1,906,942 5 ral rubber, gutia percha, bala-ta, syntlietic rtibber, or other rubber-like materials. With the detailed descriptioli given above, i-,L wili be obvious that modifications will stig-' gest tliemselves -",itho-Lit departino- from 'uhe prlp-c,-Ple of t-h-, inA,-ention, for example the proctu@l-l@t resul-'Liiig from the re.-tetion of a heto.-le aii aromttic amin-o compolind may also be pi@edared by reacting'che correspond10 ing thioke@oie or the corresponding ketone dihalide with 'uhe amiiio coliipound, aiid it is not desired to limit th-einventio,,i other-wi-se ,@-han as set f orth in the appended claims. -T-laving thus descri@,@e,-l iily ii-ivontioii, what 15 I claiin and desire to protect by Letters Pateiit is: 1. The method of treating rtibber which coiiiprises trea'iii(y rubber - @iith an aldehyde derivative of the"reactioii product of ,i, ke20 toiie and aii aromatic amilne. 2. The me@hod of treatino@ rubber Avhicl)- comprises 'u-reatin- rubber with an aldehyde ?n derivative of the reaction product of an alipliat-'Le -IL@-e@@o-,ie a-,id aii aroliiatic amine. 25 3. The riethod of tretting rubber which coinpi-ises 'Lregtliig rubber -witl-i an aldehyde der-'Lvative of the reaction procluct of a ketone alnd a-.i aromatic moiioamine. 4. The inethocl of treating rtibber whiell 30 coiiiprises treatiiig i;ubber witli an ald-ehyde clerivative o'L the reaction product of an aliphatic ketone and aii aroiiiatic monoamine. 5. The me'Lhod of treating rubber ivhich 35 @om-pi-ises 'Ureatino- i-tibber wi-th ail aldehyde cleriv,lt,ive of the reaction product of acetoiie ai-id aii aromatic amiiie. 6. The me'uhocl oT- tre,,iting rubber Nvhicli, coi-npr;lses tre,,ttiiig rubber with an aldehyde 40 derivative of the react . ion product of an alip'jiati-c ketone and a primary aromatic amine. 7. The method of treating rubber which coiliprises treating rubber with an aldehyde derivative of tl-ie reaction product of an aliphati-c I-etone and a primary aromatic mono45 am,ne. S. The method of treating rubber which comprises treating rubber with an aldehyde derivative of ti-ie reaction prod7Liet of acetone 50 and a primary aromatic amine. 9. The method of treating rtibber whieb comprises treating rtibber with an aldehyde deriv,ttive of the reaction product of acetone aiid an aromatic monoamine. 55 10. The method of treating rubber wl-iieh comprises treating rubber -with an aldehyde clerivative of the reaction prod-Liet of acetone and ,t primary aromatic monoamine. 11. The metl-iod of treating rubber which comprises treatino: ri-ibber with a formalde60 11 hyde derivative of the reaction product of acetone ,tnd a -primary aromatic amine. 13. The method of treating rubber which comprises @ui,eatino, rubber -vvith a formaldehyde derivative o@f the reactio-p- product of acetone and a primary aromatic nionoamiiie. 14. The method ol treating rtibber which 70 compri ses treating rubbei, Nvitli a formaldehyde derivative of the react-loii procluct of acetone and aniline. 15. Rtibber derivecl from rubber containing tn aldehvde derivative of the reaction 75 pi-oeluct of a !Ketoi-ie and an aromatic amine. 16. Viileaiiized rubber derived from rubber contaiiiing an aldehyde derivative of the reaction produ-,t of a ketone ,tnd an aromatic amine. 80 17. A vuletnized rubber product contaiiiing rubber which has been vulcanized in the presence of an aldehyde derivative of the reaction product of a ketone ai-id an aromatic monoamin e. 85 18. A vulc,-,nized rubber prod-Liet coiataiiiing rtibber which has been vulcanized in the presence o'L an aidehyde clerivative of the reaction product of an ali-phatic ketone and an aromatic monoamine. 