Note: Descriptions are shown in the official language in which they were submitted.
~ 3Z6~5
This invention relates to nitrogenous condensation
products and h~drolysis productQ thereof and method~i ~or their
preparation. More specifically, the invention relates to substi- ' -
tuted imidazolines, their hydrolysis products and methods for
their preparationO
The imidazoline products are of the general ~ormulas
27~ '
R,_~2 ~ I IHl_m-R10- (Rl)n ~C
~R CO M2
whsre in
.R is an alkyl or alkenyl group o 5-25 carbon atoms~ :
n is 0 to 4;
wherein m is 0 to 1,
M is ~elected from the group consisting o H or a
. cation, and
~;~. R3 is an alkylene group of 1-5 carben atoms;
LS aach RL is an alkylene of 2-4 carbon atoms and may be
the ~ame or diferent; and
I Ac is selected from the group consisting of the residue
~, ~ . .. .
o~ an ~ uni3aturated dicarboxylic acid o~ 4 to 5 carbon atom~,
the r~sidue of a partial ester of one of said acids, a salt ~f
~aid acid, a ~alt o said partial ester and -R2COOM wherein
j R2COOM i9 the saturated residue of an ~ unsaturated monocarb- -
j ~ oxylic acid wherein M iB as~defined ab~ve and R2 is alkylQne of ~ .
` I -2-
`. : ~, -
.
~3Z~
2 to 4 aarbon atoms: with the provi~o that i~ Ac i3 -R2COOM then
m i~ 1~
Various imidazoline de.rivatives particular~y those hav-
ing amphoteric propertles have been suggested and used ln surfact-
S ant compo~itionsO Thus, in United State3 Patent 3,408,361 o
Hans S~ Mannheimer dated October 29, 196~, aertaln hydroxyethyl
imidazolines are described~ Other art in United State~ Patent . -
i~ U.S~ 2,155,877 to Waldmann (1939) and 2,267,965 to Wil~on (1941)
and U,S. Patent 2,520,102 to Txyon ~1950). The~e imidazoline
produats are obtained ~y reactlng a diamine,for example, one of
tha formula NH2C2H4NHRa-OH an~ a atty acid of generic formula
R-COOH wherein R i8 5 to 25 carbon atoms and i~ alkyl or alkenyl,
~a i~ Rl ~Rlln in whiah Rl is an alkylene o~ 2 to 4 carbon atom~
and n i~ 0 to 4a ~he amines used in preparing the condensates
have primary amino groups and a second primary o~ a secondar~
amino group in 1:2 posltion to each other. In the aforesaid
Una~ed States Patent the diamine and fatty acid are reacted to
r~move water o~ reaation~ When only one mole o~ water is removed
an open-chain produat is ob~ained, considered to be for example,
in the instance where n i5 0 of th,e formula:
IJ ~
- - N - CH2 - C~2 - Rl - OH
H ,~
whiah can bo described as an amide If m~re than ~ne mole o
water i9 removed the imidazoline ring stru~tur2 i9 con~idered to
bs formed giving for exampla, in the in~tancs where n i~ 0,
produot o~ formula:
R- _ N Rl-OH
For a~nvenience the imida~oline ring struature in this speci~lca~
~¦ : - tion i~ formalizedJ the correct ormula i3. ~.
, I .
-3- ::
': .',~ :,
: . .
Z~5
~4)
~3 ~cH2~ ~
t~ I
-C _ _ N-
~2~
The imidazoline aan be aon~erted to the open-~hain ~tructure by
hydrolys~s and in the art ~he~e open-ahain products whether origin-
ally or by hydrolysis are regarded ~rom many aapect~ a3 having the
equivalent properties to the imidazolines although not demonstrat-
ing the clo~ed rlng structure. Moreover, the initial condens3tion
produot generally contain~ a mixture ~ open-chain and ring alo~ad
~imidazo~inel produc~O
The preparatien o~ an imidazolin~ substituted in tha 2-
: lO position ~y a long ahain aliphatic hydrocarbon radical i~ well
descri~ed in the literaturG and is readily ~arxied ou~ by reaction
de~cri~ed above between a carboxylic acid and a polyamine contain-
ing at lea~t on~ primary amino grQUp and at least one secondary
amino group Sinae to obtaln the product o the pre~ent inven-
lS tion it is neaessary to obta~n at ~30me time the hydroxy group on
a l-aliphatic hydroaarbon substituent usually the hydroxy ethyl
typ~ amine i~ de~lrable but a hyd~oxy,group aan be substituted ~ :
on to ~he appropriate 1-alkylene slde-chain by tho~e method~
no~mal in the art~ )
~ nltrogen on ~he ring has bean further reac~ed with
al~ylating agant~ ~or exampla, sodium ahloroaceta~e, ~United
States Paten~ 2,528,378 o~ Mannheimer 1950) to provlde struature~
oon~id~red as having the ~ormula:
~` N ~
R 1! G~ N-Rl-OH "
R3COONa o~
whe~el~ R and R1 are a~3 de~ined abova and R3 i~ an alkyl~ne ~r0up
" -4-
~, .
:`. .
~926Q5
o~ 1 to 3 carbon atoms, for example, methylene.
When in hydrolyzed or open chain form such structures
cou~d be regarded a~ having the structure:
: R - I - CH2 - CH2 - ~H ~ Rl OH
~ 3COONa ..IV
Correspondingly, the imidazolin~s may be reacted with
a monocarboxylic unsaturated acid or ester ~United Kingdom Patent
1,078,101 of Arndt, 1967 and United States Pat~nt 3,555,041 o~
Katz~ to provide structures considered as having the formula:
N~
R-C N_ RlOR2COOH
wherein R and Rl are as defined above and R2 is alkylene of 2 to
4 carbon atomsO ;
When in hydrolyzed or open chain form such structures : ;
could be regarded as having the structure-
"
~; ~ R - 1 1 ~ N - CH2 - CH2 - NH Rlo R2C
As m~ntioned, in United Stat~s Patent 2~528~378 there :~
'' i5 desaribed the preparation of a condensate o~ a diamine with a
- ~atty acid which is then further reacted with a monohalo mono- ~
carboxyli~ acid particularly a metal salt thereof :-
.~ !
