CA1070289A - Mixtures of poly-branched monocarboxylic acids and process for preparing same - Google Patents
Mixtures of poly-branched monocarboxylic acids and process for preparing sameInfo
- Publication number
- CA1070289A CA1070289A CA252,178A CA252178A CA1070289A CA 1070289 A CA1070289 A CA 1070289A CA 252178 A CA252178 A CA 252178A CA 1070289 A CA1070289 A CA 1070289A
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- Prior art keywords
- methyl
- ethyl
- butyl
- weight
- acids
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/126—Acids containing more than four carbon atoms
- C07C53/128—Acids containing more than four carbon atoms the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract of the Disclosure Mixtures of poly-branched monocarboxylic acids of the formula: H(?HCH2)nCR1R2COOH, wherein R is methyl or ethyl;
R1 is methyl, ethyl, propyl or butyl; R2 is methyl, propyl, butyl, hexyl or octyl; n = 1-5; at the following weight pro-portions of the acids:
A process for preparing a mixture of poly-branched mono-carboxylic acids resides in reaction of a carboxylic acid of the formula R1R2CHCOOH, wherein R1 is methyl, ethyl, propyl or butyl; R2 is hydrogen or methyl, with alpha-olefins of the formula RCH=CH2, wherein R is methyl or ethyl, at a molar ra-tio of said carboxylic acid: alpha-olefin equal to 1:0.3-1.5 respectively at a temperature within the range of from 50 to 180°C in the presence of a peroxide intitiator taken in an amount of from 1 to 5% by weight of the starting carboxylic acid to form a reaction mixture containing the desired pro-duct, followed by separation of the latter from said reaction mixture.
The mixture of acids according to the present invention are highly-efficient extraction agents in hydrometallurgy.They are also valuable components for the preparation of paint compositions. The process for preparation of said mixtures is one-staged and technologically simple. This process in-volves no production wastes or waste waters.
R1 is methyl, ethyl, propyl or butyl; R2 is methyl, propyl, butyl, hexyl or octyl; n = 1-5; at the following weight pro-portions of the acids:
A process for preparing a mixture of poly-branched mono-carboxylic acids resides in reaction of a carboxylic acid of the formula R1R2CHCOOH, wherein R1 is methyl, ethyl, propyl or butyl; R2 is hydrogen or methyl, with alpha-olefins of the formula RCH=CH2, wherein R is methyl or ethyl, at a molar ra-tio of said carboxylic acid: alpha-olefin equal to 1:0.3-1.5 respectively at a temperature within the range of from 50 to 180°C in the presence of a peroxide intitiator taken in an amount of from 1 to 5% by weight of the starting carboxylic acid to form a reaction mixture containing the desired pro-duct, followed by separation of the latter from said reaction mixture.
The mixture of acids according to the present invention are highly-efficient extraction agents in hydrometallurgy.They are also valuable components for the preparation of paint compositions. The process for preparation of said mixtures is one-staged and technologically simple. This process in-volves no production wastes or waste waters.
Description
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~
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 ' ' ' :
.. .
~ . : ~ ; -. :. .
~ . ."
~ :
- : , ~ . . .. ~
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 ' ' ' :
.. .
~ . : ~ ; -. :. .
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~
., .
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:
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.
'. :
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 ~ 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 - :
. ~:
:- . : , . , , . , , , ; . , : .
, .. .. ..
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~
., .
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:
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.
'. :
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 ~ 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 - :
. ~:
:- . : , . , , . , , , ; . , : .
, .. .. ..
Claims (7)
EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED
AS FOLLOWS:
1. Mixtures of poly-branched monocarboxylic acids having generic fonmula: H(?HCH2)nCR1R2COOH
wherein R is selected from the group consisting of methyl and ethyl; R1 is selected from the group consisting of methyl, ethyl, propyl and butyl; R2 is selected from the group consist-ing of methyl, propyl, butyl, hexyl and octyl; n = 1-5;
weight proportions of the acids being as follows:
wherein R is selected from the group consisting of methyl and ethyl; R1 is selected from the group consisting of methyl, ethyl, propyl and butyl; R2 is selected from the group consist-ing of methyl, propyl, butyl, hexyl and octyl; n = 1-5;
weight proportions of the acids being as follows:
2. A process for preparing mixtures of poly-branched mono-carboxylic asids having the generic formula:
H(?HCH2)nCR1R2COOH
wherein R is selected from the group consisting of methyl and ethyl; R1 is selected from the group consisting of methyl, ethyl, propyl and butyl; R2 is selected from the group consist-ing of methyl, propyl, butyl,hexyl and octyl; n = 1-5;
weight proportions of the acids being as follows:
at n = 5 20 to 5% by weight, comprising interaction of carboxylic acids of the formula:
R1R2CHCOOH wherein R1 is selected from the group consisting of methyl, ethyl, propyl and butyl; R2 is selected from the group consisting of hydrogen and methyl, with alpha-olefins of the formula RCH=CH2, wherein R is a radical selected from the group consisting of methyl and ethyl, at a molar ratio between said carboxylic acid and alpha-olefin ranging from 1:0.3 to 1:1.5 respectively, at a temperature within the range of from 50 to 180°C in the presence of a peroxide initiator taken in an amount ranging from 1 to 5% by weight of the starting carboxylic acid to form a reaction mixture containing the desired product, followed by separation of said desired product from the resulting reaction mixture.