90 19. A vulcaiiized rubber product containing rubber -,vhich has been vulcanized in the presence of an aldehyde derivative of the reaction procluct of acetone Ind In aroma@Lic amine. 95 20. A vulcanized rubber product containing rubber which has been vulcanized in the presence of an aldehyde derivative of the rea(,,tion prodliet of an aliphat ic ketone and a Primary aromatic amine. 100 21. A vulcanized rubber product containing rubber -which has been vulcanizecl in the presence of an aldehycle clerivative of 'Uhe reaction product of an aliphatic ketone a-nd a primary aromatic monoamiiie. 105 9@2. A v-Lil-canized rubber product containing rubber which has b-len vtilcanized in the presence of an aldehyde derivative of the reaction. product of acetone and a primary aro110 matic amine. 23. A vulcanized rubber product contaiiiing rubber which has beei-i vulcanized in the presence of an aldehyde derivative of the reactio-,i o'L acetoiie and an aromatic mono- 115 ainine. . 24. A vulcanized rubber product containing rubber which has been vulcanized in the presence of a formaldehyde derivative of the reaction product of acetone and a primary 120 aromatic amine. 25. A vulcanized rubber product contctinin(-, rubber whieb has beeii vii.lc,,tiiized iii the presence of a forinaldehyde derivative of the reac@Llion prodtict o'L acetone and an aro125 matic monoamine. 26. A vtilcanized rlibber product contain19-. The method of tre-,tting rubber which ng rubber which has been villeanizecl in tl-le comprises treating r-Libber with i formaldepresence of a formaldehyde derivative of the 65 hyde derivative of the reaction product of reaction product of acetone and aniline. i3ci acetone and an aromatic monoamine. 2 7. A method of improving the properties

6 1,906,942 of rubber compositions which comprises adding thereto the condensatioli product oj' formaldehyde and an aliphatic ketoneprimary aromatic amine reaction product, and vul5 canizin- the rubber. 28. Imethod of irnproving @he properties of rlibber which comprises incorporating therewitli the reaction product of an alil)hatic aldehyde and a ketone-aromatic amin@ reac10 tion product. 29. A metliod of iniproving the properties of rtibber Nvhich coniprises incorporatinozn therewith the reaction product of an aliphatic ,tldehyde and a dialkyl ketolic-aroiiiat-i-c 15 mono-amme re-,ction product. 30. A method of irnproving the properties of rubber ivhich comprises incorporatina therewith the reaction product of an alil3hatic aldehyde aiid a dialkyl ketone-arom,,ltic 20- mono-amine reaction prod-Lict. Sig.ned at Moittelair, county of Essex, State of New Jersey, this IStli day of September, 1931. WILLIAM P. TET,@ HORST. 25 30 35 40 45 50 50 60

Patented Pilay 2, 1933 199069942 UNITED STATE@.S PATEN'I' OFFICE WILLT @-AM P. TER F-ORQT, OF PACKA11TACK LAKE, NEW jE-@ISEY, ASSICT1\TOR TO THE NAUGATUCR Cl-lElVIICAL COY-FANY, OF NAUGATUCE, CONNECTICUT, A CORPORATION OF CONNECTICUT TREATIVIENT OF --RUBBER No Dra@wi-ng. Appl-"cation fled Septey-tiber 24,1931. @oerial No. 564,930. This invention relates to the i'retitinent ofrubber and similar n-iater-i,-.1s, more pt),rtictilarly to a treatment of the s,,tme inith aii hyde cleriv,,ttive of the re-,CtiOD. DI'Ocluct of s a and rtn ,iromatic aiiiine or an-iino coi-npounct. The inVe,14- o--q al o rela'es to the @i s t prodticts of such tre,@itmei-it. This case is a coiiti-ii-Liation-in-i),@trt of cas..Seri,il No. 411,665, -iil.ed December 4, 1929. 