: Such pr~ducts have been ~ound to demonstrate ~ariou~ :~
., 20 ~urfaatant or detergent properties and to be useful Ln products
~ re~uiring good ~oaming pr~perties and particularly those requi~
": lng ine bubble structure with good stability, for example,
shampoo compositionsO Nevertheless, despite the improvements
: obtained there is still a need for improvement in foam structure
-( 5_ :.
.. . . .
- , : . .. .. .,. , ~ . , .: . , . ;~ . . . . , .. :
2~
and stability of compositions particularly shampoo composition~.
~he present invention has a~ its objects imidazolines and he re-
lated open chain ~tructures which products can also be described
as modifled condensation products of diamines and fatty acids~
having improved properties for use in detergent or surfaotant com-
positions, ~or example, shampoos~
~ he present invention provides certain nitrogenou~
compounds of the formula:
R - L - Rl ~ ~Rl~)n Ac
: 10 wherein
R, Ac~ n and Rl are as defined above; and
L is selected ~rom the group consisting 0
O ~.
N ~ ~ m and -~ NHl_y~CH2cH2 IN2-~m+q~
~ R3Co2M~ m 3COOM) ~, ~R3cooM) m+q
where in
:, lSm, R3, M and n are as defined above and y is O or lo
Pr~ferably if Ac is the residuP of a monocarboxylic
acid -R2COOM then y~m~q is greater than lo
Generally in these products a preferred fatty acid
used in preparing the condensate is lauric acid giVing R as un-
2 ~ dRcy~ .
Preerably the compounds are of the ~ormula.
N
R~ -CH2-CH2-0-Ac~
wherein
. IR is alkyl of 5 to 25 aarbons and Ac is a re~idue of
' 25 un~aturate~ dicarboxylic acid of 4 to 5 carbons, and particularly
i
. -6-
. . .
.~'' , .
::- , . . :: :
:i ~ , . . : :. : ~ :
2~5
preferred as Ac is the residue from fumaric or maleic acid or
its half ester with an alcohol of 1~6 carbon a~ome~
A preferred hydrolyzed form is of the formula:
O
M3 ~CH~o ~_NH_CH2-CH2-NH2-cH2-cH2-o;
wherein
Ac is a re~idue of an aaid selected from the group con-
sisting o~ ~umaric~ maleic and itaconic acids wherein one of their
carboxylic acid groups may be neutralized with a base or esterified.
Another pre~erred product is
o ~CH2-CH2-0-AC
R- -NH-CH2-CH2~N
~ CH2~p-COONa~m
; wherein
R is alkyl o~ 5 to 25 carbons, m i5 from 1 to 2 and Ac
is a residue of an unsaturated mono or dicarboxylic acid or half
ester thereof and particularly one in which R is undecyl, p is 1
or 2, m i9 ~rom 1 to 103~ and Ac is as defined above or CH2CH2CO2o ~ .
From another aspect the lnvention comprises a modi~ied
aondensatlon product o~ a diamine which is of ~ormula N~12CH2CH2-
NHRa-OH wher~in Ra is as herainbefore defined and pre~erably is
Rl which is alkylene o~ 2 to 4 carbon atom~ with a fatty aaid o~
ormula R-~OOH wherein R is as hereinbefore de~ined which reaction .-
prQduct has from 1 to 2 mol~ o~ water removed during condensation.
Said cond~nsation product o the invention is the basic condensa- ~:
tion product which i9 modi~i~d by condensation with an unsaturat- .
J ed dicarboxylia aaid or a partial ester thereo~O The resulting `
i ~ 25 product can be further modi~ied by alkyla~ien to add the residue
o an alkanoia acid, Instead o~ a dicarboxylic acid the basia
aondensation pr~duct c~n also be modified by cQnden~ation wi~h a
. .,
,
6(~i
monocarboxylic un6aturated acid, but such a reaction product mu~t
be further alkylatad to add the residue of an alkanoic acid.
~hese compounds can be prepared ~rom a conden~ation
imidazoline product as previously described in this speci~ication.
Conden~ate~ and the preparation thereof are described
in detail in the art for example in United States Patent 3,408,361
to Mannheimer, although the preparation of the starting material~
o~ this invention is not confined to such method and any technic-
ally appropriate method for the preparation of such starting
materials can be employedD ERsentially, one method for the prepara-
tion of the starting materials is to condense a diamine and a fatty
acid~ The fatty acids aan be replaced by ester~, amides, anhydr-
`~ ides or aaid halides. When one mole of water i8 removed during
~uch ~ondensation the ~asic product will then be considered to be
o Formula I. More usually~ more than one mole of water is removed
and the product will then be considered to contain an appropriate ::
amount of imidazoline ring struature of Formula II~ Hereinafter
the term condenRate i9 applied to the immediate product o~ ~uch
condonsation of ~atty acid and ami.ne with up to 2 mols of water
being removedO As already indicated a hydroxyalkyl amine can be
employed or tha hydroxy group aan be substituted in the hydroaarbon
' ~ide ahain at the l-position after formation of the condensation
; product by techniques austomary in ~he artO The preferred method,
howev~r, is the u3e of a hydroxyalkyl alkylene polyamine f~r re-
aation with tha fatty acid~
~he nature of the fatty acid residue is preferably a
, .
reQidua of a fatty acid of 6 to 26 carbon atoms~ preferably 8 to
j 22 carbon atomsO Typical acids are coconut, lauric, oleic, tall
i o~l fatty aaids, qteario, sebacic, n-valeric~ isovaleric, caproic,
; 30 hop~oic, caprylic, peLargonic, capric, undecylic, tridecylic, :-
, .