H(?HCH2)nCR1R2COOH
wherein R is selected from the group consisting of methyl and ethyl; R1 is selected from the group consisting of methyl, ethyl, propyl and butyl; R2 is selected from the group consist-ing of methyl, propyl, butyl,hexyl and octyl; n = 1-5;
weight proportions of the acids being as follows:
at n = 5 20 to 5% by weight, comprising interaction of carboxylic acids of the formula:
R1R2CHCOOH wherein R1 is selected from the group consisting of methyl, ethyl, propyl and butyl; R2 is selected from the group consisting of hydrogen and methyl, with alpha-olefins of the formula RCH=CH2, wherein R is a radical selected from the group consisting of methyl and ethyl, at a molar ratio between said carboxylic acid and alpha-olefin ranging from 1:0.3 to 1:1.5 respectively, at a temperature within the range of from 50 to 180°C in the presence of a peroxide initiator taken in an amount ranging from 1 to 5% by weight of the starting carboxylic acid to form a reaction mixture containing the desired product, followed by separation of said desired product from the resulting reaction mixture.
3. A process as claimed in Claim 2, wherein the reaction is carried out at a molar ratio of carboxylic acid: alpha-olefin equal to 1:0.7-1.
4. A process as claimed in Claim 2, wherein as the peroxide initiator use is made of an initiator selected from the group consisting of tert-butyl peroxide and dicyclohexyl-peroxydicarbonate.
5. A process as claimed in Claim 2, wherein the reaction is carried out in the presence of tert-butyl peroxide at a temperature ranging from 140 to 150°C.
6. A process as claimed in Claim 2, wherein the reaction is carried out in the presence of dicyclohexylperoxydicarbo-nate at a temperature ranging from 55 to 60°C.
7. A process as claimed in Claim 2, wherein said peroxide initiator is taken in an amount ranging from 2 to 4% by weight of the starting carboxylic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU752130253A SU615059A1 (en) | 1975-05-19 | 1975-05-19 | Mixture of polybranched monocarboxylic acids as salt-forming agent and method of obtaining same |
| JP5772476A JPS52142008A (en) | 1975-05-19 | 1976-05-19 | Mixtures of poly branch monocarboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1070289A true CA1070289A (en) | 1980-01-22 |
Family
ID=26398787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA252,178A Expired CA1070289A (en) | 1975-05-19 | 1976-05-11 | Mixtures of poly-branched monocarboxylic acids and process for preparing same |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS52142008A (en) |
| AT (1) | AT347420B (en) |
| CA (1) | CA1070289A (en) |
| CH (1) | CH629174A5 (en) |
| DE (1) | DE2621526C3 (en) |
| DK (1) | DK218676A (en) |
| GB (1) | GB1553702A (en) |
| NL (1) | NL7605350A (en) |
| SE (1) | SE411895B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1339034C (en) * | 1988-08-22 | 1997-04-01 | Paul A. Tremblay | Platinum complexes of single isomer neoalkyl acids |
| ZA933123B (en) * | 1992-05-06 | 1993-11-30 | Shell Res Ltd | Saturated, monocarboxylic acids, the preparation thereof, and derivatives therefrom |
| JP2001520304A (en) | 1997-10-23 | 2001-10-30 | ザ、プロクター、エンド、ギャンブル、カンパニー | Fatty acids, soaps, surfactant systems and consumer products based on them |
| WO2000007971A1 (en) * | 1998-08-06 | 2000-02-17 | Exxon Chemical Patents Inc. | Neo carboxylic acids and a process for their preparation |
| US6890894B2 (en) | 2000-02-22 | 2005-05-10 | The Procter & Gamble Company | Fatty acids, soaps surfactant systems, and consumer products based thereon |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5623973B2 (en) * | 1972-02-12 | 1981-06-03 |
-
1976
- 1976-05-11 CA CA252,178A patent/CA1070289A/en not_active Expired
- 1976-05-12 CH CH595876A patent/CH629174A5/en not_active IP Right Cessation
- 1976-05-14 DE DE2621526A patent/DE2621526C3/en not_active Expired
- 1976-05-18 DK DK218676A patent/DK218676A/en not_active Application Discontinuation
- 1976-05-18 SE SE7605626A patent/SE411895B/en not_active IP Right Cessation
- 1976-05-19 JP JP5772476A patent/JPS52142008A/en active Pending
- 1976-05-19 NL NL7605350A patent/NL7605350A/en unknown
- 1976-05-19 AT AT364676A patent/AT347420B/en not_active IP Right Cessation
- 1976-05-19 GB GB20754/76A patent/GB1553702A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CH629174A5 (en) | 1982-04-15 |
| DK218676A (en) | 1976-11-20 |
| DE2621526A1 (en) | 1976-12-30 |
| GB1553702A (en) | 1979-09-26 |
| DE2621526B2 (en) | 1980-06-26 |
| NL7605350A (en) | 1976-11-23 |
| JPS52142008A (en) | 1977-11-26 |
| SE411895B (en) | 1980-02-11 |
| AT347420B (en) | 1978-12-27 |
| DE2621526C3 (en) | 1981-02-26 |
| ATA364676A (en) | 1978-05-15 |
| SE7605626L (en) | 1976-11-20 |
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| MKEX | Expiry |