'd 10 An object ol this invent'op, is t6 provi -e inaterials haviig the property o-'I' ret,@,rding the deterioration of riibbei-. Ot@lier ob@ects will L-e app--rent from the f ollonviiig detailed description. 15 Examples of rea,-tion prod@,icts of ke'uones ,ind aromatic airi--T)o com7Dou-.ids of -,-@,hich the P,Idehyde deriv,,itives form 'ulie subject n-i,,itter of @lhis ;,-iveiitlo-,,i:-acetoiieaniline, teetone20 phenvl metlia.-ie, acetone-dil@llei,-y.iai-riine, ac--- IV tone "--Iipi-ienyl formamicline, eSit3TI Ox;deani-line, diacetoiie tlcohol-aiiilirie. acetone.diphenyl loet,,t-- iaphthyl-,imiae, ,tee@one-alpha naphthylamine, acetopheT-ioiie-a,li@l.ine, cyclo25 hexanone-,inil-iiie, formaldehyde acetone coiidensalt-lion product-a,niline, n-iesityl oxideplienl,l betp, iiaphthviamine, acetone-'Uril@-henyl acetoiie - diortlio - tolyl g -Liaiiidlic,, guanidi.,@e, 30 tee'uone-,o,p'-cli(-,ia,)hthvlii-iiino) C-,i.p,i-,nyl met!-iap,e, acelu-o-ne-ethyl ,LniliDe, tetrtirethvl cli,i,mieto be@izophenone-f-@iiilille, q ,,Cetol-le-ol-tho-'Lolyl biguani-de, tcctolle-dipl-ienyl Oi@-ie'. y' ii-vl -'i@@etoiie-i) -P'-di35 @mil.@.0 cliph-,--yl inethfiiie, eti-Lyl,-Idene-,@teetoiiei-mino ,iceton P.-Iiy,tiire cf beta i,@,,tl,)bthc,!, icetone-mixtii.--- of phei-iol ,nd 40 c , ,icid co@id.-,nstte). phenyl liydrazine,, acetone diIllustrative of the invention is the treati-iient of riibber with stieli -.Idehyde, derivatives of ketones and a.romq@tic tinincr compotinds as-reaction -product of f ornaalclehyde aiicl acetone-aniline, react-Ion product 45 of formaldehyde and chloracetone-anili ne. Instc,,td of the ketoiies mentioned above tlie, following iiiay be Lised: phorone, diethyl ketone, benzo phenon-,, acetop,ienone, clichlor -one, aldol acetone, allyl-acetone, bedzal r'O ace', :?.cei'lone, @-liacetyl, acetyl-acetojie, ace'Lonylaco't-o-r@e, solicylaldel-iyde-acet6ne, furfurallcetone. Instetd of the aromatictinino ccmpolinds menti-o-.ied above there may be used mono-chloroaiiiline, ortl-io-toliii-diiie, Rlett 55. toluidine, p-,ira-toluidine, xylidines, alphanap,ithvlan-iine, beta naplithylamine, amino diphenyl, Oinaphtllylamines, asymmetric diphenyl hycirazine, di-aiiiiiio cliphenyl siilpliicle, dia,-iiino dii@,iae-Tlyl polysii,.ph-l@ies, di60 d,.naphthyl siilpliides, p-amino benzyl-anilip-e, dinaphthyl clian-iino e'thtne, ditolyl di-imino et]-iane, p-, tmino-p'naphtliylan-iit-io cliphenyl me,-hane, p,p'-diamino diphenyl dimethyl methane, p,p'-di(iiaphthyl(35 amino) diphenyl dimethyl, metllan-, syind.@lphenyl p-pho--Llylene diamine, symdinaphthyl p-phenylene diamitie, phenyl beta naphthvi gua-,qi-di-ne, ))Iieiiyl.o-'to-13TI giiaridine, dio-tolyl biguatiicle, monopheliyl biguaiiide, 70 d;.PheT-ivl bigii,,iniJo, cliphenyl acetai-aid4l.ne. The -folloi77irg ai-e to be -uinderstood as ilItistrative embodimeT-i'@,s of the invent on and iiot '@iiiiitiiig thereof: Exa??,@,7)7e !.-This type represents aldeli@Tde re,,tetion procliiets of qcetone-amines. A-ectone-piniiies ilsiially cir-.- liquids and the ,.Iclel-.vde derivatives Lisii,-Ily qre solid compolincis. As example, an excess of 36@'o 80 ,@,qiieoiis formaldehyde soliition is added to

