber stock plus 2- parts diphenyl guanidine plus 25 parts gas ‘black . 20/220—2 parts diphenyl, guanidine . 20/220-25 parts gas black ~ ' ~ . ‘20/220,—l-2~parts diphenyl guanidine plus 25 1 parts ‘gas black ‘ . 20/260-5-5 parts‘ hexamethylene tetramine . 20/260—.10»parts Ivory soap at a lowv tem materials.‘ In a basic'mate-y‘ basic material . 60/260-20 parts CaO plus 10 parts cumar . .60/260-1-20 par-ts CaO plus 10_ parts mineral required .for'entirely satisfactory ‘results depends upon the temperature employed, the length of‘ time during which the rubber *h'ydrochlorideis subjected to the temperature;etc.v For example, . -6D/26.0—:20 parts CaO ' plus '10. parts factice . 610/260-—.20 parts ,CaO plus 10 parts coal tar .- 60/:260-20 parts CaO plus ‘5 parts hexameth . ' 116.116 tetramine . 160/275-4211 narisiGaQp‘lus 5 parts hexameth in‘v molding a mixture consisting of rubber’ hy drochloride and an inorganic basiomaterial such as-CaO,'MgO or PM). it has been .found rm general that 10 parts of one of the above ‘bases . 60/260-20 parts CaO plus 20 parts gas black . ‘60/275—20 parts CaO plus 20 parts gas black and 100 parts of rubber‘hydrochloride- can'be . 60/-260+—,2.0 parts Meoxplus 5 par-ts hcxameth satisfactorily molded or curedy'a's a thin slab for 20 minutes at 260° F.; Whereas 20 parts of the base was preferred for 60‘minutes molding at this-11cm‘ perature’a'nd 30 parts for 69 minutes molding at‘, 275° F. Molding at such higher temperatures? caused'blowing on uncornpounded rubber hydro-4‘. chloride etc. - ; rlene tetra-mine ' ~ylene ‘tetrami-ne . 6il/27'5-e-20 parts 1Mgo plus‘5 parts heXameth-~ 50. ;y-1ene tetramine - . 30. '60/26'0-—2_0 parts MgO plus '20 parts gas black ' The vulcanizable rubber stock of Examples l2, l3 and 14 was composed of 100 parts ‘rubber; and in certain instances caused pitting;v ' 1 part mercaptobenzothiazole, 1 part stearic acid, 55 5 partsizinc voxide and 3 parts sulfur; 2,411,840 3 4 gen chloride over that theoretically required by 31. Somewhat over 1.5 parts glyceryl butyl phthalate were incorporated in 100 parts rubber hydrochloride on a cold mill. By incorporating 10 parts of pale crepe rubber (about 400 plas the empirical formula (C5H9C1) z. The introduc tion of hydrogen chloride is then discontinued and the reaction of the hydrogen chloride with the cement is allowed to progress ,until a washed and dried sample indicates that 29 to 30.5% of ticity) on a cold mill a product less tough than that containing no rubber was obtained; Four parts of diphenyl guanidine was incorporated into the rubber hydrochloride-glyceryl butyl . chlorine is combined with the rubber. Generally the time required is about 20 hours. The reac tion mixture is then steam distilled to remove phthalate mixture on a hot mill. Each of these products was quite ?exible. A sheet of the last 10 the benzene and the excess hydrogen chloride. The resulting mass is broken up on a rubber composition was pressed into felt at 240° F. using Washer and washed thoroughly and dried in a 4000 and 9000 pounds pressure. The rubber hy vacuum at approximately 160° F. The rubber drochloride was pressed almost completely into the felt with the latter pressure. ' 32. A dark red sheet was obtained by com hydrochloride is then dissolved in chloroform or 16 dichlorethylene in the ratio of about one part rubber hydrochloride to twenty parts of the solvent. The ageing properties of the ?lm may pounding two parts diphenyl guanidine and 0.3 part Oil Red 3B (American Aniline Company) on a hot mill. be improved by adding a small amount of an This Was pressed into felt at antioxidant. Hexamethylene tetramine and satisfactory product was obtained by pressing into 20 methylene amino aceto nitrile are effective for 240° F. using 2500 and 6000 pounds pressure. A this purpose. Where a colorless transparent ?lm is desired it is advantageous to use 3% of ditetra hydro furfuryl amine or dicycle hexyl amine with guanidine, 0.1 part Oil Red 3B and 60 parts 11/2% of hexamethylene tetramine. The anti rubber hydrochloride on a hot mill. The best 26 oxidant is dissolved in the solvent with the washed results are obtained by heating both plates. felt at 240° F. with 2500 pounds pressure a com position obtained by sheeting 1.2 parts diphenyl reaction mass. ~ 33. A good sheet was obtained by milling 1.2 The invention will be further explained in con nection with the drawing, in which hydrochloride and then molding in a press at Fig. l is a plan of apparatus showing one 240° F., heating 5 minutes before applying the 30 method of manufacturing the sheets of this in full pressure of 2500 pounds. vention. 