- . . ...... , . .. : , . . . . .. . . -
26;0~i
myristic, psntadyclic, palmitic, margaric, octadecyclic, nona-
decyclic, linoleic, erucic acid, cyclohexyl acetic and arachidic.
Naphthenic and long ahain fatty acids having an aromatic hydro-
carbon radical connected directly to the aliphatic chain may be
employed while certain unsaturated analogues may be used, as can
be substituted analogues, including fluorinated analogues. The
presence of minor or even ma~or amounts of impurity ~uch as the
unsaturated fatty acid~ for instance, is not necessarily detri-
mental and these can be used as ths primary fatty acid. The
fatty acids can also include those obtained from the oils of
fats of animal, marine or vegetable origin including coconut,
palm kernal and palm oil acids which contain fatty acids having
at lea~t 11 aarbon atoms, also from soy bean, linseed, olivs,
rape seed, cotton seed, peanut and castor oil which contain
large proportions of unsaturated hydroxy fatty acids. Mixtures
o~ ~atty acids can be employed. An ester can sometimes be em-
ployed, the alcohol being split off during the reaction and be-
ing removed as by distillation.
While the invention is primarily described in relation
to R1 as ethylene as already indiaated other alkylsne groups of
1 to 6 carbon atom~ can ~e employed for example, propylene,
particularly isopropylene, isobutylene, n-butylene or secondary
butylene and pentylene or hexylene groups depending on the
choica of amine. A preferred amine is aminoeth~lethanolami~e
whiah gives Rl as -CH2-CH2- and another preferred amine i8
A~ aminoeth~lisopropanolamine. The alkylene amide adduats ob~ained
by reaoting a product wherein Ra iq R1-OH with up to 4 mols o~
an alkyl~ne oxide eOg., ethylene oxide or propylene oxide aan b~
employed as the initiaL amine for aondensati~n with the fatty
acid. Polyoxyalkylene amine~ prepared by other technl~ues can
_ g _
. . .
Z~6~)~
al50 be employedO
The pre~ent invention 13 exemplified by a limited
number o~ conden~a~ss. However, in view of the ext2nsive art on
said condensates which are recognized a~ having equivalent
propartie~ it will readily be recognized by those ~killed in th~
art that any given ~atty acid or dlamine a~ exempliied can be
replacad and results obtained whiah are within the noxmal range
o~ properties useable in the pre~ent in~ention.
The con~ensate whether regarded as pure imidazoline or
as a mlx~ure o~ imidazoline and open-chain product or ~imply as
a aondensat2 ~ then reaated to provide tha product~ of the in-
vention. The ba~io condensate is hereinafter referred to as the
condens~te.
Generall~, the condensate i9 a mas~ which although ~olid
at room temperatures can be mel~ed wlthout deaomposition ~ften
at temperature~ below 100Co The initial reaction product of th~
invention with unsatura~ed carbo~ylic acid can be obtained ~imply
:`` by adding carboxylia acid to molten condensate, Preferably,
addltion takes place over a period suf~icient to allow even re-
a~tlon without unnecessary concentration of the acid at any given
tlme r ~he exaa~ rate of addition of ths acid to ~he moltan con-
den~te i~ simply a matter of technical expertise. Th~ xeaction
~ondltion~ ~r the re~tion betwaan un~aturated acid an~ co~densa-
~` tlon produat can vary widely providlng that th~ conditiona are
~u~i~iently ~igorous to initiate the reaa~ion betws2n th~ re-
' . actant~. A temp~rature xang2 of approximately 20C~ to 100Co i~`, available, although at to~ high a temperature one may have degra-
dation o~ 30me produat~ O Th2-unsaturated acid or e~tsr ~hould
~`,`! be addad ~t s~ch rate that the molar concentration in th~ reaa~-
`. 30 ing pro~ at an~ give~ time is ~uch a~ to minimize polymeriza ::
-10- ' - '
.'-
~9;Z~
tlon and particularly self-polyrnerizatio~ The reaction can be
aarried out in solvents or simply by addition o~ the unsaturatsd
aoi~ to the molten mass of aonden~a~ion productO In that the re-
a~tion aan be regarded essentially as a reaction of a hydroxy
gro~p w~th an unsaturated carboxylic acid, those techni~ues
available generally ~or such reactions oan be employed, having
regard to the physiaal properties o~ the reactants.
~he unsaturated dicarboxylic acid~ must have two carb-
oxylio groups on adjacent carbon atoms and either between thess
two carbons or immediately adjacent to them an unsaturated group-
ing. ~he pre~erred acids are those o~ 4 to 5 carbon atoms as
exempli~ied by maleia, ~umario, itaaonioO
The unsaturated dicarboxylia acid residues which can
be employed in the final produat inalude the partial es~ers
khereo up to the hal ester A partial ester can preferably be
~mployed having from 25 to 50% esterification. By 25% esterifica-
tion is meant that in a given amount of acid up to 25% of the
aoid groups present are e~terified and 50% esteri~ication would
~ean that the hal~ ester was formedO A prefexred ester is the
hal~-ost~r c~ "50%" partial esterl While preferably in mo~t
I in~tance~ the partial e~ter would be rsacted with the condenaate
an alternative route would be to react the free acid and then
est~ri~y pa~tially up to 50% the oarboxylio groups in the produ~t.
~arious ~onventional e~terification techniques for use in this
r~action are readily available to those skilled in th~ art. ~n
~ al~ornative technlque is to reaot a full ester and then hydrolyze
I si~h~r to a partial ester ~50% or below~ or oomple~ely to free aaid.
The partial est~rs o the dlcarbo*ylia aaids lnalude
m~thyl ~tors~ ethyl esters and other lower alkyl est0r3 o up
~: '
Z~l5
to 6 carbons, eOgO, hexyl ester~
When the resulting product is prepared substantially
from unhydrolyzed material it can be transormed into a hydrolyzed
product by forming an aqueous solution and hydrolyzing pre~exably
S in the presence o~ a base for instan~e sodium hydroxide, pota~ium
carbonate, ammonia, monoethylamin~, diethylamine, triethylamine
and mono-, di- or tri~ ethanolamine.
