Note: Descriptions are shown in the official language in which they were submitted.
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AQUEOUS HEAVY DUTY LIQUID DETERGENT COMPOSITIONS COMPRISING
MODIFIED ALKYLBENZENE SULFONATES
FIELD OF THE INVENTION
This invention relates to heavy duty liquid laundry detergent products which
are
aqueous in nature and which include particular types of improved alkylbenzene
sulfonate
surfactant mixtures adapted for use by controlling compositional parameters,
especially a
2/3-phenyl index and a 2-methyl-2-phenyl index.
BACKGROUND OF THE INVENTION
Historically, highly branched alkylbenzene sulfonate surfactants, such as
those
based on tetrapropylene, known as "ABS" or "TPBS", were used in detergents.
However,
these were found to be very poorly biodegradable. A long period followed of
improving
manufacturing processes for alkylbenzene sulfonates, making them as linear as
practically possible, hence the acronym "LAS". The overwhelming part of a
large art of
linear alkylbenzene sulfonate surfactant manufacture is directed to this
objective. All
relevant large-scale commercial alkylbenzene sulfonate processes in use today
are
directed to linear alkylbenzene sulfonates. However, linear alkylbenzene
sulfonates are
not without limitations; for example, they would be more desirable if improved
for hard
water cleaning and/or cold water cleaning properties. They can often fail to
produce
good cleaning results, for example when used in hard water areas.
As a result of the limitations of the alkylbenzene sulfonates, consumer
cleaning
formulations have often needed to include a higher level of cosurfactants,
builders, and
other additives than would have been needed given a superior alkylbenzene
sulfonate.
The art of alkylbenzene sulfonate detergents is replete with references which
teach
both for and against almost every aspect of these compositions. Moreover,
there are
believed to be erroneous teachings and technical misconceptions about the
mechanism of
LAS operation under in-use conditions, particularly in the area of hardness
tolerance.
The volume of such references debases the art as a whole and makes it
difficult to select
the useful teachings from the useless without repeated experimentation. To
further
understand the state of the art, it should be appreciated that there has been
not only a lack
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of clarity on which way to go to fix the unresolved problems of linear LAS,
but also a
range of misconceptions, not only in the understanding of biodegradation but
also in
basic mechanisms of operation of LAS in presence of hardness.
Also, while the currently commercial, essentially linear alkylbenzene
sulfonate
surfactants are relatively simple compositions to define and analyze,
compositions
containing both branched and linear alkylbenzene sulfonate surfactants are
complex. In
general such compositions can be highly varied, containing one or more
different kinds
of branching in any of a number of positions on the aliphatic chain. A very
large number,
e.g., hundreds, of distinct chemical species are possible in such mixtures.
Accordingly
there is an onerous burden of experimentation if it is desired to improve such
compositions so that they can clean better in detergent compositions while at
the same
time remaining biodegradable. The formulator's knowledge is key to guiding
this effort.
Yet another currently unresolved problem in alkylbenzene sulfonate manufacture
is
to make more effective use of current LAB feedstocks. It would be highly
desirable, both
from a performance point of view and from an economic point of view, to better
utilize
certain desirable types of branched hydrocarbons.
Accordingly there is a substantial unmet need for further improvements in
alkylbenzene sulfonate surfactant mixtures, especially with respect to those
offering one
or more of the advantages of superior cleaning, hardness tolerance,
satisfactory
biodegradability, and cost.
