Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
1(~7~Z8~
MI~URE~ OF PO~Y-BR~NCH~D ~ONOCARBO~IC AaIDS
AND P~VCESS FOR PREPAXING SAM~ :
The presen-t i~lventio~ relates to mixtures of poly-branched
monocarboxylic acids 3nd processes for preparing same.
Said m~xtures are o~ a grea~ practical interest for pain~
varnish i~dustry a~d hydr.ometallurgy.
II:L paint-varnish industry said mixtures o;~ poly~bra~ched
monocarboxylic acids make it possible to obtain siccatives
with a hi~h, almost theo~etical, co~tent o~ a metal in the
~orking solutio~ which cannot be ensured otharwise, ~or
e~ample by usi~g naphthenic acid~ ~or the same purpose.
I~ hydrometallurg~ said mixbures o~ polg-branched mono-
carboxylic acids can be used as highly-efficient extraction ..
age~ts for the- recove~y ~nd separation o~ the cation-serie~ :
metals from acidic so~utio~s of salts thereo~. fl~hese mixtures
provide for hi~h separatior- coefficients and a good capacity :-.
o~ the extraction agent, wher~eby productivity of the extrac- ..
tion process becomes substantiall~ increased~ ..
'~herefore, mixtures of poly branchsd monocarbo.xylic acids
can be uæed i~ various branches of inductr~ as a sa~b-~orming .. ~.
agent po~sessin~ spe¢ifi¢, as compared to acid~ of other cha~
racter, prop~xtiss.
~ nown in the art is a process for preparing a mixture of
branched monocarbox;ylic acids o~ the foImula H(CE2CX2~naRR,~C~OH ~` i
~hereln R and R1 ara alky~ groups such as methyl, ethyl,propy} ~:.
ebc. The process comprise~ reacti~g ethylene with lower caxbo- ~
~)'7C1 2~3~
.
xylic acids of a normal structurs corresponding to the ~ormu~a
RC~I2COOH, wherein R is and alkyl group and ~ = 1-25.
~ he process is based on a combination o~ ~elomerizatio~
and radical re-arrangement. In accordance with -this prior art
process mi~ures o~ acids are obtainad i~ one sta~e which mi~~
tures contain two substitu~nts in -the ~ -position and a lo~g
main chain. 'l'his process, however, does not ensure imp~antakion
of substituents i~to the main chain of the acid mo~ecu~e.
Also known in -the art is a process for preparing branched
mo.nocarbo~ylic acids of the ~o~mula: H(CHCH2~n~H~COOH
l1
wherein R is an alky~ ~roup containing 2 to 6 carbon atoms,
R,~ is propy~, butyl, amyl, hexsrl a~d n i~ equal mainitg to 1~
r~he process comprise~ interaction of carboxylic acid~ o~ .
normal and iso-structure with 05-C8 - ~ -olefins. In the case
of utilization o:E carboxyl~c acid~ with ~orma~ structure at the
selected combination o~ the starting rea¢tants (olefin with the
number of carbon atoms of at least 5), re-arran~ement o~
radicals in this pxocess occurs but insigIlificantl~9 whexeby
it becomes impos~ible to obtain 2 substituents in the ~ -posi-
tion at th0 same time with substituents in the main chain.
'~he use of' higher olefins a~ speci~ied ratios between
the olofin a~d acid (i. e. a great e~cess o~ the acid) in . `
this proce~s results mainly in the formation o~ an addltion
product (adduct) 1~
- 2 -
,' .. :
~ . ."
~ :
- : , ~ . . .. ~
1Q'7[)2~39
anly in the ca~e of iso-butyric acid acid~ o~ the ~ormu~a
H(C~aII~)nC(C~I3)2aOOH are obtained7 wherein R1 is an alkyl group~
R1 :`'
and n = 1. ~Iowever9 in this case ît is impossib~e to var~
the chain length and have two substituents in the alpha-posi-
tio~.