The preferred base is ~odium hydroxideO After hydro
lysi~ it is generally desirable to neutralize the base whan used
by addi~ion of an acid, particularly an inorgania strong acid
such as hydrochloria aaid HoweYer, even without hydroly~i~ tho
reaction product of aondensate and a dicarboxylic acid or an e~ter
thereo~ i9 a ~ommercially signiicant productO In neutralizing,
~arious acids can be employed inaluding hydrochloric acid,
sul~uric acid, nitrio acid, although hydroahloric acid ~s pre-
f~rred~ In the ~nal product M, if not hydrogen, can ba one of
: the cations u~ed custom~rily in the art o~ ~urfactant amphoterics
but 1~ cu~omarily an alka'li metal, for example, sodium or
potaq~iwm, but organic bases can also be employedD
In this hydrolysis as indeed in all the hydrolysis re-
action~ describ~d h~rein fis~ion of the imida~.oline ~tructure i~
, most probably be~ween the 2-carbon and l nitrogen but aan al~o
: be speaulated a~ being at least partially betwesn the 2-carbon
and 3-nitrogenO
In many circum~tances a inal commercial product iH .
obtained ~y additlon o~ wat~r to orm a solutionO The pH ~
such solu~ions will generally be from 4 to 10 but i~ usually
~lightly aald particularl~ ~or unhydrolyzed material~ to minlmize
~pontaneous hy~rolysis~
The condensation product can be reacted with a compound .
-12-
`' ' . '
~9926 [95
which generates a residue o~ an unsaturAted monocarboxylic acid
of 3 to 5 carbons for example acrylic acid or methyl acrylate.
The reaction aan be e~feated by ~imple addition of) ~or instance,
the aarylate at a temperature of from 30 to 100C. Thu~, the
acrylate aan be added over a period o~ say one to three hours
~ollowed by heating for rom 1 to 24 hours at from 50 to 110C.
The final proaes~ aan be under vaauum to remove any unreaated
acrylateO The product can then be treated with water and caustia
soda to hydrolyze and neutxalize the acid groups. Acrylate
monomer~ which are ~uitable for reaction may be acrylic acid,
methacrylia aaid, methyl acrylate, ethyl acrylate, methyl meth-
acrylate, isopropylacrylate, aorylamide and/or acrylonitrile.
: ~he reaction i~ found to go to substantial completion under
speclfic aonditions and no par~icular catalyst i5 re~uired since
' 15 it appear~3 that th~ basicity o~ the tertiary nitrogen atoms i3
~u~ficlent to ~e~-catalyze the aarylic monomer adduct reaction.
~ Adduat formatio~ can be obtained in some instances by simple
: addition o~ monomer acrylate to condensate at temperatures near
room temperature although usually it is desirabLe to increa~e
~he tamperature to 60C,-100C, with removal o unreacted m~nomer
under vacuum~ When other than ~ree acids are employed leOg~,
acrylamide or acrylonitrile~ a speciic hydrolysi~ step will be
rs~uired t~ produae the free acid, For example boiling in
.~ aque~u~ system in the pre~ence of a ba~e at 90-100C. until
ammonia .i9 Gompletely removed ~or alcohol for es~ers)0
The maleate and itaconate ~alts and hal-e3ter~ have
l~ttle odor aompared with the a~rylate compound used in exeraiz-
lng U.S. 3~555,041, and furthermore, lea~e little i~ any r~lstant :
odor in the ~lnal produats, wherein the acr~late addltion produats
alway~ have rather strong od~rs atkributable to the aaryla~e addi-
3- :
' '. ~ '~
- . .. .... - ~. . . .. .. .. . .
6~il5ii
tion bi-productsO
- There can be an additional alkylating reaction, e.g.,
with a haloalkanoic acid, for instance sodium chloracetate.
Preferably this reaation is effected wi4h hydrolyzed product~.
Since thi~ reaction involves al]cylation and possible quaterniza-
tion of one of the nitrog~n atoms the reaction is primarily avail-
able with open~chain compounds, iOe " hydrolyzates rather than
th6 imidazolinesO When the original reaction of condensate with
the unsaturated carboxylic acid i8 with a monocarboxylic acid
then 4hi~ additional step is a necessary feature of the invention.
The alk~lation can be carried out in a ~ingle stage in which both
hydrolysis and reaction with a haloalkanoic acid is simultaneous
or there can be an hydrolysis of the product followed by the re-
aotion with an alkylating agent such as a haloalkanoic acid.
lS A reaction with three molq of alkylating a~ent is
visualized as shown in the Formulae substituting onto the 1-
po~itio~ but substitution at the 3~position may be possible with
oon~equent effect on the structure o the hydrolyzed products.
However, even if a 3-position substitution is effected hydrolysi3
may re~u~t in isomerizing to form the same hydrolysis products a~
~he l-substitution,
A reaation wi~h haloalkanoic acid can be carried out
under a variety of c3nditions either in the presence of a 801v-
ent or more usually in the presence of an a~ueous s~tem, For
instanae the ~odium haloaaetate can be added to the hydrolyzed
sy~tem with heating and with or without the addition of a base.
Thus, the condensate reaction product with the un~aturat-
6d carboxyli~ acid can be reaated with a monohalocarboxylic acld
; ~ in the presence o~ ~au~tic ~oda ~odium hydroxide in a~ueou~
gs~lution) . In a preforred form one mol of the reaction mas~
--14--
, ' :'
z~s
added to an aqueous sGlution containing one mol of the monohalo
carboxylia acid and from 2,2 to 205 mols o cau~tic ~oda and the
: mix i5 then heated to a temperature of approximakely~:g~. until
there is no change in p~. The pH normally drops from about 13
; 5 to approximately 8. Additional cau~tic soda i9 added to increase
the ~um of caustic soda to approximately 3 mols and the mass is
maintained until there i5 a sparkling clear solution when adju~t
~d to a pH o~ from 9 to 10,
Another reaction is as described in United State Patent
2,407,645 to Bersworth ~946~ wherein the hydrolyzed condensate
reaction product with un~aturated acid is reacted with an alkali
metal cyanide and a ~ormaldehyde-yielding substance then hydro-
ly%ed to drive off ammonia~ Such a reaction can be u3ed to add
2 mols of alkanoia acid and then one could react wi~h halo~
alkanoic a~id to add a further carboxyalk~l group.
