Document 6bJDxR1qMV5G45Rd3zowkrbb1

F eb ru ary 1 1 , 1958 Mr. 3* H. S e h a e fe r E thyl G asoline Corporation P* B. Box 688 W ilm ington, Delaware D ear Mr# S c h a e fe rs The ite m m arked "O verhead" and charged to the te tra e th y l lead o p eratio n , as queried by your l e t t e r of February 7th , Is a proper and d ire c t ch arg e a g a in s t th e m a n u fa c tu rin g o p e r a tio n s . F or some tim e p a s t the DuPont Company has p a id f o r s e r v ic e s rendered In the m aintenance o f proper c o n tro l of the m anufacturing operations# This charge in clu d es the c o s t o f m e d ic a l s u p e r v is io n a t th e Dye Works P la n t and a t Baton Rouge, and also the co st of a n a ly tic a l se rv ic es In checking the ex creta of re p re se n ta tiv e em ployees. T his sum h as p r e v io u s ly b een p a id d i r e c t to me, to be ad m in istered by t o perso n ally # However, w ith the begin ning of th is y e a r, I suggested the im propriety of th is arran g em en t and r e q u e s te d t h a t th e sum be p a id t o the U n iv e r s ity in q u a r te r ly in s ta llm e n ts * The sum made a v a ila b le in t h i s way was b ased on th e c o s t o f th e p revious year* work w ith th e u n d erstan d in g th a t a t q u a rte rly in te rv a ls an accounting would be ren d ered to DuPont so t h a t they would n o t pay more or le s s than th e a c t u a l c o s t o f th e s e r v ic e s * I n a3 much as most of th is serv ice is rendered by the laboratory proper, i t seemed only f i t t i n g th a t i t should be paid in to the U n iv e r s ity th ro u g h th e u s u a l ch an n els# F or your own p riv a te in fo rm atio n , I m ight p o in t out that: DuPont is n o t making any c o n trib u tio n toward th e ex p e rim en ta l work of the lab o rato ry except to the extent th a t these an a ly ti cal data are u se fu l to us in our study of the g eneral problem# Very tru ly yours. RAKsls Robert A# Kehoe, m .d . 0000939 KF INTER-OFFICE CORRESPONDENCE Et h y i , Ga s o l i n e Co r p o r a t i o n Ma n u f a c t u r in g a n d T r a f f ic De p a r t m e n t MAIL A D D R E S S : B O X 1271 .W IL M IN G T O N , DEL.. F R E IG H T A D D R E S S : C A R N E Y S POINT. N.LI. TEL EPH O N E: PENNS G R O V E,N .J. 2 8 0 .EX TENSIO N 213. F e b ru ary 7, 1938 (P erso n al and C o n fid en tia l) D r. R o b ert A. Kehoe Dear Bob: A bout s i x m o n th s ag o you a s k e d me t o d e v e lo p th ro u g h I .G . fu rth e r inform ation on th e p aten t a p p lic a tio n f o r in tro d u cin g c e rta in a lk a li m etal flu o rid e s fo r s ta b iliz in g te tra e th y l lead and an ti-k n o ck m ixtures co n tain in g sam e, p a rtic u la rly by the m eth o d o f h e a t i n g a n d r e f l u x i n g ETHYL F l u i d o r t e t r a e t h y l ^ l e a d w ith the s ta b iliz e r . A tta c h e d i s r e p l y d a te d F e b ru a ry 1 , fro m Chemnyco In c * , New Y o r k . A p p a r e n t l y , a l o n g tim e w as r e q u i r e d f o r t h e i r r e p l y . You w i l l n o te a n o th e r a p p lic a tio n was p re s e n te d to th e U .S . P aten t o ffic e fo r the so lu tio n of the a lk a li m etal flu o rid e s in t e t r a e t h y l l e a d , o r ETHYL F l u i d , b y a common s o l v e n t , m o n o h y d ric a lc o h o ls , and more s p e c i f ic a ll y , m eth a n o l. Both a p p lic a tio n s a re under f i n a l r e je c t i o n and p ro b ab ly n o th in g of im portance w ill he o b tain e d . The f i r s t named a p p lic a tio n above c a r r ie s s t a t u to r y e x p ir a tio n p e r i o d o f F e b r u a r y 1 3 , and th e s e c o n d , M arch 1 . P le a s e w ire me a t once i f you have any fu rth e r in te r e s t. Yours tr u ly A :AB 0000940 CHSMNYC INCa 521 F ifth . Avenue New Y o rk F e b ru a ry 1, 1938 E th y l G asoline C orporation M anufacturing and T ra ffic D epartm ent Box 1271 W ilm ington, D el, A tte n tio n o f Mr. J . H. S c h a e fe r Gentlem en : About h a lf a year ago, you asked us fo r inform ation from th e I.G . F a rb e n in d u strie A k tie n g e se llsc h a ft on th e use of c e rta in a lk a li m etal flu o rid e s fo r s ta b iliz in g lead te tra e th y l and a n ti-k n o c k m ix tu re s c o n ta in in g th e same We a r e now in fo rm e d by o u r p a t e n t a t t o r n e y s , M e ssrs* H utz & J o s l i n , t h a t th e U .S . P a te n t A p p lic a tio n s S e r i a l Nos* 101 079 and 101 080 co v erin g th is in v e n tio n a re under f in a l r e j e c t i o n . A lth o u g h we a r e n o t c e r t a i n a s t o w h e th e r I oG0 F a r b e n in d u s tr ie c o n s id e r th e two a p p lic a tio n s a s com ing u n d er t h e i r l i c e n s e a g re e