The above-described prior art proce~se~ do not provide
~or the prsparation o~ monocarboxylic acids containing ~imulta- :
neousl~ two di~f'erent substituent~ in th~ ~ -po~itio~ in the
carboxyl group and substituents i~ the main carbon chai~
Particularities o~ structure of -the a~ove-list~d acids
H(CH2~2)nCRR1COOH and H(IHOH2)~IXCOOH (n=1) restrict the
~1
.. .
opportunities ~or an ef~sctive application thereo~ ~or the
above-me~tioned purposes.
It is an object o~ the present invention to provide mi~- I
tures o~ po~y-branched monocarboxylic acids ha~ing the ~ormula:
H(OEICH2~nCR1R2COOH, wher~in R i~ methyl or eth~l; R1 is methyl,~
R
ethyl~ prop~ or butyl; R2 is methyl, prop~l, butyl, hexyl or
octyl;~ and n = 1-5~ the acids ranging within the following ~ .
weight proportions: -
at n = 1 10 to 40% by weight;
a-t n - 2 15 to 35~0 by weight;
at n = 3 30 to 10% by weight;
at ~ - 4 25 to 10% by weight;
at n = 5 20 to 5% by weight. ~.
'~ 3 :
~ .
. . . -. . ., - . . . , . .. -: :
~,,, , . , . , . :
. ~, -. . ~-.
,, , "
, : `: : ', ~ ,
,: . ~ - :: . . ~ :
~L07~3Z~g
In accordance with the presen~ invention the proces3 for pra-
paring æaid mixtur~s o~ poly-bxa~ched monocarboxylic acids
resides in reac-ting carboxylic acids of the formula:
R1R2CH COOH, wh~reln R1 is methyl, ethy~, propy~ or butyl;
R2 is hydrogen or methyl, with ~ -o~e~in~ of the ~srmula;
RCH=CH29 wherein R i~ methyl or ethyl, taken in a molar ratio ~,
between the car~o~ylic acid a~d ~ -ole~in equal to 1:0.3-1.5
respectively at a temparature within the rang~ of from 50 to
180C in the pre~ence of a peroxide initia*or taken in an amo
ùnt of ~rom 1 to 5% b~ weight o~ the starti~g carboxylic acid,
with the ~o.rmation of a reaction mixture containi~g the desired
product, followed by ~eparatio~ of ~he latter ~rom said re-
action mixture.
As the carboxylic acids according to the present in~ention,
u~ can be made o~ lower carboxylic acids ~ith normal or iso-
structure such as propionic acid, butyric acid, iso-butyric
acid and the like.
As the ~ -ole~ins accordi~g to the present i~vention
use is made of' propylene or butene~
Undar the above-described co~ditions, radical telome~
zatio~ occurs wi~h said alpha-ole ins and carboxylic acids.
~ he use of C3 or a~ a~pha-ole~'ins in the radical telo-
meriza~ion makes it possib~e to ensure a ~avourable combina-
tion of proces8 ~actors providing~ an intensive re-arrangement
of radicals during the telomerizatio~ thus resulting in a hi~h ;
co~tent o~ acids o~ the ~ormula: H(l CH2)n~R1R2aOOH in the
X ' ' ' :
- 4 - -
.. .
~ . : ~ ; -. :. .
3~070~ 9 ?
xeaction mixture which acids are ~ree of hydrogen atom in
the alpha-position in the carbo}~rl group.
In -the case o:E using higher o~efins with a ~umber of
carbon atom~ o~ at lsast 5 ~ the radical re-arrangemen-t occurs
but to a sub~tantially lesser exte~t.
~ o obtain suf~icient amou~ts of hi~her -telomers in said
mixturQ o:E` poly-branched monocarbogylic acids1 greater amounts
of an olef`ins should be involved in the reactio:~; the l~tter
should be conducted at a molar ratio between the acid a~d ole-
fin equal to 1 O~3-1G5 respectively which corresponds to a
pressure range o~ ~rom 2 to 100 atm. Var~.a-tion o~ the molar
r~tio acid: ole~in withinLj the above-mentio~ed range makes it
possibl~ to vary proportions of lower (n = 1,2) and hi~her
(n above 2) telomers in the resu~tin~ mi~ture o~ acid~, which ;`
is very impo~tant ~or the practical app~ication thereo~.
