' John David Malkemiis, sue dale, N. J., assignor
to Colgate-Palmolive-Pcet Company, Jersey
City, N. 3., a corporation of Delaware
Application December 29, 1945,
Serial No. 688,470
10 on
The present invention relates to new synthetic
detergent compositions of the type of modified
sulphated and sulphonated organic materials hav
ing improved surface-active characteristics, and
to a process for producing said compositions.
Inorganic builders, such as carbonates, phos
phates, etc., have been employed with synthetic
detergents for modifying pH,>and various other
inorganic compounds are useful as extenders, but
such materials have not been found fully ade
quate, in general, for improving the surface
'
(in. 252-152) ‘
2
terials which are applicable for sulphonation
("true” sulphonation and/or sulphation), espe
cially those having about eight to about twenty
six (and preferably about twelve to about twenty)
carbon atoms to the molecule, including fatty oils,
unsaturated fatty acids, mineral oils, mineral oil
extracts, mono- and diglycerides, partial esters
or ethers of polyglycols, esters or ethersi of glycols,
polyglycols and polyalcohols, aromatic and al
10 kylated aromatic compounds, alcohols and ole
?nes, coal tar distillates, and numerous other
active characteristics of the synthetic detergent
to whicli'they are added. Thus, the use of these
organic compounds and mixtures of compounds.
Such compounds can be sulphonated by any of
inorganic builders with synthetic detergents does
several methods and may form any of several
not provide appreciably improved foaming and 15 products, depending upon the method of col»
detergency characteristics.
phonation employed. The sulphonated or sul
It has recently been found that certain organic
phated organic compounds include sulphonated
bodies, when added to synthetic detergents of the
type of sulphated and. sulphonated materials,
modify the properties of said detergents, espe
cially with respect to their foaming characteris
mineral oil; conventional mineral oil re?nery
sludges; sulphonated mineral oil extracts; sul
phonated fatty acids and oils, including sul
phonated castor oil, sulphoricinoleic acid, sul
phonated olive oil, and sulphooleic acid; aliphatic
tics. Such modi?cation is very valuable and use
ful in many ?elds, but, so far as is known, no
sulphonates and sulphates, including cetyl sul
signi?cant improvement in detersive properties
phuric acid, dodecyl acid sulphate, and tetra
accompanies the improved foaming charac
decanehydroxy sulphonic acid-1,2; aliphatic
teristics.
ether and ester sulphonates including the dodecyl
‘
ether of hydroxy ethyl sulphonic acid, the cetyl
It is an object of the present invention to pro
vide novel surface-active compositions of rela
ether of glyceryl sulphonic acid, and coconut oil
tively high detersive eiiiciency.
monoglyceride monosulphate; sulphonates pre=
It is also. an object of this invention to pro
30 pared by treatment of organic materials with sul
vide a modi?ed anionic surface-active agent
phur dioxide and chlorine in the presence of light
havingimproved detersive characteristics.
It is another object of the invention to provide
a novel method for producing new organic surface
active compositions of high detergency.
Other objects and advantages of this inven
tion will be apparent from the following descrip
tion.
' followed by hydrolysis of the product; sulphonates
prepared by treatment of organic bodies with
sulphuryl chloride and an activating agent in
35 the presence of light followed by hydrolysis of
the product; fatty acid amides of amino alkyl sul
phonic acids, including lauric'amide of taurine
and tall oil acid amide of amino glyceryl sulphonic
acid; sulphonic acids of naphthenes and naph
-
According to the present invention, it has now
been found that the incorporation of a proportion
40
of a cationic surface-active agent, such as an
aliphatic carboxylic acid monoester or aliphatic
monoether derivative of a N,N'-dialkanol piper
azine, with a non-soap anionic surface-active
compound such as detergents, emulsi?ers and
wetting agents of the type of sulphated or sul
phonic acid; the product of a mineral oil extract
sulphonated while dissolved in liquid sulphur
‘ dioxide; and innumerable other organic sulphonic
phonatezi organic materials, provides a composi
.and sulphuric acid derivatives or'mixtures there
of. These organic sulphate and true sulphonate
compounds include those in which the organic
tion with markedly enhanced detersive charac- _
teristics. Similarly, incorporation of a propor
tion of the sulphated or sulphonated material de- -
scribed with the piperazine derivative modi?es
its surface-active characteristics.