m e n t w i t h t h e E t h y l G .m .b .H ., we w o u ld l i k e t o d ra w y o u r a t t e n t i o n t o t h i s n a t t e r . A t t a c h e d we s e n d you a p h o to s ta t copy each of the a p p lic a tio n s s e r ia l n o s, 101 079 an d 101 0 8 0 , t o g e t h e r w i t h cme p h o t o s t a t c o p y e a c h o f t h e O f f ic e A c tio n s and amendments w hich have been f i l e d in th e s e cases# Messrs, H utz & J o s l i n comment on t h e s i t u a t i o n a s f o llo w s : " B o th c a s e s a r e u n d e r f i n a l r e j e c t i o n a n d we a r e rea so n a b ly c e rta in th a t n o th in g o f im portance can be o b tain ed i n them, by in te r v ie w in g th e A ssista n t o r P rim a ry E x am iners and a re v e ry d o u b tfu l w h e th e r a n a p p e a l would be s u c c e s s f u l. The s ta tu to r y p e rio d e x p ire s in 101,080 on F eb ru ary 13 and in 101,079 on March 1 , 1 9 3 8 ." P le a s e l e t us know w hether th e E th y l G aso lin e C orporation has any fu rth e r in te re s t in the a p p lic a tio n s. In view of th e s ta tu to ry p erio d e x p irin g v ery soon, an e a rly r e p ly would be a p p re c ia te d . Very tr u ly yo u rs, CHEMNYC0 INC. E ncls. D r . GM:S C. M ueller 0000941 \ 1 0 1 ,0 7 9 S t 3 6 5 This in v en tio n r e la te s to a p ro cess o f s ta b iliz in g lead te tr a e th y l and a n ti-k n o c k m ix tu re s c o n ta in in g th e saiae. The " a n ti-k n o c k " a g e n ts w hich have o f l a t e b een e x te n s iv e ly u sed a s a d d itio n s to m otor f u e ls and w hich c o n ta in , a s a c tiv e c o n s titu e n t, lead te tr a e th y l in adm ixture w ith o th er organic canpounds, have th e u n d e sira b le p ro p erty o f g ra d u a lly decom posing d u rin g s to ra g e , p a r t i c u l a r l y when exposed to lig h t I t has alread y been proposed to co u n teract th is tendency of lead te tra e th y l to decompose, by adding t o th e a n ti-k n o c k a g e n ts, o r th e m otor fu e ls c o n ta in in g th e sam e, w a te r-s o lu b le f lu o r id e s , and more p a r t i c u l a r l y n e u tr a l a l k a l i m etal f lu o r id e s , in extrem ely m inute doses (a few p a rts in te n thousand) These e x trem ely m inute a d d itio n s g e n e ra lly s u ffic e to p rev e n t decom position o f the le a d t e t r a e t h y l, when th e l a t t e r h as a lre a d y been added to th e m otor f u e l , sin ce the amount of a lk a li m etal flu o rid e needed to s ta b ilis e th e lea d te tr a e th y l is r e a d ily absorbed by m otor f u e ls owing to i t s b e in g s o lu b le th e r e in to an a p p re c ia b le e x te n t However, in th e case o f le a d te tr a e th y l a lo n e , o r in th e case o f th e u su a l m ix tu res o f th a t substance w ith o th e r o rg an ic su b stan ces serv in g to low er the vapour p ressu re, abso rp tio n does n o t take place to the re q u is ite e x te n t, because th e a lk a l i f lu o r id e s a re p r a c t i c a l l y in s o lu b le in le a d t e t r a e t h y l . In f a c t , when th e am ounts of a lk a li m e ta l f lu o r id e , c o n sid e re d , in accordance w ith th e form er p ro p o sa l, as s u f f ic ie n t, a re added to th e an ti-k n o ck agent i t s e l f , decom position phenomena, due to in su ffic e n t s o lu b ility of the added s ta b iliz e r , w ill n e v erth eless make t h e i r a p p e a ra n c e , d u rin g s to ra g e u n d er ex p o su re t o l i g h t , ana u ltim a te ly r e s u l t in th e m ix tu re becom ing th o ro u g h ly s p o ile d . I t h a s now b e e n a s c e r ta i n e d in a c c o rd a n c e w ith th e p r e s e n t in v e n tio n t h a t le a d te tr a e th y l can be caused to absorb th e amount of a lk a li m etal flu o rid e re q u ire d fo r i t s s ta b ilis a tio n , by adding the a lk a li m etal flu o rid e to th e lead te tr a e th y l in HE 0 0 0 0 9 42 ** 2 * * The m onohydric a lc o h o ls have been fo u n d p a r t i c u l a r l y s u ita b le f o r t h i s purpose* In th is m anner, a n ti-k n o ck ag en ts can be produced w hich b e sid e s c o n ta in in g the lead te tra e th y l in th e usual co n cen tratio n co n tain also s u ffic ie n t q u a n titie s o f th e a lk a l i m e ta l f lu o r id e n o t o n ly f o r s t a b i l i s i n g th e a n ti-k n o c k agent when added to a m otor f u e l, but a ls o fo r e n su rin g th e s t a b i l i t y o f th e a n ti-k n o ck agent by i t s e l f even d u rin g prolonged sto rag e under exposure to lig h t* For exam ple, m ix tu re s can be p rep a re d in w hich th e r a t i o of a lk a li m etal f lu o r id e i n s o lu tio n , to le a d t e t r a e t h y l exceeds te n tim es th e r a t