CA1088563A - Production of carboxylic acids from olefins and mixtures of olefins - Google Patents

Abstract

PRODUCTION OF CARBOXYLIC ACIDS
FROM OLEFINS AND MIXTURES OF OLEFINS
ABSTRACT OF THE DISCLOSURE
A process for producing carboxylic acids from olefins having from 16 to 20 carbon atoms or mixtures of olefins having from 20 to 24 carbon atoms which involves adding the olefin or mixtures of olefins without a solvent to carbon monoxide and sulfuric acid and thereafter adding water to the reaction product so formed.

Description

101~5~i3 BACXGROUND OF THE lNVENTlON .
1 F$eld of tho Invontlon This lnvontlon r-lat~ to a proc--- for produc~ng ¢ar-- -, boxylic ac$ds from olefin~ having from 16 to 20 carbon ato~s (or mlxturo- theroof) or to ~ixtures of ol~f~n~ hav$ng ~rom 20 to 24 carbon atom~

2 D~crlDt~on of the Prior Art -ln V 8 Patent No 2,831,877 to Koch thor ~- dl-clo~-d -a proces~ for pr~parlng carboxylic acid- whlch lnvolv - r ac*~ng olef~ns and carbon monoxldo ~n the liquid pha-- without th addlt$on of w~t-r and in tho pr Jence of acid cataly t- contain$ng little or no water, ~uch a~ ~ulfuric acid, and ther-aft-r taklng up tho reaction product $n water Although Koch ~ak - no ~ntion of th ., :
~ffect of a ~olvent in hi- proco--, the reac*lon lnvolvlng a low r olefin i~ carrled out, with no seemlng pr-ference, wlth and w$thout a olv nt, but wlth a h$gh r ole~in, uch a- C12 or hlgh r, with a ~olvent, uch a8 paraffin~ from the Fi~¢her-~rop-ch ynth ~i~, or ~ ~
n-hexane. ln U 8 ~at-nt~ ~08 3,053,869 to MkAll~ter t al and ~;

3,167,585 to Ander-on et al there $8 no teach$ng of th- probl-m~ ;
as~ociat-d with tho tre~tm~nt of high-r olefln- $n u¢h proc--- to $ncr-aso ~olectlv$tios to desired ¢arboxyllc acid~
SUMMARY OF THE INV~NTION
We have found, unoxp todly, that whil- the u-- of a ~olv~nt in the process doo~ make a differonc~ ln ol~ctlvlty to de~irod carboxylic aclds w$th Iower olef$ns, ~ncrea--d -l ctiv$t$~
ar~ obtalned when C16 to C20 ol-fln~ or m$xtur-~ of C~O to C24 ol-f$n~
ar~ u-~d if tho proce~s $- carr$~d out $n the ab~enc- of a ol~ nt Among the olefin~ that can bo u-ed hero$n aro alpha ol--fln~ or mixtureg thoreof having from 16 to 20 carbon atom~, ~nternal ~, ,.

10~85~3 olefin~ or mixtures thereof having fro~ 16 to 20 carbon atom~obtained by a di~proportionation reaction involving two lower olef~ns, aJ, for example, in U 8 Patent No 3,595,920 to ~
et al, or branched internal olefins or mixtureJ thor of having from 16 to 20 carbon atom~ obtained a~ ~ r ~ult of di~ rizing lower alpha olefins using a Ziegler cataly~t, ~uch a~ trii~obutylalu~inu~, as, for ex~mple, in Brltish Pat-nt No 742,642 to Xarl 81 gl-r Also used herein are ~ixturo~ of olo~n~ id ntical to tho-e d finod hereinabove but having from 20 to 24 carbon atomJ A typical mix-ture will contain fro~ about 40 to about 60 weijht per c nt of C20 olefin~, from about 30 to about 55 weight por c nt of C22 olofin~
and a~out five to about 10 wei~ht p-r cont of C24 olefin- 8pec$flc examples of olefins that can b- u~ed herein includ- l-h xadbc ne, 2-hexadecene, 3-hexadecen-, 4-hexad c n , 5-hexad c ne, 6-h xad cene, 7-hexadecen-, 8-hexadecon , l-heptad-c-n , 2-h ptAd a-n , 3-h~pt~-docene, 4-h ptad c-n-, 5-heptad c-n-, 6-hqptad c-n , 7-h ptad c-n-, 8-h-ptad-c-n-, 9-h ptadoc-n~ o¢tad c-n , 2-octadbc-n , 3-oata-d-cene, 4-octadecen-, S-octad-c-n-, 6-octa~ c ne, 7-octad c-n , 8-octadeceno, 9-octadeceno, l-nonad-c-n , 2-non~d~con , 3-nona~ en ,