The sulphated or sulphonated organic com
pounds comprised by the novel compositions of
the invention may be prepared from organic ma
thenic acids; lignin sulphonic acids; aromatic
and alkylated aromatic sulphonic acids, including
naphthalene sulphonic acid, octadecyl benzene
sulphonic acid, and dodecyl naphthalene sul
radicals of the molecule are unsubstituted or
those which contain substituents, such as hale
ogens, halogenoids, hydroxyls. nitrogen-contaim
ing groups, acyl groups, acyloxy groups, alkoxy
groups, etc.
55
~
The aliphatic carboxylic acid monoester or
> sea-‘ea,
monoether derivatives of N,N'-dialkanol piper; " phonated ingredient. may‘ be ,used. in‘ all; 'propor-' - '
azines, which may be added to sulphated and/or
tions,-in general rangingfrom about.1% to, about",
sulphonated compounds to achieve the desirable- , ' 509%,
it. is preferredto incorporate about-109% results described, are those represented by the
to about 200%, and more preferably about 20%
general structural formula:
'
to 100%, of monoester or monoether-- based upon: '
the weight of‘sulphonated material. The opti
mum proportion employed-‘will vary 'with the par- ‘ '
ticular active ingredient or mixture of- active in
gr'edients used; with thevfproportion ‘of other 4'
where R is an alkyl or acyl radical having about 10 ingredients present, if any; and to some degree
?ve to about twenty-three, preferably about eight
with the strength or concentrationof solution
to about eighteen, carbon" atoms; A and Bare ) to be formed in use;
ethylene radicals wherein any number of by:
The diaikanol piperazine monoester or mono
drogens (none, one or more) maybe replaced by
ether may be incorporated with the active sul
allgvl radicals, preferably of not more than two
phonated ingredient to form the novel compo
carbon atoms; and m and n are small integers.
sition of thisinvention at any point during the
say 2 to about 5, preferably 2. The carbon chain
vmanufacturing process at which subsequent
represented by B may be straight or branched,
operations will not destroy or objectionably mod
saturated or unsaturated, and may be either un
ify the monoester or monoether or cause a
substituted or substituted by substituents such 20 deleterious reaction between the same and any
as halogens, hydoxyls. acyl groups, acyloxy '
other material in the composition. In general,
groups, alkoxy groups, nitrogen-containing
it is preferred to add the piperazine derivative
groups, heterocyclic groups. alicyclic groups, aryl
at a point in the manufacturing subsequent to
groups, etc., although it is generally preferred
the hydrolyzing 'and/or neutralizing step. This t i
that substituent groups of hydrophilic character 25 may be accomplished by adding the piperazine
be located near or adjacent to the piperazyl alkoxy
derivative in solid form or in solution ‘to solutions
containing the active sulphonated ingredient or.
group. Where R is an alkyl or substituted alkyl
group, the organic builder 'is an ether; and where .
by adding the sulphonated ingredient in solid
R is an- acyl or substituted acyl group, the com
form or in solution'to solutions containing the
pound employed is an ester.