2 1,906,942 the acetoiie-aniline reacti-on products, aricl eiiotigli hydrochloric aci-d is aclcled to cause an acild r(,,ac-',ion to litmiis P,)-rer. The miit,,ire is warmed to -,')O' C., at ivhich temperature a, reactioii suddeiily stqrts. The tei-tiperat-Lire is l@:ei)t -,'u 700 C. cli-iripcf 30 miiiute@@ ,ii-icl tlie br;lttle product ivhich is ol)taii'led OTI cooliiig is orro-Lind to a browti po-wder. Th. iii,iterial is teste(i in the saiiie manner as d--- 10 seribecl -tL-ove. The results ,,re as folio-wsReactio2t pi-oditot of fori)zaldelbyde o7i, acetoito-aitilii?,e. +reacGreen tensiles Blank tioli 15 prodile t - Cure 50' at 45# --------------------------------- 4215 4210 Cure 601 at 45# --------------------------------- 4205 3315 Cure 75' it 45'@ --------------------------------- 4315 4025 C. re W at 45# --------------------------------- 4175 4235 20 Aged 168 hrs. in oxygen Cu.re 601 at 45# --------------------------------- 1255 2260 Cure 60' at 45# --------------------------------- 1345 1930 C.e 751 at 45# --------------------------------- 1185 1820 Cure 90' at 45# --------------------------------- 1360 2210 25 - Instead of formaldehyde otlier al(lehydes m,ty be tised sucli as aldol, butyraldehyde, croton aldel-@yde, heptaldehyde. E-ea,n?,ple @O.-To 115.5 (yrams of tl-ie reac3 0 tion product of acetone WTid diphenylainine are added 102.5 - rams of 407o aqueous formaldehyde solutioii and two drops of conceiitrated hydrochloric acicl. Heat is applieci 35 lllltil a temper,,tture of approximately 55' C. is reached, at -@,-hich point an exothermic react-ion starts, causing the temperature to rise to approximately 70' C. IVI-ieii thi-s first -r-,ther violei-it reactioti is over tl-ie temperl40 ture is rtised to ,ipproximately 800 C. by external applicition of heat and kept at 800 C. dilirin(y 6 hours. The water formed d-Lirinc, the condeiisation is then pourecl off and the form,,ildehyde re,,iction product is - washed, 1-5 dried, ilicl (yround. The procluct obt,,tined is tested in carbon bl,,tcl@ stocl@s in -wh;.ch diphenyl gilanidine is iised as the acceler,-tor. Two mixes were mtde -Lil), oiie coritainirl@Z 50 no antioxidant, ct,lled tl@e' blanli:, and anotl-ier one contiiiiiiag my form,,ildehyde acetone-diphenylamine conde I iisation product. 1.5 Greeii tensiles lbs./sq. in. Blaiak a 55 oxidi -- Cure 601 at 45@- 4690 4423 Cure 751 at 45# ------------------------------------ 4497 4713 Aged tensiles 168 hrs. in oxygen 60 Cure 601 at 45# --------------------------------- 7.50 2175 Cure 751 at 45# ------------------------------- - 837 2167 In t trucl@ inner ttibe in -which the con6,5 clensation prodtict of butyrtldehyde aiid aniline is tised as the accelerator I obtain the 'Lollo-wilig results: Green tensiles Bl@.k 70 oxidant Cure 5' at 60- ------------ 2462 2915 Cure 10' at 6i@, 3665 3542 Aged 8 hrs. at 2451 F. 100% elong. 70 air 75 Cure 51 at 60# ---------------------------------- 189 545 CLire 10' at 60# --------------------------------- 102 346 This is a verv severe agein(I test ,ind the I 80 ,teetone-diphenylamine forn-ialdeh),de condensatioii product i-s very effective in preventiii, iiiidtie softeiiilig of the stock. t, Cured white sheet-in- s'oel@s in Niliicli - u plienyi-o-tolyl glianidine , is used as the accelerator, aiid containin(, the ae-Itoi-ie-diplie- 85 iivlaiiiine-foriiif,@ldel iydt,-'con(lensation product ,Ls tli.e aiitioxidai@i, sho-@N, less discoloratioii -vvhen exposed to sunli(yht than s-Lmil,,tr stoelks tui)ntainin(r acetone-diplien-.ylamine condensago 'u-ion prodtict as the iiitioxidant. The green and agecl tensiles for this lvhite sheeting stock are givei-i belo-w: + ' p alr@ @ f.,.a 95 Green tensiles Blank dehyde