i o a tta in a b le when the a lk a li m etal flu o rid e alone is d isso lv ed in th e lead te tra e th y l* EXAMPLE. A 1$ s o lu tio n of p o tassiu m f lu o rid e in m ethanol i s p re p a re d , and is m ixed, in th e p ro p o rtio n of 6:1 w ith the anti-knock ag en t, co n tain in g lead te tr a e th y l, known in commerce a s " E th y lf lu id " * The s o lu tio n o f th e " E th y l-flu id " i n th e a lc o h o lic , p otassium flu o rid e rem ains p e rf e c tly lim p id and fre e from sig n s of decom position, even during sto rag e under exposure to lig h t* He 0000943 -3 I claim : 1) A p ro cess fo r th e p ro d u ctio n of an an ti-k n o ck agent co n tain in g lead t e t r a e t h y l i n s ta b le fo rm which, c o m p rise s d is s o lv in g an a l k a l i m e ta l f lu o r id e in th e lead te tr a e th y l in th e presence of a substance having a so lv e n t a c tio n both on le a d te tr a e th y l and on sa id a lk a l i m eta l flu o rid e 2) A p ro cess fo r th e p roduction o f an an ti-k n o ck agent co n tain in g lead te tr a e th y l in sta b le fo m w hich com prises d is s o lv in g an a lk a li m etal flu o rid e in th e le a d t e tr a e th y l in th e p resen ce of a m onohydric alco h o l* 3) A process fo r th e p ro d u ctio n of an a n ti-k n o ck agent c o n ta in in g lead te t r a e t h y l in s ta b le form which com prises d is s o lv in g an a lk a li m eta l flu o rid e in th e le a d te tr a e th y l in th e p resen ce o f m ethanol 4) A com position of m atte r c o n ta in in g lead te tr a e th y l in s ta b le form end fu rth e r an a lk a li m etal flu o rid e and a substance having a so lv en t a c tio n both on lead te tra e th y l and on said a lk a li m etal flu o rid e 5) A c o m p o sitio n of m a tte r c o n ta in in g le a d t e t r a e t h y l in s ta b le form and f u r th e r an a lk a li m e ta l f lu o r id e and a m onohydric alco h o l 6) A co m p o sitio n of m a tte r c o n ta in in g le a d t e tr a e th y l in s ta b le form and f u r th e r an a lk a l i m etal flu o r id e and m ethanol 0000944 D partaient o f Coianerce U nited S ta te s P a te n t O ffice W ashington H utz & J o s lin , 621 F if th Ave#, New Y o rk , N. Y . A p p lic a n t: J o s e f M ,M ichel S e r, No. 101,079 F ile d S e p t, 16, 1936 For Process fo r sta b iliz in g lead te tra e th y l and a n ti knock m ixtures co n tain in g same R eferences c ite d : 1 G. Fart)* (2 sh e ets) M idgely Johns (B r.) 4 1 4 ,5 8 1 1 ,5 9 2 ,9 5 4 1 ,7 5 7 ,8 3 8 Aug, 9, 1931 J u ly 20, 19^6 May 6 , 1930 44-9*01 44-9*01 4 4 -9 ,0 1 I t i s knovjn t h a t th e a l k a l i f l u o r i d e s en h an ce th e s t a b i l i t y o f le a d e th y l a s shorn by I . G. F a rb e n in d u s trie , I t i s common t o u s e a s m a l l q u a n t i t y o f a l c o h o l t o s o l u b i l i z e t h e h alo g en compounds u s u a lly u sed w ith le a d e th y l i n g a s o lin e as shown by M idgely; a lso " a lc o h o l is co n sid ered to enhance th e e ffe c tiv e n e s s of th e l e a d e t h y l a s p o i n t e d o u t b y J o h n s , A c c o r d in g ly l e a d e t h y l i n common u se may c o n ta in a s m a ll amount o f a lc o h o l, so t h a t t h e .l e a d e th y l c o m p o s itio n o f I . G, F arb * may be r e a d a s c o n ta in in g some a lc o h o l " iu to g e th e r w ith the s ta b iliz in g a lk a li flu o rid e in view o f th ese re fe re n c e s i n d i r e c t a n ti c ip a t io n of th e c la im s '0 -- ;' ::6 5 Claim s 1 -6 a re r e je c te d a s u n p a te n ta b le o v er I , G. F a rb . ta k e n i : w ith M idgely o r Jo h n s, ex p a rte W alker 1923 C. D, 3 9 , Exam iner K 0000945 IN THE UNITED STATES PATENT OFFICE J o s e f M. M ic h e l . S e r * No* 1Q1 079 F ile d Sept* 16, 1936 F o r PROCESS FOR STABILIZING LEAD TETRAETHYL AND ANTI KNOCK MIXTURES CONTAINING SAME ) ) ) ) ) ) ) ) ) ) D iv isio n 64 . Room 4708 Hon* C om m issioner o f P a te n ts * New Y o rk , N .Y ., May 2 7 , 1937 S ir:- In re sp o n se to the O ffic e L e tte r d a te d 4 th December 1936, th e Exam iner i s req u ested to reco n sid er h is re je c tio n o f th e claim s in th is ease fo r th e fo llo w in g reasons* ^ I t i s a d m itte d t h a t B r i t i s h P a t e n t S p e c if i c a t io n No* 414 581 g e n e r a lly shows th a t th e p resen ce of a lk a li f lu o r id e s enhances th e s t a b i l i t y o f lea d e th y l* The o n ly m ethod o f in c o rp o ra tin g -s u c h f lu o r id e s in le a d e th y l d is c lo s e d in th a t p u b lic a tio n , how ever, is a mere a d d itio n of v ery sm all p ro p o rtio n s of such flu o rid e s , such p ro p o rtio n s being of th e o rd er of a few hundredths o