Typical haloalkanoic acids axe the codium or potas~ium
. Balts of chloracetic acid, and ~- or ~chloropropionic acid~.
Fo~ reaction products with dicarboxylic acids up to
three mols o~ alkanoia acid residue can be substituted preferably .:
0-2. For xaaction products of monocarboxylic acids thera must
be some alkylation and again up to three mols can be added but
a preferrsd range is 1-2 molsO :~
In another method o xeacting one can react the basio
condensat~ with the un~aturated acid then simply add water and
2S alkali metal haloalkanoatsO Thereafter add alkali ~e.gO ~ sodium
hydroxide~ and heat o 100C~ for say one hourO
~ ~he $inal products ara genexally o~tained in the ~o~m :~
:: of aqu~ou~ solution and may aontain residue4 of reactants em-
:' ployed in praparing the ~inal product. The adduct o~ unsatu~a~ed :
~cid and cond~nsatlon product can be a commercial product as ~uch
-15-
.
;, ., . :. .
. . . -
~z~
without addition of waterO As is customary in this art the
pure produat i9 often not recovered from the aqueous ~olution
and determination of the structure of the product is an educated
estimate ba~ed on the chemistry involved and the properties of
khe ~olution or adductO
These pxoducts have amphoteric properties wherein the
unreacted condensates are cationic in nature, there~ore a test
~or completion of reaction is the extent to which the final product
~orms clear aqueous solutions at high and low pH values.
The products o the invention, particularly when in
aqueous solution, are of value in various surfactant aompositions
and partiaularly in emulsions, cosmetics, detergents and can be
combined w~th other suractantsO Solutions of the products of
the invention can comprise an aqueous solution with as major
organic aomponents, the product of the invention. The organic
content o~ such a solution can measure from 20 to 90~ by weight
thereo~ for exampl~ 30 to 70%0 The solutions represent finished
products o~ commerce although thay are frequentl~ later combined
. by cu~tomers with other materials to provide compositions or
20 di~erent purposes especially in the fleld of cosmetic compositions.
The product~ o~ the inven~ion are particularly valuable
in shampoo~ in assi~ting in the rendering of conditioning agents
particularly ~or instance, polycationic cellulo~e derivatives, . .
aompa~i~ls with other surfa~tants, for instance sul~atesO More
~... _ ... .
over, certain o the products o~ the invention at the same time
aan assist in improving the skin and hair conditioning pro~ertie~
o~ cosmetic products. The produGts of the invention are general-
ly water-soluble as already indicated but some have the advan-
tage o limited solubility in dilute s~lutionsO
_0 The products ~ the invention as already mentioned can
-16-
I
: .
be in,corporated in co~,metic preparations where it is desired to
emulsify an aquèous phase and the normally lipophilic phase
such as mineral oil, which may be the continuous one, The com-
pounds and their organic ~ulfate complexes are genera~ly non-
S antagonistia toward most cosmetic ingredient~",
Certain of these products can form complexes which may
; be complex salts with organic sulate~i~ e,gO, sodium lauryl
sulphate, sodium pol~oxvethylene (3"5) lauryl sulfates, Rodium
.; polyoxyeth~len,e ¢31 tridecyl sulfateO
The aomp~unds ara useful as hair and skin aonditioners,
; hai~ rinses, creams, fabric ~,o~teners, laundry applications and
aationic imulsifiers and can be gsnerally highly effiaient hair
and skin conditioners generaIly without markedly raducing foam- ;:
ing as do conventional conditioners whe,n used in solutions. The
ratio of aompound employed to water can bs from loOO to 99.9% of
the organic cornpoundO The compounds can al80 be used in textiles :~:
to improve textile finishing
one of the most aative ~reas in shampoo research i9
creating a conditioning property into the shampoo0 It would be
~,~ 20 d,~3irable i the necessity of a po.-~,t-shampoo cream rinse aould
~ be eliminatedO A most effective, and widely used conditioning
:' agent is a polycationic cellulose derivative, for example, one ~.
made by reactiny ,cellulo~,e darivatives with eplchlorhvdrln, then
. aondensing wi~h trimethylamine ~comm,eraially available as
., 25 "Polym~,r JR" which is a Trademark o~ Union Carbide Corp~,)O One
., o~ the preblem~, in using this type o~ resin ~usually at a level
. I
o~ abc~,u~ one per ce,nt o~ the shampoo formu,la) i9 that it is in-
aompatible with many compc,unds used in shampoos which are anioni¢.
h~ prcducts ef this invention ~end t~- couple and com-
0 pa~ibili~e~, suoh resin~ and organic sulfate,s" It i~ a valuable
. .
~ 17
-:',
!: .
. ~, ~ . .
60~
aspeck of the produc~s employing the residues of dicarboxylic
acids and particularl~ partial esters of such unsaturated di-
carboxylic acid~ that they act as coupling agenk~ in shampoo~
; containing such resins and organic sul~ates~ The shampoos
have all the desirable properties of this general type o
produat, foaming and conditioning very well.
Adducts o~ ester~ of maleic acid, hydrolyzed and un-
; hydrolyzed, couple organic ~ul~ates and Polymer JR, to form
clear or nearly clear solutions, whereas adducts prepared ~rom
maleic acid and itaconic acid form homogeneous but cloudy or
pearlescent mixtures.
Adducts prepared from esters of maleic acid also seem
tG foam better than tha other products, when aombined into
shampoo ormulations containing both organic sulfates and Poly-
mer JR Re~in.