4-nonadeceno, 5-nonadec-ne, 6-nonadecene, 7-nonad c-n , 8-nonadbc-no, 9-nonadeaone, 10-nonadoc-n-, l-eico~-ne, 2-eico~-n , 3--lco~-~o, 4-eico~ene, S-eico~ no, 6-eico~-ne, 7--i¢o~ens, 8-elao~ ne, 9--lco- -~ene, 10-eico~ene, l-h n-ico~one, 2-h neico~ene, 3-hen-icoaen , 4-heneico-ene, 5-heneico~one, 6-heneico~-n-, 7-heneiao~-n , 8-hen-eicosene, 9-hene~cosene, 10-hen-ico--n , ll-h neico--ne, l-doco~-ne, 2-doco~ene, 3-docosene, 4-docosene, 5-doco~ no, 6-doco~ no, 7-doco-sene, 8-docosene, 9-doaosene, 10-doco-eno, ll-doco~ono, l-trico--ne, 2-trico~en-, 3-tricosene, 4-trico--ne, 5-trico~ono, 6-trico-~n-, 7-tricosene, 8-tricosene, 9-trico~-ne, 10-trico-en , ll-trico- n-, 12-trico~ene, l-tetracosene, 2-tetracosene, 3-tetraco-ene, 10~8563 4-tetracosene, 5-tetraco~eno, 6-totracosene, 7-t-traco~ n , ~-tet-raco-ene, 9-tetraco-ene, 10-t~tracosene, ll-t-tr~co- no, 12-t tra-co~one, 2-methyl-1-p-ntadecene, 2-othyl-1-t-trad aen-, 2-n-propyl-l-trid-ceno, 2-n-butyl-1-dodecone, 2-n-p ntyl-1-undbc-n , 2-n-hexyl-l-d cene, 2-n-heptyl-1-nonene, 2-methyl-1-h xad c-ne, 2-ethyl-l-pentadecone, 2-n-propyl-1-tetrad~c~n-, 2-n-butyl-1-trid c n , 2-n-pentyl-1-dodec~ne, 2-n-hexyl-1-und~c-ho, 2-n-hqptyl-1-d c-n-, 2-~ethyl-1-heptadec~no, 2-ethyl-1-hexadeo-n , Z-n-propyl-l-ponta-dec~ne, 2-n-butyl-1-t-tradecene, 2-n-p ntyl-l-tr~d c ne, 2-n-h xyl-l-dodecone, 2-n-heptyl-1-undoc-n-, 2-n-octyl-1-d o ne, tc In order to obta n h~gh -l otivity to db-lred oarboxyllc ac~d it i~ imperative that the ol-fln b- add~d to th r act~on zone ~-contain~ng the cataly-t and r actant carbon monoxidb ~-The cataly~t u~-d h rein c~n be ~ub-tantially 100 p-r cent ~ulfur~c acid, although it i- pr ~ rred that aqu ou~ ~ulfurlc acid havlng a str ngth of about 90 to about 99 p-r ~nt, pr ~ rably about 92 to about 98 por cent, b- u~-d.
Th- r-aation i- carri-d out und r ~lld cond~tlon~ of ~ -temperature and pro~ur Thu~, the tomperatur can be in the rang of about -15 to about 100 C , preferably about 0 to about 40 C , and the pro--uro about 100 to about 5000 pound~ per ~guar ~nch gauge (~bout e~en to about 352 kilogramJ p-r ~quar~ ¢~t~eter), preferably from about 500 to about 2000 pouna~ per square inch gaug-(about 35 2 to about 140 8 kilograms per quar~ centim~te$) Reaction time of about 0 01 to about 12 hour~, pr f r~bly about 0 1 ;~ to about four hour~, will uffice.
At the end of the reaction per~od th roaction product contact-d with water to obta~n the de-ired carboxyl~c ac~d-Temperature, pre~sure and reaction time ~imilar to the above can ~ 30 be used in this ~tep The carboxylic acid- will Sor~ a -parate :`

