Note: Descriptions are shown in the official language in which they were submitted.
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
- 2 -
~, ,.
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
:`
- 4 -
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
CH3
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
- 6 -
,
~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$cally-
~tirred autoclave containlng 540 gr~mJ of 97 p r c nt aqueou~
sul~uric acid and under a carbon monoxide pre--ur of 1300 pound-
per Jquare inch gaug- ~91 6 k~logram~ p-r ~quare centl~ t-r),
there wa~ lntrodw ed, with atirring, over a period of 1.9 houra
180 gram~ of l-octéne Whon the addition o~ ol-~in waa compl t d,
the resulting mlxture wa8 permitted to react for an additlonal 18
~`
`~ minutes The teqparature durlng the reaction waa ~i~tain~d
~-~ 30 constant at about 250 C. At the end of the reaction period th~
- 8 -
lW8563
crude mix~ure in the autoclave was depre~sured into a veJ~el
containing about 1200 grams o~ wet ice and the organic layer that
formed on ~tanding was separated in a Qeparating funnel and wa~hed
several times with approximately an equal volume of a hot 15 per
cent aqueous solution of sodium chlorlde until the final washing~
were neutral to litmus paper. On work-up by distillation thore
was o~tained 185.2 grams o a fract$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
- 10 -
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
.
`:
- 12 -
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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