34. Fifteen parts butyl stearate was milled into Fig. 2 shows a frosted sheet with a clear win 124 parts rubber hydrochloride and a sheet formed dow. on the mill was then pressed into felt at 240° F. Fig. 3 shows a method of modifying a perfectly using 2500 pounds pressure. The rubber hydro chloride was quite soft after pressing but hard 35 smooth sheet. Fig. 4 shows a sheet with a protuberance there ened on standing. ' in; and 35. One part pale crepe rubber (400 plasticity) parts diphenyl guanidine into 60 parts rubber Fig. 5 shows apparatus for calendering or was milled into ?ve parts rubber hydrochloride. smoothing out a ?lm of rubber hydrochloride, as A sheet of this was pressed into felt at 240° F. using 2000 pounds pressure. There was prac 40 explained below. In making a ?lm for wrapping purposes from tically no indication of rubber hydrochloride a rubber hydrochloride solution such as described decomposition. A light coat of triethanol amine the material may be run onto a continuous belt in stearate was used on the press without detri such an amount as to produce a ?lm about 1/1000 mental effect. ’ 36. Rubber hydrochloride was sheeted out on 45 of an inch thick after the solvent has been evap orated. Heat is applied and the solvent is evap the mill at such a temperature that there was orated slowly without boiling. A clear transpar some‘ evidence of decomposition. This was then ent ?lm results. Irregularities in the under sur-‘ pressed to felt at 260° F. and 280° F. using 2500 face of the ?lm are produced by using a belt I pounds pressure without evidence of further de composition. 50 having complementary irregularities in its sur 37. On pressing rubber hydrochloride to felt at elevated temperatures which caused darkening of the rubber hydrochloride it was found that the addition of ?ve parts hexamethylene tetramine per 100 parts rubber hydrochloride reduced or 55 face. If a certain area of the ?lm is to be de pressed, that portion of the belt on which this area of the ?lm is formed will be raised or a form of suitable shape may be fastened to the belt. If a portion of the ?lm is to be raised to produce an embossed e?ect, the portion of the belt on prevented darkening. which it is formed will be depressed. If a very ' This invention also contemplates the trans thin ?lm is produced, the variations in vthickness formation of perfectly ?at sheets of rubber hydro are preferably kept at a minimum to prevent dis chloride into sheets one or both surfaces of which are irregular. By this transformation the thick 60 tortion of the ?lm in drying. If a thicker sheet is to be formed somewhat greater Variations in mess of the ?lm in certain areas may be decreased thickness are possible without causing distor or increased, or a limited area of the sheet may tion of the sheet. The raised or depressed por be stretched to a desired size and shape. The tions may constitute a trade-mark or other de rubber hydrochloride may be formed in the fol 65 sign which may be merely for decorative purposes lowing way. or they may comprise printed matter or may be Twenty pounds of plasticized pale crepe rubber used for any other purpose. are dissolved in 313 pounds of benzene, giving a In Fig. 1 the apparatus for forming a sheet is rubber cement of approximately 6% concentra shown as comprising two rollers, 5 and 6, ‘over tion. The cement is cooled to about 10° C. and hydrogen chloride gas is introduced into it while 70 which a belt ‘I is passed. A rubber hydrochloride solution is supplied to the belt through the pipe, it is vigorously agitated. After about six hours 8 and a perforated header 9. The belt travels the increase in weight of the composition due in the direction of the arrow. The rubber hy to the introduction of hydrogen chloride gas drochloride solution after being applied to the should be approximately 11.6 pounds which cor responds to a slight excess of available hydro-' 75 belt is passed under the scraper or knife I0 to 2,411,840 5 , form :a .very thin ?lm, and the guides I i are pro. vided to prevent the excess of ‘the ?lm from run. ning over the edges of the belt. The belt and tuberances of large area and varying depth may be formed by stretching a limited area of a sheet of the rubber hydrochloride. Where a consider able amount of stretching is required, it is prefer‘ through which'air or gas is circulated and the U1 able to apply heat before or during the stretching. solvent evaporated. After passing over the roll Such stretching may be accomplished by the er 6, and returning to the roller 5,. sui?cient gradual application of pressure between plates or solvent has been evaporated to allow the ?lm 12 rolls or in apparatus particularly designed for to be removed from the belt. The'?lm is then the purpose in which the stretching may be ef passed through further drying apparatus if nec l0 fected by the movement of one or more members essary to remove the last traces of the solvent. after the area surrounding the part to be Any desired design is