Generally, products which are not alkylated may have
~uperior aonditioning properties to alkylated produat~ but the
latter are ~uperior in oaming and lathoringO
The inven~ion will now be illustrated by Example50
It i~ to be understood 1:hat the structures shown ~or
th~ re~idues o~ the ~ un~aturated dicarboxylic aaids ar~ only -.
representa~ive of the various isom~xia forms and are not meant
to limit the claimed scope o the inVontiOn to any specifia i~o- . :
mori~ produat~.
,` '
-18
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EXAMPLE I
: Lauric acid aminoethylethanolamine condensate i~
-. prepared a~ described in Example 1 of TJnited States Patent
3,408,361 by charging aminoethylethanolamine to a vessel contain- -
ing lauric acid heated at about 100C. and a mole of ratio of
said fatty acid to diamine of ~rom 1 to 1.096.
~his product ~ay be con~idered as consisting sub~tan-
tially of a product believed to be o the formula:
'
. .
CH3~CH2)1o ~ ~-CH~CH2OH . ~:
Having regard to the particular method used for making this
product it was considered to have primarily the afore~aid
structure but it will be appreciated that certain small pro-
portions o~ amide be present and different met~oas of preparation
might give greater amounts of amide o~ the structure:
'' ~ ''
; CH3~cH2)lo-~-NH-cH2-cH2-NH-cH2-cH2oH
The approximate molecular weight o~ th~ condensate
starting material o~ the pre3ent invention i~ 268.
P~EPA rIoN o ~LA-~-ON PRODUCT OF ~NVENTION
Lauric Conden~ate plu9 Itaconic ~cid
A glass 1ask e~uipped with stirrer:and thermometer
wa~ chaxged with 1185 g. ~approx. 4.4 mole3) molten c~ndensate.
;~ Over a period of two hours, 664 g. (approx. 5~1 mole~) itaconicacid was 910wly added t~ the mass, s~arting at 55C. and
ending at 71C. Temperature was maintained at 69 to 7~C.,
or 19 ~ours when 1849 g~ o~ water was added. ~he resulting
thin, clear, amber colored prsductp cooled to room temperature
:!
.~ 19 ~ ~ .
: ' ,
had a pH of 4.3.
A 40% aqueoui solution of this material, neutralized
to pH 4.3 to 7 wi~h 50~ NaOH solution, vigorously mas~aged onto
the ~calp and hair a~ter shampooing, foamed copiously, left the
hair, after rin~ing, relatively static- and snarl-free~ with a
s~ooth, 30~t feel.
The active content of this product is ~elieved generally
to conorm the ~ormula:
:
li ~
CH3(CH2)10C ~ -CH2CH2-o-AC9
H
wherein Ac is a saturated residue of itaconic acid,
EXAMPLE IT
Lauric Condensate plus Itaconic Acid, Hydrol~zed
A glas~ ~la~k equipped wit~ stirrer r thermometer
, .
~nd re1ux condenser was charged with 1849 g. (approx. 4.4
moles) o~ the product o Example I just prior to addition of
water. With stirring, the mass WclS heated to 70C. and 1849 g,
o water and 500 g. of 50% aqueous NaOH solution were added,
lowering the temperature to 62C. I~ was heated to 70C. Fi~ty ~ -
per c~nt a~ueous iodium hydroxide solution was added to the
8tirred ma9s at 70 to 72~C., over a three hour period, keeping
the pH, measurad at 30C~, at 9.0 to 9.4. A total o 668 g.
50~ a~ueous sodium hydroxide solution was used. The mass was
co~led and 265 g. o 31.5~ hydrochloric acid ~olution was used
"` to neutralized khe product to pH 7.8. The ~ianl product wa~
25 cle~r and viscous. -
A 40% aqueous ~olution of thi~ material, neutralized
to pH 4 to 7 with hydxochloric a~id, ~igorou~ly masYaged
-20~
. :
`''' '.,-..,-.. '','''`': .'''.''. ~'''.','',
2~
onto the scalp and hair after shampooing, foamed copiously, left
the hair, after rinsing, relatively static- and snarl-frèe, with
a smooth, soft feel.
The active content of this product is believed to con-
form to the ollowing formula: :-
CH3(c~2)lo~-NH-cH2cH2-NH2-cH2cH2-o-A
wherein Ac is as defined in Example II.
EXAMPLE III
Lauric Condensate plus Maleic Acid
A glass flask equipped with stirrer and was charged
with 474 g. (approx. 1.77 moles) molten condensate of Example
I. Over a period of two hour~, 237 g. (2.04 moles) maleic
acid was slowly added to ~he mass, starting at 65C. and
; ending at 73C. ~he mass was maintained at 66 to 74C., for
; 15 19-1/2 hours, when 711 g. of water was added~ The resulting
thin; clear, amber colored product, cooled to room temperature,
` had a pH o~ 2~98.
`` A 40~ aqueous solution of this material, neutralized
:- to pH 4 t~ 7 with 50% NaOH solution, vigorously ma~saged onto
~. 20 the scalp and hair after shampooing, foamed copiously, left
: ~ the hair, after rinqing, relatively static- and snarl-free,
... . .
with a ~mooth, ~oft feel~
~he active content of this product is believed to
conorm to the ormula:
CH3tCH2)10 ~ -CH3CH2-o A ~
-~, wherein A~ is a saturated residue of maleic or fumaric acidO
-21-
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.~9Z~
EXAMPLE IV
Lauric condenRate plu9 Maleic Acid, Hydrolyzed
Example III was repeated using 1232 g. (approx. 4.6
mole~) condensate of Example I, 616 g. ~5.31 moles) maleic acid
and 1849 g. o water. The heating period wa~ 16 hourR at 72~
to 85C. After the water had been added, 555 g. of 50~ ~odium
hydroxide solution was added. ~he mass was heated six hours
at 68 to 72C~, as an addi~ional 100 g. of 50~ sodium hydroxide
solution wa~ 910wly added to maintain the pH at 9.0 to 9.2.