f one percent* I t i s noted th a t l in e s 75-79 on page 1 o f th a t p a te n t o n ly su g g e st a method f o r in c o rp o ra tin g th e p ro te c tiv e flu o rid e in the f u e l co n tain in g lea d e th y l, but not in th e lead e th y l its e lf * The M id g e ly p a t e n t U*S* 1 592 9 5 4 d i s c l o s e s m i x t u r e s o f t e t r a e t h y l , t e t r a p h e n y l, t e t r a m eth y l, t e t r a am yl, or o th e r s im ila r compound of le a d , w ith v a rio u s c h lo rin e compounds ad ap ted to su p p ly c h lo rin e w hich com bines w ith th e le a d d u rin g th e com bustion to form a le a d - c h lo r id e compound (com pare l* c* page 1 , l in e s 23-32)* The p a t e n t g o e s on to s t a t e t h a t th e c o r r e s p o n d in g io d id e an d brom ide com pounds may be employed in th e p la c e o f th e c h lo rid e compounds; b u t i t rem ain s s i l e n t w ith r e s p e c t to th e l a s t and o n ly halogen compounds, v iz* th e f lu o r id e s , w hich are e s s e n tia l in th e -2 p r e s e n t c o m b in a tio n , and i t may be ta k e n t h a t i f a s im ila r e f f e c t co u ld be o b ta in e d w ith th e a id o f f lu o r id e compounds th en th e e a r l i e r in v e n to r w ould n o t have f a ile d to s t a t e t h i s . The M idgely p a te n t, on i t s f a c e , th e r e fo r e i s an im p lied sta te m e n t c o n tra ry to the su p p o sitio n b a sic to th e E xam iner's argum ent, th a t a l l halogen compounds w ith re s p e c t to the M idgely p a te n t m ust be co n sid ered eq u iv a len ts* M oreover, th e M idgely p a te n t on page 1 , lin e s 84-9 2 , s ta te s th a t a lk y l d ih a lid e compounds o f le a d and th e t r i a l k y l m onohylide compounds o f le a d are g e n e ra lly le s s so lu b le in th e u su a l m otor fu e ls th an th e t e t r a a lk y l compounds, and su g g ests t h a t a lc o h o ls may be em ployed to a s s i s t i n b le n d in g th e s e a n ti-k n o c k compounds w ith th e f u e l; t h i s acco rd in g to a p p lic a n t's view can o n ly be ta k e n a s m eaning th a t th e re i s no rea so n w hatever to em ploy a lc o h o ls i n c o n ju n c tio n w ith t e t r a a lk y l compounds. a n d th e E x a m in e r' s s t a t e m e n t t h a t " l e a d e t h y l i n common u s e may c o n t a i n a s m a ll amount o f a lc o h o l" , is th u s n o t su p p o rted by th e M idgely p a te n t. I t i s b e lie v e d th a t th e fo re g o in g argum ents e f f e c tiv e ly d isp o se of th e M idgely p a te n t as a re fe re n c e to be u sed in th e r e je c tio n of th e p re se n t claim s. As t o t h e J o h n s p a t e n t U .3 . No* 1 757 8 3 8 , i t i s n o t e d t h a t t h e s u g g e s t i o n th e re i s to econom ise th e use o f t e t r a e th y l le a d in th e doping of m otor f u e ls by adding a sm aller amount th an u su a l o f t e t r a e th y l to th e f u e l, and c o in c id e n ta lly m odify the petro leu m hydrocarbons ( i . e . the fu e l) by th e a d d itio n o f a sm all p ro - ' p o rtio n of an alcohol* The l a t t e r f e a t u r e th u s i s in s e p a r a b ly t i e d up w ith th e tre a tm e n t of th e f u e l, and the Exam iner' s assum ption th a t le a d e th y l as such w ould co n ta in a c e r ta in p ro p o rtio n of alco h o l is thus no t supported by the Johns patent* C o n sid erin g th a t fo r th e fo re g o in g reaso n s b o th th e M idgely and th e Johns p a te n ts c a n n o t be made to re a d on th e c la im s in t h i s c a s e , i t i s b e lie v e d t h a t th e r e j e c t i o n o f th e cla im s a s u n p a te n ta b le o v e r I , G. F a rb e n in d u s trie ta k e n w ith e i t h e r M idgely o r Johns i s u n ten ab le* In view of th e u n d isp u ted f a c t th a t th e s o lu b ility of a lk a li m etal flu o rid e s in te tr a e th y l lead is s u b s ta n tia lly in creased by th e presence of an alco h o l He 0 0 0 0 9 47 -3over th e s o lu b ility a tta in a b le by a mere a d d itio n of f lu o rid e s to t e t r a e th y l le a d in th e ab sen ce o f a lc o h o ls , and t h a t o n ly th e l a t t e r p ro ce d u re i s shown in B r i t i s h P a te n t S p e c ific a tio n No. 414,581, i t i s subm itted th a t th e claim s in th is case are p a te n ta b le and should th e re fo re be allo w ed . Such a c tio n i s r e s p e c tf u lly s o lic ite d # R esp ectfu lly subm itted, A ttorneys fo r A p p lican t. HP 0000948 H utz & J o s lin 521 F i f t h Ave New Y o rk , N . Ya DEPARTMENT OF COMMERCE U nited S ta te s P a ten t O ffice W ashington A p p l i c a n t : Jo M. M ic h e l 3 e r . No 1 0 1 ,0 7 9 F iled S ep t. 16, 1936 F o r PJROCESS FOR STABILISING LEAD