-
30 piperazine derivative to form concentrated solu- .
tions or solutions ready for use; by mixing the
piperazine derivative with the solid sulphonate'd
ingredient in comminuted form; or by‘ adding
In the case of the compound’s being an ester,
the acyl group may be the residue of any suitable
carboxylic acid, including lauric acid, myristic
acid, palmitic acid, stearic acid, hydroxystearic
acid, oleic acid, iinoleic acid, linolenic ‘acid,
ricinoleic acid, caproic acid, isocaprylic acid,
a-aminocapric acid, undecylenic acid, lignoceric
acid, erucic acid, lauryl succinic acid, chloro
palmitic acid,‘ mixed coconut oil fatty acids,
the piperazine derivative to a solution of the sul
phonated ingredient and thereafter subjecting _
the solution containing active sulphonated in- .
gredient and piperazine monoester or monoether
to spray-drying, roll-drying, etc., to form a solid
' composition.
acids, etc. Where the compound is an ether, the
- Thus, the novel compositions provided may be
made up in solutions, preferably concentrated,
alkyl group may be any corresponding to a suit
or a dry or partially hydrated solid product or a'
able carboxylic acid, such as the above-men
paste may be formed. The product may be‘ made ‘
in a more or less ?nely divided condition, which
- mixed tallow fatty acids, mixtures of any of these
40
tioned, including lauryl, myristyl, palmityl,
stearyl, hydroxystearyl, oleyl,‘ linoleyl, linolenyl,
ricinoleyl, hexyl, isooctyl, p-aminodecyl, etc.
permits its ready transformation into ?akes or
The dialkanol piperazine residue of the ester or
ether employed may be symmetrical or mixed.
tween a pair of properly spaced rolls, or by mill
ing or pressing into cakes, or by other means,
other physical forms, for example by passing be
That is, m and n may be the same number or
with or without addition or modifying agents. _
they may be different numbers. In general, it is 50
Adjuvant materials may be-admixed with the
preferred to employ symmetrical N,N"-dialkanol
sulphonate salts by mixing the adjuvant mate
piperazines, such as N,N'-diethano1 piperazine,
rials with the sulphonated organic compounds
and/or the neutralizing agents before ‘neutrali-'
zation or flashing, by simultaneously flashing a
N,N'-dipropanol piperazine, N,N'-diisopropanol
piperazine, 3,6-dimethyl-1,4-(p-hydroxy ethyl)
piperazine, 3,6-dimethyl-l,4-di(p-hydroxy pro
55
pyl) piperazine, etc., and especially the symmet
rical dialkanol piperazines having both hydroxyl
groups in omega position with respect to the
piperazyl radical. However, mixed piperazines
of the type of 1-?~propanol-4-,8-ethanol pipera
zine, l-?-ethanol-éw-butanol piperazine, etc.,
can also be used.
'
second solution containing such adjuvant ma
terials, and/“or by mixing ‘the ?nal product there
with. When added. after neutralization, the
adjuvant materials may be added before, after,
or simultaneously with the dialkanol piperazine
60 derivative.‘ Such adjuvant materials may include
any of the substances employed by the art in-ad
'
mixture with sulphonated organic , detergents
7 Suitable esters for use in the compositions of
generally, care being exercised to avoid the use‘
this invention include N,N'-diethanol piperazine
monolaurate, ricinoleic acid monoester of 3,6
of any material which would remove orotherwise
substantially diminish the e?ectiveness of the
dimethyl-lA-dK?-hydroxy propyl) piperazine,
di-w-butanol piperazine vmonostearate, coconut
dialkanol piperazine monoester or monoether in--v I
corporated. The type of addition agent will de
oil fatty acid monoesters of N,N'-diethanol pi
pend upon the ultimate use of the new compo
perazine, etc. Ethers suitable for employment in ‘ sition.
the novel compositions include l-(?-lauroxy 70 Certain inorganic builders, such as sodium
ethyl) -4-(p—hydroxy ethyl) -piperazine, 3,6-di
methyl -1- (p-myristoxy propyD- 4.- (?-hydroxy
propyl) -piperazine, etc.
‘ '
While mixtures of the N,N'-dialkanol pipera
zine monoester or-monoether with active sul
_
,
phosphate, sodium pyrophosphate, sodium car
bonate, and the like, which raise the pH .of the
composition in solution may advantageously be
added, as will appear hereinafter. other inor
75 ganic builders which do not appreciably‘ aifect
the pH, such as sodium chloride, sodium sul
phate, etc., serve as extenders.