1535 g. Of this inal reaction ma~s was neutralized
to pH 7.58 with 81.0 g. 31.5~ HCl solution.
A 40% aqueous solution o~ thi~ mater~al, neu~ralized
to pH 4 to 7 with 50% NaOH ~oluti~n, vigorously massaged onto
the scal~ and hair after shampooing, oamed copiously, left
the hair, a~ter rinsing, relatively static and ~narl-ree, with
a 3mooth, so~t feel.
The active content of this product is thou~ht gen-
erally to conform to the following formula or one of it~ isomer~:
C~3 (CH2) lo~-N~-cH2cH2-NH2-c~l2cH2-o-cH-coo~3
CH2-COONa
.
EX~MPLE V
Lauric Condensate plus Maleic Acid plu~ Sodium Monochloro-
acetate
A glas~ ~lask equipped with stirrer, thermometer
and conden9~r wa~ charged with 2772 g. (approx. 2.93 mole9)
~ o~ the renction product o Example IV prior to having been
; ~ neutralized wi~h HCl. To this was added 512 g. ~approx.
1 4.39 moles) sodium monochloroace~ate over a 2~ minute period --
;~ be~ween 5ao and 53C. The man~ was heated to 97C.~ over a
l 30 period of 1 lt2 hours, while 512 g. water slowly was adaed
l . ,, ~ .
-22-
~9z~s
and 50% sodium hydroxide solution was added ~o maintain the pH
o the reaction mass at 8~ to 9.4 (measured at 30C.). Stirring
with heating at 97 to 100C., was continued for an additional
2 1/4 hours, maintaining the pH (30C ) at 8.7 to 9~4. In all
a total of 400 g. of 50% sodium hydroxide solution was used,
With coolingr an additional 1000 g. water was added to ~ield
a thin, clear, light amber colored product having a pH of 9.42,
non-volatlle content o~ 41.1% and a sod~um chloride content
o~ 5.02%.
A 40% aqueous solution of this material, neutralized
to pH 4 to 7 with ~1 gave a good head of foam when used as a
hair shampoo, leaving the hair soft and manageable, It was
practically non-irritating to the eyes of rabbits as tested
according to the method of Draize.
~he active content of this product is believed generally
to conorm to the ollowing ormula or one of its isomers:
, ~ ~ ~ H2CH2-0-CH-C~
CH3(CH2)10- NH-CH2CH2 l~\ H2-COONa
H \ (CH2COONa)1-1.5
\ EXAMPLE VI
Lauri~ Conden3ate plu~ Acrylic Acid plu9 Sodium Monochloro-
acetate
A gla~s 1ask e~uipped with stirrer, thermometer
and reflux condenser was charged with 1400 g. (5.22 moles)
~ondensate o Example I. Wi~h ~tirrer, 434 g. (6.03 moles)
aarylic acid was added o~er a 4 hr. 10 min. period at between
65 and 70C~ The mass was stirred and maintalned at 57 to
77C., for 21-1/2 hours, after which 1834 g. water wa~ added.
~¦ ~o 680 g. (approx. 0.97 moles) of this reaction
- material wa~ added 174.8 g. (1.5 moles] sodium monochloro-
acetate ovcr a 20 minute period, rom 50 to 60C~ ~he mass
-23-
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~260~ii
-
was heated ~o 98C~, ovex a period of 1-3/4 hour~, while 50%
qodium hydroxide solution was added to maintain the pH 0~ the
reaction mass at 9.0 to 9.6 (measured at 30C.). Stirring with
heating at 98C., was continued for an additional 3-1/4 hours,
maintaining the pH (30C ) at 9.0 to 9.3. In all a total of
194 g. of 50~ sodium hydroxide solution waq used. With cooling,
175 g. water was added to yield a thin, clear, light amber
colored pxoduct having a pH of 9.36, non-volatile content o
49.4% and a ~odium chloride content o~ 7.22%.
A 40% a~ueous solution o this material, neutralized
to pH 4 to 7 with HCl gave a good head of foam when used
as a hair shampoo, leaving the hair soft and manageable~ It
~ was practically non-irrita~ing to the eyes of rabbits as
: te~ted acco:rding to the method of Draize.
~he active content of ~hic product is thought gen-
erally to conform to the ollowing formula or one of its isomers:
~ ~CH2CH2-0-CH2CH2COO(~
CH3tCH2)10- -NH CH2CH2 t~ ~ CH2~00Na)l 1 5
EX~MPLE VII
A condensa~e is prepared according to Preparation
:~ 20 I rom each o the following acids:
Run 1 Caproic acid
2 Capric acid ~:
~ 3 Myristic acid
.~ 4 Behenic acid ;~
5 Oleic acid
6 Linoleic acid
7 Palmi~ic acid
: .
Eaah o the condensation products is individually
-24-
~; ~.",: '
... : . .
: ., , ~ : . . , ,:
DZS~S
reacted with:
~1~ Maleic acid
~2) Itaconlc acid
(3) Fumeric ac~d
(4) The half ethyl e~ter of malelc acidO
Runs 1, 3 and 7 are repeated wi~h aminoethyliso-
propanolamine and eac~ of the products i~ reacted separately
with maleic acidO
The metho~ emplo~ed is that of Example I in each case.
In e~ah ca6e a product i obtained which is soluble in
water and ha~ good foaming properties.
EXAMPLE VIII
._ .~. :
~ Each of the condensation products of Runs 1 to 7
; i~ reacted with maleic acid and hydrolyze~ following the pro-
cedure o~ Example. IVo A satisfactory produ~t is obtained i~
each cA~e in term~ of foaming pr~pertie60
BXAMPLE IX
Each of the products from the reaction with maleic
I acid i6 hydrs}yzed a~ in Example V and reacted with sodium
ahloroaceta e u~ing the c~ndi~i~ns of Example V. The product
i~ satisfactory in eaoh case in tenms o~ ~oaming properties.