1()8~563 pha~e on the surface of tho r~actton mixtur- and can b rocov red therofrom, for example, by decantation If desirod, rocov ry can b- effected by di~tillation Thus, only four components aro noodod in th roaction zono in accordanco with the proco~ d-finod and cla~mod heroins olefin or mlxturoJ of oleftns, carbon monoxide, ~ulfurio acld and water In order to obtain the desired convorsion at loa-t equimolar amounts of olefins, carbon nox~do, ~ulfurlc acld and wat-r aro roguired As noted, increa~ed s-loctivitio~ to do~ired carboxylic acid aro obtainod when no solvent i~ pr ~ent and the r action i-carried out ~ololy wlth olefin,aarbon ~onoxt~e, ulfurlc acid and water A~ hown in our Applicatlon 8-rlal ~umb-r 367,177, ontltled COMP08ITION CONTAI~ING ~IGH~R FATTY ACIDB, now U 8 Patent ~o 3,~42,106, when tho ol-f~n u~-d ~ an alpha ol-fin or an olef~n obtalned by a dt~proportionation r aatlon, th carboxyllc acld obtalned can be defined a- ~alllng within th followlng two goneral ~tructur--s T-rtl~rY (N o~ CarboxYllc Aa~ds a~3 (CH2) x-n-2 (CH2)n-2 whor-ln x i~ tho number of carbon atom~ in tho reactant ol-fin, that is, from 16 to 24 carbon atom~ and n i~ the int ger 2,3,4 up to ~ for even ~nteger~ botween 16 and 24 and 2,3,4 up to _~_ for odd integers betwe-n 16 ana 24, and ;~

:; :
", ~..
.... . . . . .. . . .