reaction product Cure 301 at 40# ------------------------------ 3125 3555 Cure 451 at 401@ ------------------------------ 3598 2947 100 Aged 168 hrs. iii oxygen Cure 30' at 40# --- ----------------------- --- 1SG2 2640 Cure 451 at 40# ------------------------------ Too poor 1910 to test. 105 A rubbeir tilino, stocl@ containincy .06@'o o I' the fornialdehycce derivati-ve of a'cetone-di-Dhenylaniine re,@tetioii product is vulcanized for IS rnini-ites at 60 lbs. sL-e,,iin pressure. A s,@imple of the stock is then subjected to oxy- 'lo -en at 600 C. an(I at a pi-essure of 300 lbs. per sq. in. The sample f ails after 240 hotir.,@, iihereas a similar s4uock containincr no antioxidant fails in 24 hotirs. Sami@ies of the 115 cured stocli:s are a'so exposed to brigl-it sunL ligiitfortwoweeks. Thesamplecontaiiiinthe antioxiclaiit is found to be discolorecl n@o' iiiore th,.in the blank stock. Example 3@In a second preparation of the acetone diphenlyamiiie-formaldehyde 120 condensatio,,i product,,t much smaller,,tii-iouiit of f orn-i'aldel-iyde is used. To 100 araiiis of acetone-dipl,envl,,tn-iip.e condensatioii I)rodvict ,@ireqdded26'(rrainstqueoiis foriiialdclivde Z-- 125 soli.,,tioii 37@'o by ivei,(r t and tivo droj)s co-,i,11 centrated hydrochloric acid. At 500 C. a reaction stiddenly s'Larts catisin- the temperattire to rise to approxii-nqtely '@OO.C. witlioli'Ll ,ipplin, tion of external heat. The temperl- 130 ture is kep'Ll at 50 to 55' C. durin.-I 15 mintites.

1,906,942 3 The, rcaotion mixture is then warmed to containidy the antioxidant is still con-ipara105" C. in orde to remove the @ng and resilietit. r , water which tively sti, was formed durinu the reaction. The prod- Example 4.-A third type of acetone di-uiet becomes soli(f on coolin- ,tnd can be phenylimine foi-maldehyde condensation ground to t reddish brown @owder. This prodi-ict is prepared simpl'y from the acetonewhic'ii has ,i, meltino- rano-e of apdii)he nylai-nine condensition product and iaaterial, n n - proxi mately 40 to 50' C. is tested in a carformal -dehy(le, omittiiig the teicl citalvst. bon black stock in which dii)henyl o-Litnidiiie To 50 (yrains of the acetone-diphenylamine is used a,s the acceler,- @tor. conde nsation product Pre added 30 grams 10 37 @'o forn-ialdehyde solution. The mass is Stocl @ heat@ ecl to 800 C. at -whiel-i teml)ei,ature a ret - 0'2 alliGreen tensfles Blank irkg I pl@rt action starts aiid proceeds rather violently. antioxiThe temperattire is kept at 900 cluring onedant h,,tl'L boiir ap-d the reac@uion mixttire is allowed 1 5 Ctire 601 at 45# -------------------------------- 4712 4537 to stand eluring 16 ho-Lirs. Tlae water wliic'h 80 Cure 75' at 45# -------------------------------- 4423 4417 f ormed diiring the reution is then poilred off a@id the reaction product is washed and Aged tonsges 168 hrs. in oxygen air-dried. A light brown resin is obtainecl. This material possesses excellent antioxidant 20 Cure 60' at 45# ------- ----------------- 1456 2736 85 Cure 761 at 45# --------------- properties , as shown bv the followinc, results: ----------------- 1495 3248 Green abrasloi2s + I part Green tensiles Blank antioxidant Cure 60' at 45# -------------------------------- 132 120 @5 Cure 761 at 45# -------------------------------- 144 139 Cu-,e 60' at 45# --------------- ----------------- 4577 4508 90 C ure 751 at 45# -------------------------------- 4600 4890 Abrasions after 168 hrs. in oxygen Aged 168 hrs. in oxygen Cure 601 at 45# -------------------------------- 