The novel and improved synthetic detergents,
emulsi?ers and/or wetting agents of this inven
tion, comprising sulphated and/or sulphonated
organic compounds (with or without adluvant
materials) and a proportion of the diallranol pi
perazine monoester and/or monoether described,
produce solutions which, under controlled condi
tions, have higher detersive e?iciency than either
the active sulphonated ingredient or the mono
ester or monoether alone. Thus, employing a
standard multiple swatch launderometer test on
wool soil at 105° C. over a five-minute period,
the detersive e?ciencies of (a) a synthetic de
tergent comprising 40 parts by weight of coconut
oil monoglyceride monosulphate sodium salt to
60 parts of sodium sulphate, (b) a composition
comprising approximately 50% coconut fatty
acid monoester of diethanol piperazine, and (c)
a novel composition according to the present in
The solution containing 00% of monoglyceride
monosulphate agent and 10% or diethanol piper
azine monoester is then adjusted from a DH of
8.8 to a pH of 10.4 by addition of sodium pyro
phosphate, and the detersive e?iciency, upon re
determination, is found to have increased to 93% .
EXAMPLE II
The monosulphate Of monogylcerides of coco
nut oil fatty acids, as prepared, is purified by
extraction with ether and is dissolved in water
to form an aqueous solution containing about
40% by weight of solids. Oleic acid monoester of
N,N'~diethanol piperazine in an amount equiva
lent. to about 10% by ‘weight of said active sul
phated ingredient is added to the solution. The
solution is then roll-dried to produce a surface
active material having excellent detersive charac
20 teristics in aqueous solution.
vention comprising about 70% of the synthetic
EXAMPLE 111
detergent (a) and 30% of the composition (b)
were compared. These materials (a), (b) and
One part by weight of 1- (?-lauroxy ethyl) 4-03
(ciwere made up in aqueous solution of about 25
hydroxy ethyD-piperazine is added to about 20
equal concentration, the pH of solution (0) being
adjusted to a pH of 6.0. It is notable that, while
solution (a) showed a detersive e?iciency of 44%
in removing carbon soil from wool and solution
(1)) gave only 58% emciency, solution (0) showed
a detersive e?lciency of 67%.
The following examples, described hereinafter,
are merely illustrative of the present invention,
and it will be understood that the invention is not
limited thereto.
EXAMPLE I
parts of a sulphonate prepared by treating a
Pennsylvania white mineral oil of paramn base
and having an average molecular weight of 235
with sulphur dioxide and chlorine in the presence
of light and neutralizing the product with sodium
hydroxide. Sodium sulphate is then added, and
the ingredients are thoroughly mixed. The re
sulting detergent composition provides aqueous
solutions of excellent detergent characteristics.
v
EXAMPLE IV
The monosulphate of monogylcerides of coconut
oil fatty acids is disposed in a mixture in the pro
portion of about 40 parts by weight to about 60
parts of sodium sulphate. Solutions of this active
organic material are made up containing varying
proportions of coconut oil fatty acid monoesters
of N,N_'-diethanol piperazine (that is, monoesters
of 1,‘i-di(,8-hydroxy ethyl) piperazine), and the
pH and detersive e?iciency of each successive
mixture is determined.
In each case a total con
centration in aqueous solution of 0.25% of mono
glyceride monosulphate agent and the diethanol
pi-perazine monoester is employed, and the aque
ous solution also contains 300 parts per million
of calcium and magnesium hardness (calculated
as calcium carbonate). The detersive emciency
The Edeleanu extract of a naphthene base min
eral oil is dissolved in about twice its volume of
liquid sulphur dioxide and sulphonated with ole
um. A dry, ?u?y powder containinng about 96%
of active ingredient is obtained. An amount of
tallow fatty acid monesters of 3,6-dimethyl-L4
diqB-hydroxy propyl) piperazine equivalent to
about 20% of the weight of the total solids present
is stirred into the mixture. The composition
thus produced provides solutions of ?ne detersive
characteristics.