~s it has been alreadg mentioned hereinabov~, fox the . :
reaction o~ telomeriz~tion use is made of pero~ide initiators.
'rhe process is performed at a te~perature within the xan~;e of
:~rom 50 to 180CJ.
Conce~tration of the ini-tiator is seleeted within the
ra~ge of ~rom 1 to ~% by weight o~ the starting acid. Withi~
said limits, the yield o~ a mi~ture o~ poly-branched monocar-
boxylic acids is proportio~al to the initiator concentration,
which makes it possible to avoid losses o~ such a traluabl~
product as peroxide. Wibh low concentratio~lo~ the initia~or
a ~all con~ersion o~ the acid per cycle is achieved, while
with high concentration~ o~ the initiator unreasonably excessi~i~
:
- 5 -- :~
, ~, - . . .. . ...
,, - ~ - - . . ,. .. ~ . : : .
,, ~
- - ,: :, , , , : : ~:
~cr7~ Z8
vc amounts thereof are consumed~
I-t is advisable to per~'orm the proces~ at a molar rabio
~etween said carbo~ylic acid and olefin e~ual -to 1:0.7-1.
As -the peroxide initiators it is advisable to employ such
compounds as dicyclohexylperoxydicarbonate, ter~$bu~yl pero-
xide. In the latter cas~, the b~st condi-tions are ensured ~o~
the production o~ the d~sir~d produc-t wi~hin the temperature
ra~ge of ~rom 140 to 150C for a perlod o~ ~r~m 1 to 3 hoursO
The process can be performed with th~ same pero~id~ at lower
temperature~ of the order o~ 120~130a for a period of 5-6
hours which enables a ~uller use o~ the initiator~ This~ ~:
howe~er~ results in a longer process duration which is less
efficie~ ~or a co~tinuously per~ormed prOC~S
In the caQe where as the peroxide i~itiator use is made
of dicyclohe~ylpexoggdicarbonate 9 it i9 ad~isable that the
process be conduc~ed at a temperature o~ ~rom 55 to 60C.
Optimal concentration for said peroxide initiators
is a concentration ranging from 2 to ~% by weight of the
starti~g carbo~ylic acid.
Com~i~ation of all the above-listed conditio~s makes it :.
possible to prepare mi~*ure~ of poly-branched monocarboxylic
acids contai~ing Bimultaneousl~ two ~ubstituen~s in the alpha-
position and substi-tuents i~ the main chain of the aGid
molecule with a yield o~ up to ~0% b~ weight per cycle.
The above-me~tio~ed structùràl particularities make it ~:
possible -to provide an effectiv0 use of said acids in dif~e-
- 6 - ;
' ~:
~ 7~ Z ~
rellt appl~cations. ~1hus, u~e o~ tha acids in extractio~ pro-
cesses make~ it possible to achieve, at a certain p~ ~a~u~
substantially ~omplete separation of a mixture o~ sa;Lts
o~ copper and iron, aluminium and iron, a~d the ~ike.
The degree of recover~r o~ aluminium ~rom ~ mi~cture of
salts o~ alumi~ium and iron i~ as high as 99.8709 Therewith,
only 0,18~o Of iron pa~ses i~to the solution~
~ t a p~I value OI about 2-2~5 almost complete separa~lon
of the s~stem copper-iron is ensur~d.
~ he u~e o~ the a`bove~mentioned mix*ure~ o~ acids accord-
ing to the presen~ invention a~ a base ~or the preparation
of siccatives gi~ the ~ollowing results.
Content o~ a lead salt in a solution can be brought to .
as high as 30r5%~ that o-~ rnanganese - up to 10~o~ that of zi~c
tq~i2%.
~ he process a¢cording to the present invention can be
per~ormed both periodicall~ and continuously. ..