71 99 Cnre 751 at 45# ------- ----------------- ------- 71 95 Care 601 at 45#- ---------- 1168 2901 95 --------------------- CLir e 751 at 45# -------------------------------- 1477 2972 The acetone-diphenylamine-formaldehyde condei-isation product was effective in ret,"dThe stockLTsed in this test is a carbon blacli: ing the loss in resistance to abrasiori of tire stock i-i)- which dipheliyl giianidine is Lisecl tread stocks. The green flex cracking valLies -ts the Pceelerator. i(O for these stocks ,tre ai-, en below: Values are Iii a trti@-k iiii-ier t-Libe this type of acetopegiven in kilocycles, @ne l@ilocycle indicating di.pl-ienylainine forn-ialdehyde condensation a complete cycle of stretchin- and bendipg, product s'iloivs -Lip very well. repeat@ed 1,000 times. Definite crackinu of the stock indicates the end point. Stock cont. 1 105 Green tensiles Blank part Number of kiloantioxicycles to cause dant failure Green fle-x cracking - 5' at 60# --------------------------------------- 2965 2880 + I part 4 5 Blank antiox3-10 id ailt Aged 8 hrs at 245' F. 100% clong. 70# air. 60' at 45# -------------------------------------- 87 121 5' at 60# ------------------------------ -------- 116 462 7 Iii @i truck inner tube in whicti -,t butyralcleEyxci7np(,e 5.-2@-cetaldol-,-@celone-diphe.,iyl115 hyde-aniliro condensation prccluct is iis-,d as im-'--ne condensatioia product. To 103.5 t'ne accelerator I obtain the f oloiving result@-, - o,,t,aiiis o:L' aceton-l-diphonylanaine condensatio, .i prodiiet and 40 grams acetalclol are + tdd ed 2 drops of concentrated hydrochloric Green tensilos Blank antioxacid. 117heii heat is applied, t reaction 120 5 ri idant stprts t'Ll i@pproxiin,-,tely 550 C., causina the Cure 51 at 60# ---------------------------------- 3995 3110 te-,iipertiture to rise to approximately 7@5'0 C. Ciire 101 at 60# -------------------------------- 3355 3397 '1-'he temper,,,ttire is kept ,it 80 to 90, C. dur- ing 6 hoiirs, The excess aldol and the water Aged 8 hrs. at 245' F. 100@' , elong. 70# air formed ditring the retictioii are removed by 1 2 clistill,,itioi-i. 114 parts of solid product are Cure 51 at 60#- @ ----------------------------- 65 444 Cure 101 at 609 -------------------------------- 65 319 ob'Lainec i - This iiiateritl is tested iii a carboll bl@,,,ck s"L-,,)clc l@l ivhl,,I-i li(@-- ,c,,,riiethi7lene'UeluAfter the above ageino- test the blaiik stoci@ rfin-iiiie fiiicl Ctiplie-nyl are used 9.s i-s very soft and gticky, where,,i,s the stock the accelerators. The stoelks are stibjec'Led to 130

4 1,906,942 ageincr ancl abrasion tests, -with the results @ng stock in which ' enyl 0-tolyl guanidine n indicated iii the following t,,Lble: Stock 5 co'at. 1.5] Green tensiles BI@.k parts antioxi dant Cure 601 at 45'@ -------------------------------- 4310 3904 C.re 76' at 45# -------------------------------- 4149 4630 10 Aged 168 hrs. in oxygeri. Cure 601 at 45# -------------------------------- 1598 3189 Cure 751 at 45# ------------------- ------------- 2026 3092 1 5 Relative wear,before ageing Cure 60' at 45# -------------------------------- 144 142 Cure 75' it 45# -------------------------------- 149 144 20 Relativo wear after ageing 168 hrs. in oxygen bomb Cure 60' at 45# -------------------------------- 87 lig Ciire 75' at 45# -------------------------------- 88 121 25 These results sho-w the acetaldol-acetonedipbenyl condensation product to be an excellent antioxidant. ,E,,Tample 6.