The use of the term “sulphonated” with refer
ence to organic compounds in the following claims
will be understood to include sulphated as well as
“true” sulphonated materials.
is determined by the multiple swatch launder
The piperazine derivatives and the method of
ometer test on cotton soil at 115° F. ,over a twenty
preparing them form the subject matter of ap
minute period, and the standard employed for 55 plioant’s copending application Serial No. 638,471,
comparison is the detersive e?‘lciency of a 0.55%
?led December 29, 1945, now Patent No. 2,421,707.
aqueous solution of tallow soap which gives an
issued June 3, 1947.
arbitrary emciency in this test of 100%. The fol
Although the present invention has been de
lowing table shows the results obtained:
scribed with reference to particular embodiments
60 and examples, it will be apparent to those skilled
Table
in the art that variations and modi?cations of
this invention can be made and that equivalents
can be substituted therefor without departing
Ratio
Mono-
glyceride
mono-
D_ietha1_iol
piperazmo
sulphate
agent
monoester
Per cent
Per cent
P
H
Deter
sive
am
ciency
I claim:
1. A detergent composition comprising essen
tially a, surface-active organic sulphuric reaction
Per cent
100
0
_- _ _
83
90
80
70
60
10
20
30
40
50
8. 8
9. 15
9. 30
9. 45
88
94
97. 5
99
50
from the principles and true spirit of the inven
tion.
9. 55
100
product in the form of a water-soluble salt hav
ing detergent properties and having in its molec
ular structure a radical selected from the group
consisting of sulphonic acid and sulphuric acid
ester radicals, and an amount of a piperazine
derivative equivalent to about 1% to about 500%
75 by weight of said sulphonated organic compound,
2,491,099
is
7
said piperazine derivative being represented by
where R is a member of the group consisting of
alkyl and acyl radicals having about 8 to about 18
the structural formula:
A
carbon atoms, and m and n are integers of 2
to about 5.
’
no-(cno..-i~/ \N-(cn.).-on
\/
5. A detergent composition comprising essen~
tially a surface-active organic sulphuric reac
tion product in the form of a water-soluble salt
having detergent properties and having in its
molecular structure a radical selected from the
group consisting of sulphonic acid and sulphuric
acid ester radicals, and having about 8 to about 26
carbon atoms per molecule, and an amount of a
where R is a member of the group consisting of
alkyl and acyl radicals having about 5 to about
23 carbon atoms, A and B are members of the
group consisting of an ethylene radical and alkyl
derivatives thereof wherein any number of hydro
gens in the ethylene radical are replaced by alkyl
radicals of not more than two carbon atoms, and
piperazine derivative equivalent to about 20% to
about 100% by weight of said sulphonated organic
2. A detergent composition comprising essen 15 compound, said piperazine derivative being rep
tially a surface-active organic sulphuric reaction
resented by the structural formula:
m and n are integers of 2 to about 5.
product in the form of a water-soluble salt hav
ing detergent properties and having in its molec
ular structure a radical selected from the group
consisting of sulphonic acid and sulphuric acid
ester radicals, and an amount of a piperazine de
rivative equivalent to about 10% to about 200%
by weight of said sulphonated organic compound,
said piper-azine derivative being represented by
the structural formula:
26
I where R is a member of the group consisting of
alkyl and acyl radicals having about 8 to about 18
carbon atoms, and m and n are integers of 2
to about 5.
6. A detergent composition comprising essen
tially a surface-active organic sulphuric reaction
product in the form of a water-soluble salt hav
A
no-(cn,)..-N/ \N-(om).—on
\B/
ing detergent properties and having in its molec
ular structure a radical selected from the group
where R is a member of the group consisting of 30 consisting of sulphonic acid and sulphuric acid
I alkyl and acyl radicals having about 5 to about 23
> ester radicals, and vhaving about 8 to about 26
carbon atoms, A and B are members of the group
carbon atoms per molecule, and an amount of a
consisting of an ethylene radical and alkyl deriva
derivative of N,N'-diethanol piperazine equiva
tives thereof wherein any number of hydrogens in
lent to about 10% to about 200% by weight of said
the ethylene radical are replaced by alkyl radicals 35 sulphonated organic compound, said derivative
of not more than two carbon atoms, and m and n
are integers of 2 to about 5.
being represented by the structural formula:
.