BACKGROUND ART
US 5,659,099, US 5,393,718, US 5,256,392, US 5,227,558, US 5,139,759, US
5,164,169, US 5,116,794, US 4,840,929, US 5,744,673, US 5,522,984, US
5,811,623,
US 5,777,187, WO 9,729,064, WO 9,747573, WO 9,729,063, US 5,026,933; US
4,990,718; US 4,301,316; US 4,301,317; US 4,855,527; US 4,870,038; US
2,477,382;
EP 466,558, 1/15/92; EP 469,940, 2/5/92; FR 2,697,246, 4/29/94; SU 793,972,
1/7/81;
US 2,564,072; US 3,196,174; US 3,238,249; US 3,355,484; US 3,442,964; US
3,492,364; US 4,959,491; WO 88/07030, 9/25/90; US 4,962,256, US 5,196,624; US
5,196,625; EP 364,012 B, 2/15/90; US 3,312,745; US 3,341,614; US 3,442,965; US
3,674,885; US 4,447,664; US 4,533,651; US 4,587,374; US 4,996,386; US
5,210,060;
US 5,510,306; WO 95/17961, 7/6/95; WO 95/18084; US 5,510,306; US 5,087,788; US
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3
4,301,316; US 4,301,317; US 4,855,527; US 4,870,038; US 5,026,933; US
5,625,105
and US 4,973,788. See Vol 56 in "Surfactant Science" series, Marcel Dekker,
New
York, 1996, including in particular Chapter 2 entitled "Alkylarylsulfonates:
History,
Manufacture, Analysis and Environmental Properties", pages 39-108, "Surfactant
Science" series, Vol 73, Marcel Dekker, New York, 1998 and "Surfactant
Science"
series, Vol 40, Marcel Dekker, New York, 1992. See also copending U.S. Patent
applications No. 60/053,319 Attorney docket No 6766P filed on July 21st, 1997,
No.
60/053,318, Attorney docket No 6767P filed on July 21st, 1997, No. 60/053,321,
Attorney docket No 6768P filed on July 21 st, 1997, No. 60/053,209, Attorney
docket No
6769P filed on July 21st, 1997, No. 60/053,328, Attorney docket No 6770P filed
on July
21 st, 1997, No. 60/053,186, Attorney docket No 6771 P filed on July 21 st,
1997 and the
art cited therein. Documents referenced herein are incorporated in their
entirety.
SUMMARY OF THE INVENTION
The present invention provides aqueous heavy-duty liquid detergent
compositions
comprising modified alkylbenzene sulfonate surfactant mixtures.
Specifically, the present invention comprises an aqueous heavy-duty liquid
detergent composition.
The aqueous based heavy duty laundry detergent compositions herein preferably
contain a surfactant system comprising surfactants selected from nonionic
detersive
surfactant, anionic detersive surfactant, zwitterionic detersive surfactant,
amine oxide
detersive surfactant, and mixtures thereof.
Specifically, the first embodiment of the present invention comprises an
aqueous
based heavy duty laundry detergent composition comprising:
(i) from about 5% to about 70% by weight of composition of a modified
alkylbenzene sulfonate surfactant mixture comprising:
(a) from about 60% to about 95%, preferably from about 65% to about
90%, more preferably from about 70% to about 85%, by weight of
surfactant mixture, a mixture of branched alkylbenzene sulfonates having
formula (I):
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O
RI R2
\ L~
A [Mq~]b
S03
a
(n
wherein L is an acyclic aliphatic moiety consisting of carbon and
hydrogen, said L having two methyl termini and said L having no
substituents other than A, R' and R2; and wherein said mixture of
branched alkylbenzene sulfonates contains two or more, preferably at least
three, optionally more, of said branched alkylbenzene sulfonates differing
in molecular weight of the anion of said formula (~ and wherein said
mixture of branched alkylbenzene sulfonates has
- a sum of carbon atoms in R', L and RZ of from 9 to 15, preferably from
to 14;
- an average aliphatic carbon content, i.e., based on R', L and RZ and
excluding A, of from about 10.0 to about 14.0 carbon atoms, preferably
from about 11.0 to about 13.0, more preferably from about 11.5 to about
12.5; M is a cation or cation mixture, preferably M is selected from H, Na,
K, Ca, Mg and mixtures thereof, more preferably M is selected from H,
Na, K and mixtures thereof, more preferably still, M is selected from H,
Na, and mixtures thereof, M having a valence q, typically from 1 to 2,
preferably l; a and b are integers selected such that said branched
alkylbenzene sulfonates are electroneutral (a is typically from 1 to 2,
preferably 1, b is 1); R' is C1-C3 alkyl, preferably C1-CZ alkyl, more
preferably methyl; RZ is selected from H and C1-C3 alkyl (preferably H
and C1-C2 alkyl, more preferably H and methyl, more preferably H and
methyl provided that in at least about 0.5, more preferably 0.7, more
preferably 0.9 to 1.0 mole fraction of said branched alkylbenzene