~ he process according to the present invention is techno-
logically simple~ it does ~ot require any complicated equip-
ment and is preferably embodied in the followin~ man~er.
Into a ~tandard type au~oclave (either swinging or pro-
vided wi~h a hi~h ~peed impaller) a ~olution o~ a pero~id~ ~-
ini-tiator in a car~oxylic acld is charged and cooled to a
temperature o~ -30 to -50C. 'rherea~ter, alpha-ole~in is added
to -the cooled solution. ~he autoclave is hermetically sea~ed
a~d placed into a heating ~urnace9 wherei~9 under continuous
~winging or stirring, the autoclave contsnts are heated to a
predetermined temperature.On complet~on o~ the reaction, tho
: . , . . . ~. ,.
- ~07~289
autoclave is cooled to room temperature and tha unreacted ga-
seous olefin is re~eased therefrom~ ~he u~reacted ~tarti~g
acid is distilled-o~ rom the resulting reaction mixture~he
remainin~ desired product is vacuum-distilled under a residu-
al pres~ure of 2 to 6 mm Hg.
For a better understanding o~ -the presen~ i~ve~tion, the
following speci~`ic ex~le~ illustrating~ its embodiment~ are
given hereinbelow.
Example 1
Into a s-teel autoclave there is charged a 2~o solution of
tert~-butyl peroxide (16 g) i~ iso-but~ric acid (800 g) and co-
oled to a tempexatur~ o~ -50C. ~he cooled solutio~ is added
with propylene at the molar ratio o~ isobutyric acid: propylene
equal to 1:0.5. ~he au-toclave is hermetically sealed a~d placed
into a heating fur~ace,~iwherein the reactor contents are hea-ted
for 2.5 hours at a temperature ranging fxom 150 to 155C. On
, ~ .
completion o~ the reaction -the autocla~ cooled to room
temperature and tha unr~acted propy~s~e is discharged there
~romO The u~reacted isobut~ric acid is disbilled-o~f from
the r*~ulting reaction mixture. ~he remai~i~g product is
subjec~ed to di~tillatlon thus giving 56 g o~ a mixture o~
the formula: ~ :
h(lHCH2)n a (CX3~2 COOH (~ , where n _ 1-5).
3 :
Tha yield of said mix~ure is 7yO by weight of the starting
isobutyric acid. The boiling range o~ the mixture is 75-190C
under 3 ~m Hg pressur0. ~ = 1.44; aeidic number is 250, mèa~
., .
- 8
107~Z~
moleculare wei~h~ is 220; ethereal number l~
Composition o~ the resul~in~ mixture o~ acids: ~1 25~o b~
weight; '~2 25yO by wel~ht; ~3 20% b~ weigh~; T4 20% b~ weight;
10% by weight.
~xample 2
Into a steel autocla~e -there is charged a 3.8% solu~ion
o~ tert -butyl peroxide (~0 ~) in i~obutyric acid (800 g)
and cooled down to the temper~*ure o~ -50C. The cooled solu
tion is added wi-th propylene iTl the molar ratio o~ isobutDric
acid: propylene equal to 1~ he autocla~ hermetically
sealed and placed into a heating ~`urnace, wherein the auto-
clave contents is heated ~or 3 hour~ at a temperature within `~:
the range of ~rom 1~0 to 150a. 0~ comp~.etion of the reaction, -
.. ~ . . . .
the autoclave is coo~ed to room temperature and the unreacted :gas~ou8 ole~in is discharged therefrom. I'he unreacted isobuty- :
ric acid is distill~d-o~f ~rom the reaction mixtu~e.~he remain-;
ing desired product is distillsd to give, as a reault, 10~.5g
o~ a mi~ture having the ~ormula ~imilar to that o~ ~gampl8 1- `.
~ he mi~turs yield is 13%:by wei~ht o~. the starting isobu- ;
t~Tr~c acidO Boilillg range o~ the mixture is 75-190C u~der ~ ~
mIIL Hg pressure. I12DO - 1.44; aci~ic number is 230; mean moleGular
.. . . .
weight ls 250; ethereal number ls 15. Co~po~ition o~ the re~ult-.