-The butyraldehyde condenF@@,tion prodliet of acetone-diphenylamine reloWs: 100 action rodtict is prepared as fol p graiiis of butyraldehycle are added to '78 urq.ms of teetonecliphenylaiiiine re@iction I)rodtict containidg 2 drops of concentrated illtdrochloric acid, and heat is applied. -@-t 660 C. a reaction starts. The temperature is ]@ept durino- 6 holirs at approximately 60" C. 47 parts of unreacted butyraldehyde are recovered by distillation. . The reaction prodliet is @q black plastic mass. Yield, 104: crrams. This material is tested in -which hexai-iietliyleiie tetrai-iiine ,i,nd diphenyl guanidine are used ,is the accelerators. Tensile and abrasion t@ests were made before and after acrei-ng, as ibove: 4.5 + I part Greeii tensiles Blank antio-.ndant Cure 60' at 45# -------------------------------- 4177 4399 50 Cure 75' at 45# -------------------------------- 4163 4377 Aged 168 hrs. in oxygen C,ur 60'at 45' ----------- 1392 3150 C.ree 75'.t 45,; ------------ -------------------- 1360 3003 55 Relative wear before ageing Cure' 6 at 45# -------------------------------- 128 133 70, Cure 5 at 45# -------------------------------- 133 135 6(i Relative wear after ageing 168 hrs. in oxygen Cure 60' at 45@ --------------- ------------------ so 112 Ctire 751 at 45# --------------- ----------------- 84 114 65 This material when tested in a white -,heetp is'Llsed as the accelerator sho-ws the f ollowing excellent antioxidant properties: Stock 70 containing I part Green tensi]6s Blank butyraldehyde cond. prod. - 75 30' at 40# ------------------------------------ 3125 3555 451 at 40# ------------------------------------ 3598 2947 Aged tonsiles 168 hrs. in oxygen 30' at 40# ------------------------------------ 1862 2640 80 451 at 40# ------------------------------------ Too poor 1910 to test. Insteacl of the alde'ii@,des iiientioned, other ,ilclehydes may be used such is acetaldeliyde, ,85 paraldehyde, crotoiialdeli3,de, hel)taldel-ilTcle, ete. Where, the aldehyde has a lo-w boiliii(@ poiiit the reactioii liaay be carried out tindp-r rD pressure. Inste,,id of using,-t sino-le aldehyde a mixture of aldehydes may be used. The rubber also ma3, be treated -with a mixture 90 of the ,tntioxidants instead of a sijiale antioxidaiit iiiaterial. Also in prep,,Lring the lietone-amine coinpotiiids, a ii-iixture of ketones or a sino@le ketoile may be reacted ivith a 95 s'ngle an-lino compound or -with .i inix'Lliire J-1 Oi amillo CoInpounds. It is to be uncierstood that -L mixtilire of the reactioii prodiicts iiiay be iised in rtibbei, instead of a single reaction produe'. Als LI 0100 that a mixture of l@eto7ies or ,t sin-le ketone zn may be reacted with a sinale amino con-ipound or ivith a lilixture of aiiiiiao coii-ipotinds to give products that may be used iii rubber in the saiiie niinner. 105 The chemicals cliselosed iiiay be used to improve the properties as mep-iioned herein of inner tubes, tires, thread, hose, dipped goocls, mechiiiical n-oods, latex or' articles m,,ide froin 1,,ttex, etc. 110 ITi the eltims the term "Ii:etone" is to be understood as meaning or(ranic compounds containitig one or more keto (Troups zn C-C-C) 11 115 ( but coiitaining no carboxylic acid 0 \(H) 120 or ester gtoups 0 \0 and the terms "mono-aiiiine" aiid "11'10110- 125 amino" as meaning or(yanic - coiiipouiicls iii tn which there is oiily one a;i-ilino (rroii]) tncl in -which compounds there are no plieiiolic liydroxyl or pl-ienol ether groups. The term C( rubber" is to be construed @is includinu natu- 130 zn