TETRAETHYL AND ANTI-KNOCK MIXTURES CONTAINING SAMS R e sp o n siv e t o arg u m en t f i l s d May 2 8 , 1 9 3 7 . A p p lic a n t's argum ent i s n o te d . As to B r itis h 414,581 a p p lic a n t contends t h a t i n s u f f i c i e n t a l k a l i f lu o r id e s a re u se d . The d iff e re n c e i s th a t le a s le a d e th y l may have been s ta tiliz e d th a n h e r e in , hence more a l k a l i f lu o r id e m ust be added t o s t a b i l i z e t h e i n c r e a s e d q u a n t i t y o f l e a d e t h y l . The d i f f e r e n c e , c c o u r s e , i s m e r e ly one of degree. H ow ever, th e p r o p o s a l h e r e i n i s t o a d d a common s o lv e n t t o in c r e a s e th e s o lu b liz e d q u a n tity o f a l k a l i f lu o r id e s . The commonest s o lv e n t g e n e ra lly used f o r w ater s o lu b le compounds in hydrocarbonaceous liq u id s , even such as le a d t e t r a e th y l would o b v io u sly be a lc o h o l. L i t e r a l l y dozens o f p a te n ts co u ld be c ite d showing c o n v e n tio n al u s e o f a l c o h o l a s a common s o l v e n t t o i n t r o d u c e v a r i o u s d o p e s i n t o g a s o l i n e s . I t d o e s n o t appear th a t in, the p re se n t in sta n c e th e s e le c tio n o f a lc o h o l i s v ery e ffe c tiv e sin c e anhydrous a lc o h o ls a re n o t so lv e n ts f o r a lk a l i flu o rid e s Hence no p a r tic u la r s o l v e n t a d v a n ta g e i s fo u n d i n t h e u s e o f a l c o h o l h e r e i n . When t h e a l l e g e d i n v e n t i o n th e re fo re i s co n sid ered in l ig h t o f the o th e r re fe re n c e s of re c o rd , T o r exam ple, M id g ely who p ro p o se s to u se a lc o h o l to in c r e a s e th e s o l u b i l i t y o f le a d a lk y ls In g a so lin e p a r t i c u l a r l y th o se whose s o lu b ility has been im p aired by th e p rese n ces of h a lo g e n , no in v e n tio n i s fo u n d . So a ls o d o es no in v e n tio n a p p e a r o v er Jo h n s who te a c h e s th a t lea d e th y l and alc o h o l d e s ira b ly a re used in com bination in a fu el A p p lican t ^ can urge to Johns only the fu rth e r ad d itio n o f a lk a li flu o rid e s to s ta b iliz e h is lead ^ 0000949 Ser* No. 101,079 - 2- a lk y ls , b u t t h is i s a lre a d y ta u g h t by B r itis h 414,581,, A p p lica n t may urge to B r itis h 414,581 th e d e s ira b le f u rth e r a d d itio n of a lc o h o l, b u t th is is a lre a d y ta u g h t by Johns The norm al p r a c tic e s o f w hat th e a r t a lre a d y te a c h e s , su g g e sts a p p lic a n t's co m b in atio n ; hence no in v e n tio n i s p re se n t Ex p a rte W alker, 19S3, C. D. 39 S in c e a c l e a r i s s u e i s r e a c h e d , t h e c la i m s a r e a g a i n a n d FINALLY r e j e c t e d upon the referen ces as applied of rec o rd Exam iner Kg 0000950 1 0 1 ,0 8 0 S t, 364* T his in v en tio n r e la te s to a p ro cess of s ta b ilis in g lead te tr a e th y l and a n ti-k n o c k m ix tu re s c o n ta in in g th e same* ' The "an ti-k n o c k " a g e n ts which have o f l a te been e x te n s iv e ly used a s a d d itio n s to m otor f u e ls and w hich c o n ta in , a s a c tiv e c o n s titu e n t, le a d t e t r a e th y l in adm ixture w ith o th e r organic compounds, have th e u n d e sira h le p ro p e rty of g ra d u a lly decom posing d u rin g s to ra g e , p a r tic u la r ly when exposed to lig h t* I t has alread y been proposed to co u n teract th is tendency o f lead te tra e th y l to decom pose, by adding to th e a n ti-k n o ck a g e n ts, o r th e m otor fu e ls c o n ta in in g the same, w a te r-so lu b le flu o r id e s , in ex trem ely m inute doses (a few p a rts in te n th o u san d ). These ex trem ely m inute a d d itio n s g e n e ra lly s u ffic e to p rev en t decom position of th e le a d t e t r a e t h y l , when th e l a t t e r h as a lre a d y been added to th e m otor f u e l, s in c e the amount of a lk a li m etal flu o rid e needed to s ta b ilis e the le a d te tr a e th y l is re a d ily absorbed by m otor f u e ls owing to i t s b ein g s o lu b le th e r e in to an a p p re c ia b le e x te n t. However, in th e case, of lead te tr a e th y l alo n e, o r in th e case of th e usual m ixtures of th a t su b stan ce w ith o th er organic su b stan ces serv in g to low er th e vapour p re ssu re , ab so rp tio n does n o t take place to the re q u is ite e x te n t, because th e a lk a li flu o rid e s are p r a c tia lly in s o lu b le in le a d te tr a e th y l* In f a c t , when th e amounts o f a lk a l i m etal f lu o r id e , co n sid ered , in accordance w ith the form er proposal as s u ffic ie n t, are added to the a n ti-k