formed by providing inden stretched'has been tightly clamped in place. The tations or raised areas on the ‘belt, depending upon protuberance may be shaped in a heated mold whether the design is to be embossed on or en if this is, desired. graved into the ?lm. The drawing shows diamond 15 If the sheet is to be stretched to any consider shaped depressions l3 in the belt which produce able extent, this may be advantageously accom raised areas M on the ?nished ?lm. plished by treatment of the sheet during its for— By pebbling or cross-hatching, a frosted effect mation, before all of the solvent has been evap may be produced. By frosting only a portion of orated from it. For instance, in the manufac the surface and leaving another portion un 20 ture of the rubber hydrochloride ?lm from a solu frosted a ?lm is formed which when used for tion of chloroform, after evaporating mostof the wrapping directs attention to that portion of the solvent, for example when the solvent content has wrapped package which isseen through the un been reduced to about 10%, certain areasmay be frosted portion. Fig. 2 shows a section of the ?lm stretched vto form desired protuberances, partic 20 which is frosted over its entire surface except ularly if the stretching is effected while the film for the clear window 2! which may be made of is still Warm. The balance of the solvent may any shape desired. Various novel'eifects in Wrap then be evaporated. ' ping ?lms may be produced by forming a ?lm If considerable stretching is required to form. on a belt having an irregular surface. the desired‘ protuberance, the portionof the sheet Instead of forming films of irregular thick which is to be stretched may be made somewhat ness in this way a perfectly uniform sheet of the thicker than the surrounding portion by form rubber hydrochloride may ?rst be formed on a ing it on a belt with depressed areas to give the belt having a perfectly smooth surface and this desired thickness at the required portions of the may be after-treated to produce the effects de sired. The rubber hydrochloride is thermoplastic Although the invention relates more partic and while still warm from the process of manu ularly to the manufacture of transparent ?lms, facture or by heating, if necessary, the surface it includes sheets of greater thickness and sheets rollers are preferably enclosed in a chamber ?lm. may be altered as desired and certain alterations in the surface may be made at room temperature by the proper application of pressure; The un saturated hydrochloride produced in the manner above described is slightly extensible and can be marked by stamping without destroying its tex ture and waterproo?ng‘ properties. Although stamping at room temperature produces some effect on a sheet or ?lm, it is preferable to stamp in a press heated to 80—85° C. for example, or to - which are not transparent. . ‘ Colored sheets may be formed by'the addition of dyestuffs. The‘invention also contemplates spreading a solution of‘ rubberhyd'rochlo'ride ‘in a volatile sol ' vent on a suitable surface and after evaporating solvent from the exposed surface subjecting it to a “smoothing out” operation. This smoothing out is preferably effected while the ?lm still con tains a small amount of solvent and then the balance of the solvent is evaporated. ?rst heat the sheet and then stamp it. Where The ?lm may advantageously contain between depressed or raised areas of large dimension are 5 and 15% by Weight of solvent when subjected to be formed, the sheet should be heated until it 50 to the smoothing out operation to remove irreg softens somewhat. The sheet may also be marked ularities from the surface. For example, to pro by passing it through rolls, after ?rst passing it duce a ?lm of high transparency from rubber through heated rolls if necessary. Fig. 3 shows hydrochloride a solution of 7% of a partially sat rollers 30 and 3|. The upper roller 30 is pro urated rubber hydrochloride (for example, rub vided with raised lines or ridges 32 which in 55 ber hydrochloride containing 29-30.5% chlorine) pressing against the smooth surface of the roller dissolved in benzene is spread out as a thin ?lm 3|’ cause depressions 33 to be formed in the ?lm on anendless smooth surfaced belt in such a Way 34. In this way lines may be pressed into one or as to produce a continuous ?lm. The benzene both of the surfaces or ridges may be raised on one is allowed to evaporate, preferably with a forced or both surfaces. Any desired portion of one or 60 draft, until its solvent content has been reduced both surfaces may be altered to produce an en to about 5 to 15% of the Weight of the rubber hy graved or embossed effect. drochloride. It is then passed between highly It often happens that for wrapping articles of polished pressure rolls. This removes