EXAMPLE X
,
Aminc~ ethyl ethanolamine ~NH2C2H4NHC2H4ûH) is re-l
acted a~ ~escribed in United States Patent 2,528,378 to Mannheiner --:
with lauric acid ~Example I~ references are the Examples ~f
~,528,378, capric acid (Example 3~, linsee~ fatty acid
(Example ~), caproic acid ~Example 5), stearlc acid (Example 6),
d~decyl banzoic acid (Example 7), myristlc acid (Example 8).
~he~ea$ter each Qondensate ob~ained .~5~ reàcted :~ .
'30 with ~ne of ~he following unsaturated carboxylic
: -25- :~
091126(~S
acids, maleic, fumaric or monoethyl maleate following the pro-
cedure of present Example I~
Each of the products when formed into ~olution as in
Example I have satisfactory foaming propertie~. The condensates
5 with lauric acid and caproic acid are reacted with acrylic acid
as in Example VI and the resulting product is then reacted with
i~ one instance sodium chloracetate and in the second instance
with sodium bromopropionate following the procedure of Example
VI to obtain an aqueous solution. The resulting solutions have
10 satisfactory foaming properties.
EXAMPLE XI
A glass flask equipped with stirrer and t~ermometer
waB charged with 938 g. ~approx. 3,5 moles3 molten condensate.
Over a period of about two hours, 616 g. (approx. 4 moleg~ of
a 94~ ethanol solution of monoethylmaleate was 810wly added to
the mass, startin~ at 60C. and ending at 73C. The tempera-
- ture was maintain~d at 70C. to 75C., for about 22 hours.
1554 G. water was added, to yi~ld a clear, ligh~ am~er li-~uid
having a pH of 4.1 and a solids con~ent of 46.7~.
EX~PLE XII
Lauric Conden~ate plus Eth~l Maleat~, ~y~rol~zëd
`~ 2138 G. of the product of Example X wa~ heated, ~i~h
stirxing, with 122 g. 50~ NaOH, to 90C., the boiling point of
~` 25 the solutionO ~ ~otal of 300 ml~ distillate was collected and
replaaed ~ith water as the temp~rature 810wly rose to 100C.
Fifty per cent NaOH was added during this time to ~ep th~ p~
above 9Ø A total of 339 g. of 50~ NaOH was used i~ all. When
the boiling point of 100C. was reached, indi~ating ess~ntiall~
. . .
all tho oster was hydrolyzed and th~ ethan~l ~a~oved, and the
-26-
~1~9Z6~5
reaction product was cooled, 300 ml~ of water was added ~ack ~o
the reaction mass. The resulting clear, amber solution has a
pH of 10.0 and a solids content of 44.3%.
EXAMPLE XIII
~
To 10 mols of the produc~ of Example III is add~d 4
; mols of caustic soda, eight mols of sodium cyanide are added and7.5 mols of formaldehyde are added. The conditio~s and methods
of addition are as descri~d in Example I of United States Patent
2,407,645. Addition of sodium cyanide and forma~dehyde is rQ-
peated after evolution of ammonia ceases for each batch addition.
The resulting product in aqueous soltuion has excellent fo~ming
properties, -
EX~MPLE XIV
A numb~r of example~ of shampoos were prepared. S~me
typical formulations follow:
% bY w~ % aati~e
~ . . . ~ ,
A~ Condensate of lauric acid and
aminoethyl~than~lamine react-
~d with monoethylmaleate,
hydrolyzed 22,6 1~.0
Sodium polyoxyethylene ~3)
tridecyl sulfate 11.6 8.~
Polymer JR 400, 2~ aq. soln. 50.0 1.0
Water 15 8 0
g, O .
neutralized to pH 6.7 with
ECl,
This shampoo formula is ~ clear, syrupy liquid whlch foams very
woll whsn u3ed as a hair shampoo. After rinsing, the hair i~
loft with exceptional wet-comb and untan~ling properties~
:,~
:~
; :
~ -27-
:` ~
~L09Z605
Product of Invention ~ ~ active
.
B. Condensate of lauric acid and
amino~thylethanolamine react-
ed with monoethylmaleate, un-
hydrolyzed 30.0 14.0
C. Condensate of lauric acid and
aminoethylethanolamine react-
ed with monoethylmaleate,
hydrolyzed 31.6 14.0
D. Conden~ate of lauric acid and
aminosthylethanolamine react-
ed with monoethylmaleate 29.2 14.0
E. Condensate of lauric acid and
aminoethylethanolamine react-
ed with monomethylmaleate,
hydrolyzed 29.6 14.0
Sodium polyoxyethylene (3.5)
lauryl sulfate 20.0 5.0
Polyme:r JR-400 1.0 1.0 ~.
Water q.~. 0
all neutralized by pH
: 6,7 wi~h either NaOH
~ or HC1.
S Results:
B, Clear, syrupy liquid with good cream rinse action and con-
d~tionin~ properties when used as a hair shampoo. :
C. Very slightly hazy, syrupy liquid. Good wet-comb and un-
tangling pr~perti~s wh~n used as a hair shampoo.
D. Very slightly haz~, syrupy liquid. Very goad cream rin~e
action and wet-comb properties when used as a hair shampoo.
E. Very slightly hazy, syrupy liquid. Very good wet-aombing
25 properties when used as a hair skampoo.
%_~y wt. % active
Condensate of lauric acid and
aminoethylethanolamine r~act-
: ~d with monoi~opropylmaleate26.8 12~7
Sodium polyoxyethylene (3.5)
lauryl ~ulfate 18.2 4.6
30 Dimathylcocoamine oxicle 9.1 3.6
-28-
632605
%_~ Y activ~
Polymer ~R-400 0 . 9 0, 9
Water 4 5 .
neutralized to pH 6 . 7 with
NaOH.
This is a very slightly hazy, syrupy liquid, which foams well
when used as a hair shampoo.
' :
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