n o ck agent i t s e l f , decom position phenomena, due to in s u f f ic ie n t s o lu b ility o f th e added s t a b i l i s e r , w i l l n e v e r th e le s s make t h e i r a p p e a ra n c e , d u rin g s to ra g e un d er exposure to l i g h t , and u ltim a te ly r e s u l t in th e m ix tu re becoming th o ro u g h ly s p o ile d * I t h a s now beeh a s c e r ta in e d in ac co rd a n ce w ith th e p r e s e n t in v e n tio n , t h a t the lea d te tr a e th y l can be caused to absorb th e amount of a lk a li m etal flu o rid e re q u ired fo r i t s s ta b ilis a tio n by m ain tain in g in suspension in th e liq u id lea d te tr a e th y l, or in m ix tu re th e re o f w ith o th e r o rg an ic compounds se rv in g to low er i t s vapour p ressu re --2 w f o r a c o n sid e ra b le p e rio d and p re fe ra b ly a t e le v a te d te m p e ra tu re , a la r g e r amount o f f in e ly d isp ersed a lk a li m etal flu o rid e than is d ire c tly so lu b le in th e lead te tr a e th y l . In th is m anner, th e amount of a l k a l i m e ta l f lu o r id e combined by th e le a d f t e t r a e t h y l, p o s s ib ly a s an on ly g ra d u a lly form ed a d d itiv e compound, can be in c re a se d f o r exam ple, to about te n tim es th e amount absorbed under o th e r c o n d itio n s and th e a n ti-k n o c k agent can th u s be ren d e re d p r a c tic a lly lig h t- p r o o f , even when s to re d f o r a long tim e by its e lf , The p r o c e s s o f th e p r e s e n t in v e n tio n c a n be c a r r i e d o u t i n v a r io u s ways, Good r e s u l t s a re a lr e a d y o b ta in e d by sh a k in g or s t i r r i n g th e two com ponents o f th e d e s ir e d m ix tu re t o g e t h e r f o r some c o n s id e r a b le tim e , f o r ex am p le, s e v e r a l h o u r s , and th en se p ara tin g the liq u id an ti-k n o ck agent from th e undissolved re s id u a l a lk a li flu o rid e by syphoning or f i l t r a t i o n , B e tte r r e s u lts a re however o b tain ed by b o ilin g the lead te tra e th y l, or the an ti-k n o ck m ix tu re, w ith an excess of a lk a li m etal flu o rid e tinder a vacuum, in th e re f lu x condenser, ESg-MPLE 1000 c c , of a known a n ti-k n o c k m ix tu re c o n ta in in g 60$ o f le a d t e t r a e t h y l, 30$ of dibrom oeth y len e and 10$ o f m onochloronaphtalene, a re b o ile d a t 40 - 50C, in a r e f lu x co n d en ser, f o r 1 to 2 h o u rs and under a vacuum of 10 to 15 m , w ith 10 grams o f a m ix tu re o f e q u a l am ounts o f p o ta ssiu m - and sodium f lu o r id e . The l iq u id i s th e n f i l t e r e d o f f fro m th e u n d is s o lv e d se d im e n t. The l i q u i d now c o n ta in s 0 ,0 5 $ o f f lu o r id e * Ho p r e c i p i t a t i o n due to d e c o m p o sitio n o f th e le a d t e t r a e t h y l i s o b se rv a b le i n th e a n ti-k n o c k ag en t tr e a te d in t h is m anner, even a f t e r i t h as been s to re d f o r m onths under exposure to lig h t* KE 0000952 - 3- I claim : 1) A p ro cess of s ta b ilis in g lea d te tr a e th y l and an ti-k n o ck m ixtures c o n ta in in g th e same w hich c o m p rise s d i g e s t i n g s a id le a d t e t r a e t h y l o r a n ti- k n o c k m ix tu re c o n ta i n in g th e same w ith f i n e l y d i s p e r s e d a l k a l i m e ta l f l u o r i d e in a q u a n t i t y exceeding i t s s o lu b ility in said lead te tr a e th y l or a n ti-k n o ck m ix tu re, fo r an extended p e rio d of tim e so a s to cause in cre ase d d is s o lu tio n , and th en rem oving th e u n d isso lv ed re sid u e 2) A process of s ta b ilis in g lea d te tr a e th y l and an ti-k n o ck m ixtures c o n ta i n in g th e same w hich c o m p rise s d i g e s t i n g s a i d l e a d t e t r a e t h y l o r a n ti- k n o c k m ix tu re c o n ta in in g th e same w ith f i n e l y d is p e r s e d a l k a l i m e ta l f lu o r id e i n a q u a n tity exceeding i t s s o lu b ility in said lea d te tr a e th y l or a n ti-k n o ck m ix tu re, fo r an extended p e rio d of tim e and a t an e le v a te d tem p eratu re 3) A p ro cess of s ta b ilis in g lea d te tr a e th y l and an ti-k n o ck m ix tures c o n ta in in g th e same w hich c o m p rise s s u b je c tin g s a id le a d t e t r a e t h y l o r a n ti- k n o c k m ix tu re c o n ta in in g th e same to g e th e r w ith f i n e l y d is p e r s e d a lk a l i m e ta l f lu o r id e in a q u a n tity exceeding i t s s o lu b ility in said lea d te tr a e th y l or an ti-k n o ck m ixture to b o ilin g , w hile condensing the vapours form ed and re in tro d u c in g th e condensate in to th e b o ilin g m ix tu re , and f in a l ly rem oving th e u n d isso lv ed re