1o88s63 ~-Secondarv (Iso) CarboxYlic Acld-C,H3 ,, ~C,H2)x-n-1 --;
H - C - COOH
(C,~2)n-2 ' "' '' C~3 wherein x i- a8 defined above, and n 1- th~ int~g-r 2,3,4 up to x for even integer- betwe~n 16 and 24 and 2,3,4 up to ~ for '~
odd integer~ betw~n 16 and 24 About half of tho carboxyli¢ '~
acids obtained are tertiary and bout half ~econ~ary ~h-n a ,~
branched internal ol-fin i~ u~od, obtaln~d a- a r--ult of di~or~
lzing a lower alpha ol-~in, the carboxylic acid will be a t~rtiary carboxylic acid corr~ponding to th~ r actant ole~n but h~ving on- more carbon atom with th~ carboxyl group b-lng ~tta¢h-d to a carbon carrying a methyl group and two additlonal alkyl ~ub-tituont-Th- proc--~ ¢an b- und rJtood by r f r nc- to th~ followlng '' ~-ci~ x~pl~
,~xamDle I
; , About 180 grum- of l-octo~e and S40 gra~J o~ 9~ p-r c nt , ~u~ou~ ulfuric ~cid w r- ch~rged into a one-lit-r, 316 ~talnl~
, ~~teel, magn-tically-atirred autoclav , pr~a~ur ~ wlth oarbon ~on-,, 30 ox~de to a pre~-ur of 1100 pound~ p-r a~uar i~ch ~au~ l77 S
i u ~" ~, ~llograms per quar- c nti~eter) and allowod to react for two hour~ ~', ,, ,, ~. ~, t 28 C The crude rea¢tion ~xtur wa~ pourod ov r 1000 gr m#
'',~ of ~ce and the organic layer waa #qparat~d in a qparatory funnol and~thon washed ~ev ral time~ with hot 15 p r c~nt a~uooua ~odium ~-, dhloride until tbo f~nal washinq~ wor~ neutral toward lit~u- pap-r On dl~til~ling t~ p wduct, ono ma~or fraction of 59 5 gr,~# hav~ng a boiling ~ange of 160 to 195 C at 10 millimet~r of meraury , ~0885~;3 was obta~ned Analy8i8 of this materlal by vapor pha-- chro~ato-graphy ~how d that, at b~t, seven weight p-r c~nt of Cg oarboxyli¢
acid~ wore in th~ mixture Mo~t of th~ produot app-ar d ln th high boll~ng re-idue ~91 5 gr~-1 h~ving a boiling polnt ~u¢h greater than 195 C at 10 mill~ t-r- of ~r¢ury Mo-t of thl-re-~du~ iJ bel~ev~d to re-ult mo-tly from ~ul~atlon and poly~r~-zation reactlons rath~r than tho d~ d r-d carboxylation r actlon 8~mllar product~ have b~en not~d from th- r aotlon of l-o~t-n~
w~th aulfurlc acid in th aba~no- of carbon ~onoxido ~xamDle II
About 160 gra~ of l-oct-n , 160 gram- of n-h xuno and 400 gr~m~ of 97 p~r o~nt ~uluri¢ a¢id wor ¢harg d into a on--liter, 316 ~talnl~s~ ateel, magn~tlcally-~tirr~d autoclav and reacted aa in ~xa~pl~ I for two hour- at 9S0 pound~ p r ~guar~
~nch gauge (66 9 kilograa~ p-r ~quar o-nti~ot-r) o~ carbon ~on-oxid~ prea~ure and 27 C Th r a¢tlon product waa dlaah~rg-d lnto 1000 gram- o~ 1¢-, th- organl¢ lay r wa~ ~-parat-d by db¢~nt~ng ànd thon wa-h-d J-v ral time- wlth 15 p~r ¢-nt aqu~ou- ~od~um ¢hloride ~olution untll final wa-hing- w-r n utral tow~rd lit~u~
paper Thl~ layer wa~ th n ~tripp-d of n-hexane ln a rotary vapo-rator to obtain 169 4 gram~ of organi¢ protuct having a n utral equivalent of 399 (theor ti¢al 157) Analy~i- by vapor pha~
¢hrom~tography ~howod about 30 weight per c nt of th product to be the de~ired Cg aarboxylic acid-, the ~i-trlbution o~ whlch wa- a~
follow~ 4-methyl-4-o¢tanoi¢ acid (16 4 woight per c-nt), 3-m-thyl-3-octanoi¢ a¢ld (44 7 weight per c~ntj, 2-m~thyl-2-o¢tanoic acid ~ (32 1 weight p~r cent), 4-nonanoi¢ acid ~1.0 weight por ¢ nt), `~ 3-nonanoic acid (2 4 w~lght per cent) and 2-nonanoic acid ~3 4 welght per ¢ent) ,., ~0~8563 ExamDle III
A one-liter, 316 8ta~ nlo~ Jte~l, magn t$c~11y--t~rr~d autoclave wa~ ch~rged with 440 gra~ of 97 p-r c-nt ~gu-ou~ -~ulfurlc acid and 100 grams of n-hexane and th n pr~--ur d to -1150 pound- per square lnch gauge ~81 0 pound- p r guaro $nch ~i gaug~) with carbon monoxido lB0 gr-m~ of l-oct n- wa~ th n addod .
to the autoclave over a p-r$od of two hour- wh$1- ma$ntainlng th temperature in th- autoclavo in the rang- of 25 to 30 C The product wa~ thon addod to ic- a~ abov- and work d up to pro~uc-, upon distill~tion, on- ma~or fraction of 173 2 gram havlng a boillng range of 125 to 147 C at 10 m$11~m-t-r~ of ~ rcury nd a res$due of 25 7 gram~ An~ly-i~ of th product how d 147 6 gram~ of Cg carboxylic acld~ to bo $n th- ma~or fraation coxr -ponding to an effic$on¢y of 67 1 welght p-r c-nt. Th- di-trlbu-tion o~ lndividual i~o~er~ in ord~r of th ir em rgenc- o~ th chromatographi¢ column w~ a- ~ollow-~ 4-mothyl-4-octanoic acid ~12 2 w lght p~r c-nt), 2-mothyl-2-octanoia w 1~ ~26.2 w ight p-r c~nt), 3-mothyl-3-octano~c aa~d ~35 6 w ~ght p-r c-nt), 4-nonanolc ~ -acid ~10 4 w~ight por cont), 3-nonanolc acid ~11 1 wo~ght per a nt) and 2-nonanolc a¢~d ~4 5 w ight per c-nt) ~x~mDle IV
Into a ono-llter, 316 ae~inl~ to l, magn t$cally-~tirred autoclave containlng 540 gr~mJ of 97 p r c nt aqueou~
sul~uric acid and under a carbon monoxide pre--ur of 1300 pound-per Jquare inch gaug- ~91 6 k~logram~ p-r ~quare centl~ t-r), there wa~ lntrodw ed, with atirring, over a period of 1.9 houra 180 gram~ of l-octéne Whon the addition o~ ol-~in waa compl t d, the resulting mlxture wa8 permitted to react for an additlonal 18 ~`
`~ minutes The teqparature durlng the reaction waa ~i~tain~d ~-~ 30 constant at about 250 C. At the end of the reaction period th~