sulfonates, R2 is H); A is a benzene moiety (typically A is the moiety -
C6H4- , with the S03 moiety of Formula (1] in para- position to the L
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moiety, though in some proportion, usually no more than about 5%,
preferably from 0 to 5% by weight, the S03 moiety is ortho- to L); and
(b) from about 5% to about 40%, preferably from about 10% to about
35%, more preferably from about 15% to about 30%, by weight of
surfactant mixture, of a mixture of nonbranched alkylbenzene sulfonates
having formula (In:
O
Y
[Mq~~b
3
a
wherein a, b, M, A and q are as defined hereinbefore and Y is an
unsubstituted linear aliphatic moiety consisting of carbon and hydrogen
having two methyl termini, and wherein said Y has a sum of carbon atoms
of from 9 to 15, preferably from 10 to 14, and said Y has an average
aliphatic carbon content of from about 10.0 to about 14.0, preferably from
about 11.0 to about 13.0, more preferably 11.5 to 12.5 carbon atoms; and
wherein said modified alkylbenzene sulfonate surfactant mixture is further
characterized by a 2/3-phenyl index of from about 275 to about 10,000,
preferably
from about 350 to about 1200, more preferably from about 500 to about 700; and
also preferably wherein said modified alkylbenzene sulfonate surfactant
mixture
has a 2-methyl-2-phenyl index of less than about 0.3, preferably less than
about
0.2, more preferably less than about 0.1, more preferably still, from 0 to
0.05;
(ii) from about 0.1 to about 8% of a co-surfactant composition selected from
the
group consisting of alkyl polyhydroxy fatty acid amide, alkyl amidopropyl
dimethyl amine and mixtures thereof;
(iii) from about 30% to about 95%, of an aqueous liquid carrier; and
wherein said composition is further characterized by a 2/3-phenyl index of
from about
275 to about 10,000.
In accordance with the second embodiment of the present invention, there are
encompassed herein a number of alternate embodiments, such as those in which
there is
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blending of the novel modified alkylbenzene sulfonate surfactant mixture of
the
invention with one or more other alkylbenzene sulfonate surfactants. In
practical terms,
such blending is usually encompassed before sulfonation and detergent
formulation, but
the outcome is a an aqueous based heavy duty laundry detergent composition
containing
a blend of the novel modified alkylbenzene sulfonate surfactant with other,
known,
alkylbenzene sulfonates. Such alternate embodiments of the invention
nonlimitingly
include those termed herein as "medium 2/3-phenyl surfactant system". Such
surfactant
system essentially contain useful amounts of the modified alkylbenzene
sulfonate
surfactant, along with other known alkylbenzene sulfonates subject to specific
provisions
of the 2/3-phenyl index of the overall composition. Such an aqueous based
heavy duty
laundry detergent compositions include:
(i) from about 0.1% to about 95% by weight of composition of a medium 2/3-
phenyl
surfactant system consisting essentially of
(1) from 1% (preferably at least about 5%, more preferably at least about 10
%)
to about 60% (preferably less than about 50%, more preferably less than about
40 %), by weight of surfactant system of a first alkylbenzene sulfonate
surfactant, wherein said first alkylbenzene sulfonate surfactant is a modified
alkylbenzene sulfonate surfactant mixture, said surfactant mixture
comprising:
(a) from about 60% to about 95% by weight of surfactant mixture, a
mixture of branched alkylbenzene sulfonates having formula (n:
O
R1 R2
\ L~
A [Mq~]b
S03
a
(
wherein L is an acyclic aliphatic moiety consisting of carbon and
hydrogen, said L having two methyl termini and said L having no
substituents other than A, Rl and R2; and wherein said mixture of
branched alkylbenzene sulfonates contains two or more of said branched
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alkylbenzene sulfonates differing in molecular weight of the anion of said
formula (n and wherein said mixture of branched alkylbenzene sulfonates
has
- a sum of carbon atoms in Rl, L and RZ of from 9 to 15;
- an average aliphatic carbon content of from about 10.0 to about 14.0
carbon atoms; M is a cation or cation mixture having a valence q; a and b
are integers selected such that said branched alkylbenzene sulfonates are
electroneutral; Rl is C1-C3 alkyl; RZ is selected from H and C1-C3 alkyl; A