s id u e , 4) A process of s ta b ilis in g lead te tr a e th y l and an ti-k n co k m ixtures c o n ta in in g th e same w hich co m p rises s u b je c tin g s a id le a d t e t r a e t h y l o r a n ti-k n o c k m ix tu re c o n ta in in g th e same to g e th e r w ith f i n e l y d is p e r s e d a l k a l i m e ta l f lu o r id e i n a q u a n tity exceeding i t s s o lu b ility in sa id lead te tra e th y l or anti-k n o ck m ixture to b o ilin g a t re d u c e d 'p re s s u re , w hile condensing th e vapours form ed and re in tro d u c in g th e condensate in to th e b o ilin g m ix tu re, and f in a l ly rem oving th e u n d isso lv ed re s id u e , 5) An a n ti-k n o c k a g e n t c o m p risin g le a d t e t r a e t h y l in s t a b i l i s e d form co n tain in g an a lk a li m etal flu o rid e in so lu tio n in a p ro p o rtio n exceeding the lim it o f s o lu b ility under norm al c o n d itio n s. H B /G a/ DEPARTMENT GF COMMERCE U nited S ta te s P a ten t O ffice W ashington A p p l i c a n t : J o s e f M. M ic h e l H utz & J o s lin , 521 F ifth A ve., New Y o rk , N. Y , S e r. No. 101,080 F ile d S e p t. 16, 1936 For Process fo r sta b ilisin g lead te tr a e th y l and a n ti knock m ixtures co n tain in g sam e. R eferences c ite d : > ... I.G-. F a r b . (B r,,) 4 1 4 ,5 8 1 Aug. 9, 1934 ,4 4 -9 .0 1 (2 sh eets) Sm ith, "In tro d u c to ry to In o rg an ic C hem istry", 3rd ed8 (1921) C entury Pub. Co. N. Y . (Copy in D iv, 59) Pages 190-196. Jourdan 1 ,9 7 6 ,5 6 4 O ct. 9, 1934 23-32 I . G. F e rb . d e s c r ib e s b ro a d ly th e s o lu tio n o f a l k a l i f lo u r id e s in le a d t e t r a e th y l m ix tu res. A pplicant proposes to d isso lv e th e d iff ic u ltly soluble s a lt by u sin g h e a t, w ith a r e f lu x to av o id lo s s o f th e s o lv e n t. Such m ethod of d iss o lv in g a r e la tiv e ly in so lu b le s a lt by h e a tin g th e so lv en t i s obvious to anyone fa m ilia r w ith elem entary ch em istry . The claim s a re a l l r e je c te d a s u n p a te n ta b le o v er I . G. F a rb . ta k e n w ith Sm ith showing th a t m ost s a l t s a re in c re a s in g ly so lu b le in s o lu tio n , w ith in c re a se d tem p eratu re and th a t c a re fu l cooling w ill allow a su p e rsa tu ra te d so lu tio n to r e ta in i t s so lu te ; a ls o ta k e n w ith Jourdan showing th e sim ple le a c h in g o f an in o rg a n ic su b stan ce by h e a tin g th e s o lv e n t and r e f l u x in g th e same by c o n ta c t w ith a co n d en sin g d e v is e - a ls o in co n tact w ith an excess of substance to be leached - a ls o having the u n d isso lv ed resid u e sep arated a fte r leach in g . v::-*;:---/..> . . .v;. , E x a m in e r. . K F 0000954 N 5669.08 IN THE UNITED STATES PATENT OFFICE J o s e f M. M ic h e l ) 8 e r . No*. 101 080 ) F ile d S e p t, 16, 1936 ) F o r PROCESS FOR STABILIZING LEAD TETRAETHYL AND ANTI KNOCK jiCDCTUEE CONTAINING SAME ) ) ) D iv isio n 64 Room 4708 New Y o rk , N .Y . ' May 2 7 , 1937*. Hon. Com m issioner of P a te n ts* SIR : * I n resp o n se to O ffic e A c tio n d a te d 4th. December 1936, th e Exam iner i s re q u e s te d to rec o n sid er h is re je c tio n of th e claim s in th is case f o r the fo llo w in g reasons* The E xam iner' s p o s itio n w ith r e s p e c t to th e c laim s i s u n d ersto o d to be th a t B r i t i s h P a t e n t S p e c i f i c a t i o n No* 414 581 b r o a d ly d i s c l o s e s t h e f a v o u r a b le e f f e c t o f th e p rese n c e o f a l k a l i f lu o r id e s on le a d t e t r a e t h y l m ix tu re s , a n d th a t i t would n o t am ount t o in v e n tio n t o em ploy m ethods g e n e r a lly known t o le a d t o a n in c re a s e d d i s s o l u ti o n of d if f ic u ltly so lu b le compounds in in c o rp o ra tin g a lk a li flu o r id e s in such te tr a - e th y l m ixtures. The g e n e ra l a p p lic a b ility o f th e in fo rm a tio n su p p lie d by th e Sm ith and Jo u rd an p u b lic a tio n s , is n o t d en ied ; i t is b e lie v e d , how ever, th a t i t was n o t obvious in th e p r e s e n t c a se t h a t th e a p p lic a tio n of th e p r in c i p le s l a i d down in S m ith , would le a d t o n r in creased so lu tio n of a lk a li m etal flu o rid e s in te tra e th y l lead a t th e tem peratures of s to ra g e , i , e , room te m p e ra tu re s. T his i s so f o r th e reaso n th a t th e re i s n o th in g to show t h a t th e s o lu tio n s o b ta in e d in acco rd an ce w ith th e p re s e n t in v e n tio n a re s u p e rs a tu ra te d a t room te m p e ra tu re * O b serv atio n s r a th e r ten d to show t h a t th e c a p a c ity o f te tr a e th y l le a d fo r d iss