lW8563 crude mix~ure in the autoclave was depre~sured into a veJ~el containing about 1200 grams o~ wet ice and the organic layer that formed on ~tanding was separated in a Qeparating funnel and wa~hed several times with approximately an equal volume of a hot 15 per cent aqueous solution of sodium chlorlde until the final washing~
were neutral to litmus paper. On work-up by distillation thore was o~tained 185.2 grams o a fract$on consi~ting es~entially of Cg carboxylic acid~ having a bo~ling point range of 108 C. to 113 C. at 4 millimeterQ of mercury. Analysi~ of the product 10 mixture by vapor phase chromatography Jhowed the presen¢e of the --following isomeric acid~s 4-nonanoic acid (9.0 weight por cent), 3-nonanoic ac~d (lO.S weight per cent), 2-nonanoic a¢id (4.8 weight por cent), 4-methyl-4-octanoic acid (16.4 weight per cont), 3-methyl-3-octanoic acid (34.3 weight per cent) and 2-methyl-2-octanoic acid l25.0 weiqht per cent). The ratio of ~ethyl protons to methyl-ne ~nd methine by nuclear magnetic re~onance wa~ about 0.96:1 in complete agreement with detail-d chromatographic analy~
The amount of i~olated Cg acids correspond to ~n efficiency of about 74 we~ght por cent and had a neutral ~uivalent value o~ 162 (theoreti¢al value 158), Examples I ant II show that wh n the operation i~ car~
out in batch the presence of a solvent or ~llu~nt, for examplo, n-hexane, subJtantially increa~e~ the ~electivity to carboxyl~c acids when a lower olefin i8 used. However, as shown in ~xamples SII and ~V, introducing the same olef$n into a reactor containing carbon monoxide and sulfuric acid re~ults in evon higher ~electi-v~tie~ to carboxylic acid. In the latter ca~e, about the same level of ~electivity i~ reached whether or not a solv~nt or diluent i~ present. In Example III with n-hoxane ~electivity of 6~.1 was obtained, while in ~xample IV in the ab~ence of n-hexane ~electivity was increased slightly to 74 weight per cent.