,~ .
ing mix*ur~: ~1 15% by weight; ~2 20% by weigh*; ~3 25~o by
weight; ~4 25~o`by we~ht; ~5 15~o by w9i~ht.
, ., ~
Exampls 3
~ to a ~teel ~toclave thsre i~ ch~rged a 4% ~olutiorl of ;:
terb. butyl peroxide (30 g) in propienic acid ~800 g) a~d cooled
_ g _ :
,
, ~
11~7()2139
down to the temperature of -50~C. r~he cooled ~olu~ion i~ added
with propylene at the molar ratio o~ propionic acid: pxopylene
equal -to 1~ . 'l'he autocla~e is herme~ically sea~ed and placed
into a heating ~urnace~ wherein tha reactor conten-ts are hea-ted
for 2 hours at th~ temperatUre o~ 150-160C. On completion o~
the reaction the autoclave i8 cooled to room temperature a~d
the unreacted ~aseous propylen0 is discharged therefrom ~ rrhe
unreacted propionic acid is dis-tilled-o~ from the resulting
reaction miæture. rl`he remainin~ product is di~tilled to give,
as a result~ 88 g oX a ~ixture o~ acid~ havi~g the ~ollowing
~eneric formula:
1 3
H(CHC~2)~ - C - COOH (~n' where n ~ m - 2-5)~ ;
3 ( 21 )m
rrhe mixture yield iæ 11% by weight of the starting acid; the
boiling raage is 50 to ~70C under 2 mm Hg pres~ure; ~ 44;
acidic numbex is ~20; mea~ molecular weight i~ 260;~ enhereal ;~
number i~ 15. Compositios o~ the resulting mi~*ure is as fol-
lows: ~1 10% b~ weigh-t; '~2 25% by weight; ~ 30% by weigh~;
20% by weight, T3 15~o by weight.
E~ample 4
Into a steel autoclave there i~ charged a 6Yo ~o~ution o~
tert~-butyl peroxide (48 g) i~ bu~yxic acid and csolea to the
temperature o~ ~50C. ~he cooled solu-tion is added with propy-
`'~ .
-~ 10 :
:"
z~
lene at the molar ratio o~ but~ric acid: propy~ene equal to
1:1.5. ~'he autoclave is hermatically sealed and placed in~o a
heating ~urnace, wherein the reactor conte~ts are heated ~or
2 hours at the temperatu~e of 155QCr On completion of the reac~
tion the autoclave is cooled to room temperatur~ and the unxeac-
ted-propylene 19 discharged there~rom. From the resultin~ reac- ~ .
tion mixture the unreactad butyric acid is dis~illed of~ ~o .
give, as a result~ a mixture o~ a~ids having the followi~g
generic formula~
~2 5
H(CE:aH2)n I COOl~ m whe:re ntm = 2-5).
3 (C~2~FI)
~3 : `~
~he resulti~g produot is subjected to ~ractionation to giva,
as a result, 78 g (10~o by weight o~ butyric acid) of a ~raction :
with t~e boiling ~ange o~ ~rom 75 to 1sooa under the pressure
,
of 3 mm Xg~ ~ = 1~4~; acidic ~umber is 250; means molecular
weight is 220, ethereal number i~ 15. Composition of the result~
ing mixture is as ~ol1Ows: T1 15~o b~ weight; T2 20% by weight;
:30~0 by weight~ ~3 20y by`wëigh~; ~3 15.~o by wèiBht~
Example 5
Into a glass flask fltted with a heating ~acket there is
charged a ~.5% solution of tert.-butyl peroxide (15 g) in cap-
ronic acid (92 g) a~a GOOled to a temperature o~ -30C. The
cooled solution is add0d with 25 ml of bute~e-l. Tha flask is :~
;
, , ~ . . . .