o lv in g a lk a li f lu o r id e , is q u ite s u b s ta n tia l even a t room ^ te m p e ra tu re , b u t t h a t f o r seme r e a s o n o r o th e r su ch s o lu tio n p r o g r e s s e s v e ry much m ore S' 2-. slow ly th an in otherw ise sim ila r cases Since u s u a lly d ig e stio n o f a substance of even lim ite d s o l u b i l i t y w ith th e d is s o lv in g medium a t no rm al te m p e ra tu re le a d s w ith in a c o m p arativ ely s h o rt tim e to a s u b s ta n tia lly s a tu r a te d s o lu tio n , i t co u ld n o t be a n tic ip a te d th a t th e q u a n titie s o f a lk a li f lu o r id e s which a re d iss o lv e d by te tr a e th y l lea d w ith in a p e rio d of th is o rd e r, w ould be o n ly a f ra c tio n of th e d is s o lu tio n c a p a c ity o f te tr a e th y l le a d , w h ic ty in c id e n tally , of c o u rse , was not known. It'w a s only th e d isc o v e ry th a t by a very prolonged treatm en t o f te tr a e th y l lea d w ith a lk a li"m e ta l'flu o rid e s , re s u lte d in p ro g re s s iv e ly in c re a se d p ro p o rtio n s o f f lu o r id e s becom ing d is s o lv e d , w hich le a d to attem p ts to sh o rte n the d u ratio n o f such treatm en t by the a p p lic a tio n of h ig h er tem peratures a s shown in th e p r e s e n t s p e c if ic a tio n '" To sum u p , i t co u ld n o t be a n ti c ip a t e d t h a t th e a p p lic a tio n o f th e u su a l.m e an s f o r d is s o lv in g d i f f i c u l t l y so lu b le su b sta n c e s in f lu id s would in th e p re se n t case r e s u l t in * . . . an ap p reciab le in crease of the co n cen tratio n in re sp e c t of the flu o rid e of the so lu tio n s - o b ta in e d , and i t i s b e lie v e d th e r e fo r e th a t th e a p p lic a tio n o f such known m ethods w ith an e n tir e ly unobvious and advantageous r e s u lt m e rits th e g ran t o f a p aten t ... - -5 i ' : R e sp e c tfu lly subm itted ,, A tto r n e y s f o r A p p lic a n t, If HB/ Ga 0000956 DEPARTMENT OF COMMERCE U nited S ta te s P a ten t O ffice W ashington H utz & J o s lin 521 F if th Ave, New Y o rk , N Y* A p p l i c a n t : J . M. M ic h e l S e r. No8 101,080 P iled S e p t. 16, 1936 F o r PROCESS FOR STABILISING LEAD TETRAETHYL AND ANTI-KNOCK MIXTURES CONTAINING SAME. R e sp o n siv e t o argum ent f i l e d May 2 8 , 1937* - The claim s a re ag ain and F in a lly r e je c te d a s showing no procedure fo r d is s o lv in g a s a l t o th e r th a n would be e x p e c te d of one s k i l l e d in th e a r t i n view o f I , G. Farb* r e c itin g the d e sira b le com bination i . e 6 a s o lu tio n o f a lk a li flu o rid e w ith lea d t e tr a eth y l* A pplicant fin d s th a t th e solvent w ill n o t d isso lv e s u ffic ie n t s a lt in the c o ld s t a t e , h e n ce h e p ro p o se s t o h e a t th e s o lv e n t Such s o l u t i o n oY th e p ro b le m , i f i t is a problem , i s obviously elem entary, nor does the so lu tio n acq u ire the d ig n ity of in v e n tio n by reaso n o f the a d d itio n a l p ro p o sal to c a rry out th e h e a tin g by a conventional e x tra c tio n , w ith a reflu x in g condenser to prevent lo ss of so lv e n t, or a t reduced p ressu re to p rev en t decom position th ereo f* A p p lican t argues th a t th e re is no evidence th a t th e so lu tio n i s su p e rsa tu ra te d ; th a t r a r e l y does sim ple a g it a ti o n f a i l to e f f e c t s o lu tio n A p p lic a n t does n o t know th a t th e so lu tio n is not su p ersatu rated , and ra re r s t i l l does h eatin g f a i l to enhance the s o lu b ility of so lu te in a so lv e n t, both as to ra te o f so lu tio n and q u a n tity d isso lv e d * Exam iner 0000957 N 5669.1 P erso n al and C o n fid e n tia l F eb ru ary 11* 1938 Hr* J . H. S c h a e fe r E thyl G asoline C orporation P. 0 . Box 688 W ilmington, Delaware Dear Mr. S ch aeferi Thanks fo r your l e t t e r of February 7^ w ith i t s fu rth e r inform ation concerning the use of c e rta in a lk a li m etal flu o rid e s fo r s ta b iliz in g t e tr a e th y l lead * I d id n o t w ire you b ecau se th e re seemed to be no p o in t in o b ta in in g f u r t h e r in fo rm a tio n . I have ^u st had a l e t t e r from H r. Bevan, a sk in g me when I e x p e c t to v i s i t him in E n g lan d . I have r e p l i e d t h a t to the b e s t o f my knowledge i t would prcfcably be in e a r l y May* I f you now o r a t a l a t e r d ate have any inform ation which in d ic a te s th a t th is date should be moved e ith e r forw ard or backward I would a p p r e c ia te y o u r l e t t i n g me know as soon as possible* Very tru ly yours* U K is Ro b e rti '"K 7 Ke h o e * k . D . K 0000958