_ g _ 10885~i3 ExamPle v About 180 grams of l-hexadecone and 530 grams of 97 per cent aqueous sulfuric acid were charged into a one-lit-r,316 stainle~s steel, magnetically-stirred auto¢lave, pr--~ur d to 1050 pounds per square inch gauge (74 0 k~lograms per ~guare centimeter) with carbon monoxide and allow d to react for two hours at 28O C The reaction product was taken up in water and worked up a~ above to give an efficien¢y of about 36 weight per cont to the desired C17 c~rboxyl~c acid~
ExamDle VI
A one-litor, 316 ~tainles~ 8t-ol, magneti¢ally--tirrod autoclave was char~ed w~th 366 gr~m~ of 97 per ¢ent aqu ous ~ul-furic acid, pressured with carbon monoxid to 1000 pound~ por ~quare inch gauge (70 5 kilograms p-r J~uar centi~ot-r) and 180 grams of l-hexadecene in l00 gram~ of n-hoxane wa~ add d gr~dually to the auto¢laYe over a p-rlod of two hour- whil~ th t-mporatur- -th-rein wa~ malntain-d at 28 C On addlt~on o~ wat-r an~ work-up a~ befor-, followed by dl~tlllatlon, a ~a~or fractlon of 144 3 ~rams having a boiling point rang- of about 207 to 212 C at l0 millimeters of mercury wa~ obtalnea along wlth 47 0 gr~m~ of residue Analy~is of produ¢t by vapor pha~o chrom tography indl-cated an effi¢ien¢y of 56 weight per cent to the d -ired C17 aar-boxylic acids ~he foll~wing acid~ aro pr ~ent in th produ¢ts 2-methyl-2-hexadeaanoic acid, 3-methyl-3-hexadocanoi¢ acid, 4-methyl-4-hexade¢anoic acld, 5-methyl-5-hexadec ic ~cld, 6-m~thyl-6-hexadecanoic acid, 7-methyl-7-hexadecanoic acid, 8-m~thyl-8-hexadecanoi¢ acid, 2-h-ptadecanoic acid, 3-h ptadecanoic acld, 4-hepta~ecanoic acid, 5-heptadocanoic acid, 6-heptadoc lc ~cia, ~
;~ 7-heptadecanoic acid and 8-heptadocanoic acid $h ratio of t-r-, , tlary acid~ to secondary wa8 52 2 47 8 108~5~3 ExamPle VII
The run of Example VI wa~ repeated except that the op~ration was carried out in th~ ab~ence of n-hexane On work-up, as before, an efficiency of 73 8 weight per cent to the d~sired C17 carboxylic acid wa~ obtained with the ratio of tertlary acid-to ~econdary acids, a~ determinod by vapor pha~- chromatography, being 53 1 46 9 Comparing ~xamplo~ V, YI and VIl with the previou~
oxample~, it can bo seen that while batch op-ration with higher olefins is not attractive, somewhat higher yield~ ar- obtained with the hlgher oleflns than with lower ol-fin~ Thu~, although selectivity to Cg carboxylic acids in the batch run of ~xample I
wa~ only sevon per cent, selectivity to C~7 carboxylic acids in Example V was 36 weight por cent ~ho gradual addition of C16 olefin in ~xample VI with n-hexane pre~-nt waJ u~ici-nt to rai~e the Jelectivity to C17 carboxylla acld~ to 56 welght p-r c-nt ~owover, when th- Nn wa~ rep-ated in ~xa~plo VII w~th n-hexan-ab~-nt, seloctivity wa~ unexp~ctodly rai~ed to 74 w ight per c-nt, an increase of about 32 per cent ovor that of Exu~pl~ V~
Bxa~Dle VIIl ~nto a one-litor,316 Jtainl~ teol, magn t~cally-~tlrr d autocl~ve there wa~ ¢harged 534 gram~ of 96.7 w~ight p-r cent aqueou~ sulfuric acid and 180 gra~ of l-eicosene Tho a~toclave wa~ pre~sured to 1000 pounds per square inch gaug- (70 5 kilograwJ
per square centimeter) with carbon monoxide and the content~ wore perm~tted to react with each o~her for 8~X hours at 30 C On ~ addition of water and work-up a~ before there wa~ obtained a 46 ; weight per cent yield of C21 carboxylic acid~
~xam~le IX
Into the sa~e autoclave used above thero was charqed 375 grams of 97 per cent aqueou~ sulfuric acid and the autoclave ~0~85~3 was then pre8~ured with ¢arbon monox do to 1200 pound- p-r qpar inch gauge ~84 5 kilogr~s per ~quare c nt~ot-r) Nh$1- th t _ perature WaJ maintained at 29 C thor wa~ lntro~ua-d into th- auto-clavo 160 gr~s of l-eico~one in 85 gra~J o~ n-h~x~n- ov r a p rlod of two houra Aftor addition of water and work-up ~- bov , an~ly-i-of the product by chromatography and n utral ~guival-nt d-t-r~in~tion indicatod that tho product cont~inod 45 6 weight p-r a-nt of th d-Jirod C21 carboxylic acid~
Exam~le X
Th run of Example VIII wa~ r p-ate~ xc pt tpat th ol--fin w~ addod g A dually to th- autoclave ov r a p rio~ o~ ~our hour and the r action w~- p-r~lttod to proc--d for an addltlon~l two hour~ On w~rX-up, a~ b fore, a 76 wo~ght p-r ¢-nt yl-ld o~ C
¢~rboxylic acid~ wa~ obtained Th~ ro~ult~ obtain d in ~x~pl-~ VIII, I~ and X aro CO~r pardble to tho~e obtain-d in ~xampl-~ V, VT and VTT Batah op-ratlon in ~xampl- VIII ro-ulted in ~-lectivlty to d~ir d c-rboxylla acid-of only 45 6 $ho gradual ad4ition of C20 ol-~n to th r a~tlon zon in ~x mp~ IX r~-ult~d ln no i~prov ccnt. ~ t~v~ty to d~ir d aa~boxylic ac~da in Exampl- X, ~ilar to ~xa~pl- r~ but , carried out i~ the ab~-nce of ~-h xan-, r ~ult-d in a 66 p~r c-nt L~cr a~e in selectivity to C21 carboxyllc acid~
Bxa~ XI
Th- sa~o autoclav~ uJed above wa~ ¢h~rg-d ~th 445 gra~J
of a 97 per cent aqueou~ sulfuric acid und 220 gr~ of an alpha ol~fin mlxture ~for practical purpo--- r f rr d to h-r in a~ a UC20 to C24" alpha olefin mixtur~") of the following coqpo~tion AlDha Ol~fin Weiaht P~r Cent C18 3 3 -;
~30 C20 51 0 ' C22 37 9 ~`~ C24 7 8 .
`:

5t~3 The reactor was pressured to 1000 pound~ por ~quare inch gaug-~70 s kilograms per squ~re centimeter) with carbon monoxide and the reaction wa~ permitted to proceod for thr-e hour~ at 28 C
The reaction mixture was taken up in wator and worked up as b-fore Analysis of the product by titration and vapor pha~e chromatography ~howed only 10 weight per cent of tho product con-i-ted of the desir,ed Clg-C25 carboxylic acids~
ExamDlo XII
Into the Jame autoclave u~-d above conta~ning 440 gram~
of 97 per cent aqueous sulfuric acid and under a darbon monoxido pre~sure of 1340 pounds per ~quar- inch gauge (94 4 ~llogram~ per square centimeter) and a temperature of 30~ C th-r wa~ introduc-d over a period of 8ix hours 220 gram- of tho C20-C24 alpha olofin mixture in 220 gr~mJ of cyclohexane Reaction wa~ ¢ontinu d for 30 minuteJ and thc roaction wa~ tak-n up in water an~ work~d up a-before A ma~or fraction w ighing 141 8 gramJ wa~ obtain-a ¢on-taining Clg-C25 carboxylic acld~ 8el-ctlvlty wa~ d ter~ined to be 44 w ight per cent ~xamDle XIIS
The run of Examplo XII waJ repeated except that no cyclo-hexane was present 8el-ctivity to d ~ir d carboxyllc acld~ wa~
found to be 69 wolght per cent Again, the runs of Ex~mple~ XI, XII and XIlI were found to be comparable with the previou~ run~ ~he batch run of ~x~mple XI re~ulted in poor ~electivitie~ to carboxylic acid, while tho run of Example XIII wherein ~he olefins wore introduc-d into the ~ reactor in the ab~ence of cyclohex~ne re~ulted in ~n incr a~e in ;~ selectivity of 56 weight per cent over the Jame proce~s in ~xample XII but wherein cyclohexane was also pre~ent 108~5~3 The carboxylic acida produaed her-in can b- react-~ with a polyalkylsne polya~ine to obtaln a poly d de which can b add-d to a lubrlcating oil to improvo it- pour and detergency charact-r-i-tic~
High~r carbon number olefin~ are v ry vl~oou~ uld~, ;
some even ~olids, and bringing these into solution~ wa~ ~Xp ct~d to induc~ mobility and diJper~ion ne¢eJ~ary ~or contacting o~ th ~ulfuric acid with the hydrocarbon pha~e for ionizat$on and for~ation of reactive $nter~di~ta~ W , un~xp ctedly, found -~
that ~olv~nt- ~uca~fully ~mploy d with the low r carbon nu~b r d olef$ns ~C4 to about C12) $n carboxylation- are not Juitabl- ~or reaction~ with the olefin~ clal~ed by u-Obviou-ly, many mod$f$cat$on- and var$ation- of th~
~nventlon, a~ hereinabove s-t forth, ¢an b- ~ade without d parting fro~ the ~pirit and ~cope ther of, und, th r for , only uah limitation- ~hould b~ i~po~ed a- ar indiaat d in th- app-n~-~alalm-.