1~7~Z~
close~ and its contents aro heated at a tamperature withi~l
the range of :~rom 140 to 1~5C :Eor 6 hour~. On comp~etion o~ the
reaction the :Elask is cooied to room tem~erature and the unreac-: .
ted butene-1 is discharged therefrom. From the resulti~g mix-
ture the unreacted capronic acid i~ distill~d-of:E to give,
as a result~ a mi~ture of acid~ o~ the ~ormulas
1 4~9
H(C~ICH2~ C - COOH
a2~I5 C4H9
( ~ , where n _ 1~5).
~ he resulting p~oduct is subjected to fractionation to
give, as a re~uIt, 15 g (17% by weight of capronic acid) o:E a ;~
~raction with the boiling range of :Erom 50 to 170~C at 2 mm Hg.
~ = 1.44. Acidic number lS 230; aYerage molecular weight is
245; ethereal number îs 13. Composition o~ the resulti~g mix~
ture is the followlng: ~1 15% by weight; ~2 15~o by weight;
25% by weight; ~4 ~5~0 by weight; ~5 0~0 b~ weigh*.
Example 6
Into a ~las~ ~las~ ~itted with a hsating aacket there ls
charged a 4~5% so~ution of dicyclohexylperoxydicarbonate (5 g~
in capronic acid (90 g) and cooled -to a temperature o~ -40C.
~he cooled soLution is added with 30 ml o~` butene-1. Further
stages of the experiment are carried out as in the ~ore~oi~g
Example 5, except that the ~la~k con~ents are heated at a :
temperature o~ ~rom 55 tov60C for the period o~ 5 hours.
'. :
- 12 -
1~702~39
As a result, 13 g of a mixture are obt~ined, which has ~,
characteris-tics similar to tho~e of the mix*ure as obtai~ed
in ~xample 5 hereinabovs, the mixture composltio~ being as
follows: ~1 3~o by weight; T2 25~ by weight; ~3 20Yo by weight;
15% by weight; ~5 10% by weigh-t.
~xample 7 ;:~
Into a steel autoclave there is charged a ~.5% ~olution
of tert -butyl peroxide (5 g) in val~ric ~cid (200 g) and
cooled down to the tempera~ure o~ ~50~C. The cooled ~olution
is added with 60 ml of propylene at the molar r~tio of valeric
acid: prop~lene equal to 1:0.5. ~`he autoclave is hermetically
sealed and placed into a he~ting furnace, wherein the reactor
conte~ts are heated at a temperature within the range of from
120 to 125a ~or a period of 6 hours~ On completion o~ the
reaction the autoclave is cool~d to room temperabure and the
unreacted prop,ylene i~ di~oharged there~rom. From the resulting
reaction mixture the unreacted valeric acid is distil~ed off. ~:
A~ a result, 8 mixture~of acids is obtained, sald mixture
having -the formula:
: ~ 13 7
(~, where n~m - 2-5).
a~ (aH~) H)m
CH3
~ he re~ulting mi~ture is subjected to fractionation bo
give, as a result, 28 g of a mi~ture (13% b~ weight o~ ~aleric
acid) with the boiling rarlgs of from 50C a~ 5 }~ Hg to 195C
~ ,:
,,;,' ~,
- 13 - :
~ ' ' .
.,. . . :, ,.,. : ., . : -
~m6~%~
at 2 mm Hg; nD = 1.46; acidic number is 208; mea~ molacular
wei~ht is 265; ~t~real number is 19. ~he resulti~g mi~ture
has the ~o~lowing composition:
~1 15% ~y wsight; ~ 30% by weight; ~2 25% bg wei~ht;
~`3 15% by wei~h-t; ~3 15~o by weight~
i
Example 8 ;~
The experiment is carried out in the man~er similar to
that described in Example 7 hereinbe~ore, except that the reac-
tor content~ are heated at a temperature within the ra~ge o~ `~
~rom 160 to 1sooa ~or the period of one hour.
~ he yield o~ the thus-prepared mixture iæ 21 g (10% by ,.
weight of the starti~g valeric acid).
~.'.'.
, .
- 14 - :
. ~:
:- . : , . , , . , , , ; . , : .
,
.. .. ..