irregulari irregular shape or for enclosing them in a pro ties in the surface of the ?lmfrom which the tective layer which comprises a part of the article 65 benzene has been volatilized. The ?lm is then itself, or for covering or protecting an inner con subjected to ‘further drying to allow evaporation sistuent of a fabricated article a sheet which is of the balance of the solvent. The highly polished not altogether flat is preferred to a perfectly ?at rolls may if desired contain some marking or sheet. For example, in wrapping a perfectly design to impress or emboss a ?gure or design square articleon which is a protruding handle, 70 upon the ?lm, but the major portion of the rolls a sheet with a protuberance shaped to ?t the han will be smoth and highly polished. A minimum dle is preferable to a perfectly ?at sheet. Fig. 4 temperature of about 150° F. is advantageously shows ?lm 4i} on which a protuberance 4| has employed and for usual operating conditions 190" been formed which is of predetermined shape. or 200° F. is preferred. Thimble-like or ?nger-like protuberances or pro 75 Various methods of smoothing out the ?lm 2,411,840 7 8 surface may be employed. For example, pressure is festooned over rollers 59 and 60. Here air cir may be applied to the ?lm before it is removed culation means (not shown) removes the balance from the surface on which it is formed as by ap of the solvent through suitable vents (not shown). The rubber hydrochloride may be made in any plying pressure to the ?lm before it is removed from the endless belt. If rollers are employed for smoothing out the surface of the ?lm it may be advantageous to use a rubber covered roll or a hard rubber roll in combination with a steel suitable way, such for example as that described in my issued Patent 1,989,632. It may advanta geously contain a stabilizer such as those there mentioned. For example, it may contain about one per cent of hexamethylene tetramine. Films roll, with the steel roll contacting with the sur face of the ?lm from which solvent has been 10 of any thickness may be prepared, which may be .005 to .002 inch thick, or thinner or thicker as evaporated, because of the di?iculty in obtaining described in said patent. two steel rolls with surfaces of the exact uni From the above it is seen that rubber hydro formity required to calender a ?lm with a thick chloride can be compounded with a variety of in ness of the order of a thousandth of an inch. By using a roll with a resilient surface in com 15 gredients and utilized in many ways. It can be molded to fabrics, etc. It can be molded into all bination with a steel roll any deviations from sorts of shapes for use in the manufacture of uniformity in the surface of the steel roll are com electrical instruments and a, multitude of other pensated by the resilient roll and uniform pres articles now made from other plastics. sure on the ?lm is obtained. This application is a division of application .The invention is illustrated diagrammatically Serial No. 133,172, ?led March 26, 1937, which is in Fig. 5 of the accompanying drawing. The in part a continuation of my applications 682,116,‘ coated belt is indicated by numeral 5|. The hood ?led July 25, 1933, and 102,225, ?led September 52 is provided to carry off vapors of the solvent 23, 1936, which latter is in part a continuation of from the chamber enclosing the ?lm. The solu my application 2,843, ?led January 22, 1935. tion of rubber hydrochloride is fed onto the belt I claim: through suitable means attached to the feed pipe 1. A composition of matter comprising a rub ' 53. A spreader or scraper to regulate the thick her hydrohalide and litharge. ness of the film is indicated at 54. The ?lm 55 2. A plastic composition comprising as an es after the majority of the solvent has been evap sential ingredient a rubber hydrochloride inti orated is passed through the pressure rolls 56 and mately admixed with a minor proportion of a 51. The roll 58 is a steel roll. The roll 51 is pref solid lead compound. erably covered with rubber or other resilient ma 3. A plastic composition comprising as an es terial. The upper surface of the ?lm from which sential ingredient a rubber hydrochloride inti solvent has evaporated contacts with the pres sure roll 56. It is somewhat irregular as the film 35 mately admixed with a minor proportion of lead oxide. enters between the rolls 56 and 51, but the highly 4. A plastic composition comprising as an es polished surface of the roll 56 smooths out ir sential ingredient a rubber hydrochloride inti regularities present in the surface of the partially mately admixed with a minor proportion of formed ?lm, From these rolls the ?lm passes through further drying means of suitable design 40 litharge. here indicated by the drier 58 in which the ?lm WILLIAM C. CALVERT.