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Claims (10)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for the production of carboxylic acids solely from olefins having from 16 to 20 carbon atoms or mixtures of olefins having from 20 to 24 carbon atoms, aqueous sulfuric acid of at least 90 per cent strength, carbon monoxide and water which con-sists in adding an olefin having from 16 to 20 carbon atoms, mixtures of olefins having from 16 to 20 carbon atoms or mixtures of olefins having from 20 to 24 carbon atoms in the absence of a solvent to a reaction zone containing carbon monoxide and sulfuric acid of at least 90 per cent strength, adding water to the reaction product so formed and thereafter recovering the desired carboxylic acid product.

2. The process of claim 1 wherein said olefins are alpha olefins.

3. The process of claim 1 wherein the strength of the sulfuric acid is about 90 to about 99 percent.

4. The process of claim 1 wherein the strength of the sulfuric acid is about 92 to about 98 percent.

5. The process of claim 1 wherein the temperature is in the range of about -15° to about 100°C. and the pressure about 100 to about 5000 pounds per square inch gauge (about seven to about 352 kilograms per square centimeter).

6. The process of claim 1 wherein the temperature is in the range of about 0° to about 40°C and the pressure about 500 to about 2000 pounds per square inch gauge (about 35.2 to about 140.8 kilo-gram per square centimeter)

7. The process of claim 1 wherein said olefin is 1-hexadecene.

8. The process of claim 1 wherein said olefin is 1-octadecene.

9. The process of claim 1 wherein said olefin is 1-eicosene.

10. The process of claim 1 wherein the olefin charge is a mixture of C20 to C24 olefins.