3. A detergent composition comprising essen
tially a surface-active organic sulphuric reaction
product in the i'ormv of a water-soluble salt hav
ing detergent properties and having in its molec
ular structure a radical selected from the group
40
where R is a member of the group consisting of
alkyl and acyl radicals having about 8 to about 18
carbon atoms.
'7. A detergent composition comprising essen
rivative equivalent to about 10% to about 200% 45
tially a surface-active organic sulphuric reac
by weight of said sulphonated organic compound,
tion product in the form of a water-soluble salt
said piperazine derivative being represented by
having, detergent properties and having in its
the structural formula:
molecular structure a radical selected from the
group consisting of sulphonic acid and sulphuric
50
acid ester radicals, and having about 12 to about
consisting of sulphonic acid and sulphuric acid
ester radicals, and an amount of a piperazine de
20 carbon atoms per molecule, and an amount of
a derivative of N,N'-diethanol piperazine equiva
where R is a member of the group consisting of
lent
to about 20% to about 100% by weight of
alkyl and acyl radicals having about 8 to about 18
carbon atoms, A and B are members of the group 55 said sulphonated organic compound, said deriva
tive being represented by the structural formula:
consisting of an ethylene radical and alkyl deriva
tives thereof wherein any number of hydrogens in
CHr-CH,
the ethylene radical are replaced by alkyl radicals
of not more than two carbon atoms, and m and n
are integers of 2 to about 5.
'
30-01m-
N-mmon
CHr-C 3
4. A detergent composition comprising essen
tially a surface-active organic sulphuric reac
where R is a member of the group consisting. of
alkyl and acyl radicals having about 8 to about 18
tion product in the form of a water-soluble salt
carbon atoms.
having detergent properties and having in its
8. A detergent composition comprising essen
molecular structure a radical selected from the 05 tially an alkali metal salt of the sulphuric acid
group consisting of sulphonic acid and sulphuric
ester of a coconut oil fatty acid monoglyceride,
acid ester radicals, and an amount ‘of a piperazine
and an amount of a fatty acid monoester of
derivative equivalent to about 10% to about 200 %
1,4-di(p-hydroxy ethyl) piperazine equivalent to
by weight of said sulphonated organic compound,
about 10% to about 200% by weight of said alkali
said piperazine derivative being represented by 70 metal salts and-wherein the fatty acid residue
the structural formula:
'
contains about 8 to about 18 carbon atoms.
. 9. A detergent composition comprising essen
tially an alkali metal salt of a sulphuric acid ester
of a coconut oil fatty acid monoglyceride, and an
amount of the coconut oil fatty acid monoesters
memes
9
I
of 1,4-d1(p-hydroxy ethyl) plperazlne equivalent
to about 10% by weight-er said alkali metal salt.
10. A detergent composition comprising essen-
tlally a mineral oil sulphonate produced by treatin: a mineral oil with sulphur dioxide and chlo- 5
line in the presence of actinic light and substantially neutralizing the product of said treatment,
10
‘
REFERENCES CITED
The following references are of record in the
?le of this patent:
'
UNHED STATES PATENTS
Number
Name
Date
‘and an amount of l-(p-lauroxy ethyl) -4-(?-hy—
2,174,506
Fox ------------- __ Sept. 26, 1939
'droxy ethyl) -piperazine' equivalent to about 5%
by-ziweight of said mineral oil sulphonate.
10
2,206,923
2,236,328
‘Ulrich et a1- ---- --'-- July 9, 1940
Muncie __________ __ Apr. _1, 1941
2,383,737
Richardson ______ __ Aug- 28, 1945
JOHN DAVID MALKEMUS.