is a benzene moiety; and
(b) from about 5% to about 40% by weight of surfactant mixture, of a
mixture of nonbranched alkylbenzene sulfonates having formula (I~:
O
Y
[Mq~~b
3
a
wherein a, b, M, A and q are as defined hereinbefore and Y is an
unsubstituted linear aliphatic moiety consisting of carbon and hydrogen
having two methyl termini, and wherein said Y has a sum of carbon atoms
of from 9 to 1 S, preferably from 10 to 14, and said Y has an average
aliphatic carbon content of from about 10.0 to about 14.0; and
wherein said modified alkylbenzene sulfonate surfactant mixture is further
characterized by a 2/3-phenyl index of from about 275 to about 10,000; and
(2) from 40% (preferably at least about 50%, more preferably at least about 60
%)
to about 99% (preferably less than about 95%, more preferably less than about
90%), by weight of surfactant system of a second alkylbenzene sulfonate
surfactant, wherein said second alkylbenzene sulfonate surfactant is an
alkylbenzene sulfonate surfactant mixture other than said modified
alkylbenzene sulfonate surfactant mixture ( 1 ) (typically said second
alkylbenzene sulfonate surfactant is a commercial Clo-Cia linear alkylbenzene
sulfonate surfactant, e.g., DETAL ~ process LAS or HF process LAS though
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in general any commercial linear (LAS) or branched (ABS, TPBS) type can
be used); and wherein said second alkylbenzene sulfonate surfactant has a
2/3-phenyl index of from about 75 to about 160;
provided that said medium 2/3-phenyl surfactant system has a 2/3-phenyl index
of
from about 160 to about 275, (preferably from about 170 to about 265, more
preferably from about 180 to about 255);
(ii) from about 0.1 to about 8% of a co-surfactant composition selected from
the group
consisting of alkyl polyhydroxy fatty acid amide, alkyl amidopropyl dimethyl
amine
and mixtures thereof; and
(iii) from about 30% to about 95%, of an aqueous liquid Garner.
Specifically, the third embodiment of the present invention comprises an
aqueous
based heavy duty laundry detergent composition comprising:
(i) a modified alkylbenzene sulfonate surfactant mixture comprising the
product
of a process comprising the steps of:
(I) alkylating benzene with an alkylating mixture;
(II) sulfonating the product of (I); and
(11T) neutralizing the product of (II);
wherein said alkylating mixture comprises:
(a) from about 1 % to about 99.9%, by weight of alkylating mixture of
branched C9-CZO monoolefins, said branched monoolefins having
structures identical with those of the branched monoolefins formed by
dehydrogenating branched paraffins of formula R1LR2 wherein L is an
acyclic aliphatic moiety consisting of carbon and hydrogen and
containing two terminal methyls; Rl is C~ to C3 alkyl; and R2 is
selected from H and C1 to C3 alkyl; and
(b) from about 0.1% to about 85%, by weight of alkylating mixture of C9-
C2o linear aliphatic olefins;
wherein said alkylating mixture contains said branched C9-CZO monoolefins
having at least two different carbon numbers in said C9-CZO range, and has a
mean
carbon content of from about 9.0 to about 15.0 carbon atoms; and wherein said
components (a) and (b) are at a weight ratio of at least about 15:85;
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(ii) from about 0.1 to about 8% of a co-surfactant composition selected from
the
group consisting of alkyl polyhydroxy fatty acid amide, alkyl amidopropyl
dimethyl amine and mixtures thereof;
(iii) from about 30% to about 95%, of an aqueous liquid Garner; and
wherein said composition is further characterized by a 2/3-phenyl index of
from about
275 to about 10,000.
Specifically, the fourth embodiment of the present invention comprises an
aqueous based heavy duty laundry detergent composition comprising:
(i) a modified alkylbenzene sulfonate surfactant mixture consisting
essentially of
the product of a process comprising the steps, in sequence, of
(n alkylating benzene with an alkylating mixture;
(I~ sulfonating the product of (I]; and
(IIn neutralizing the product of (II);
wherein said alkylating mixture comprises:
(a) from about 1 % to about 99.9%, by weight of alkylating mixture of a
branched alkylating agent selected from the group consisting of
(A) C9-C2o internal monoolefms R1LR2 wherein L is an acyclic
olefinic moiety consisting of carbon and hydrogen and
containing two terminal methyls;
(B) C9-CZO alpha monoolefins RiAR2 wherein A is an acyclic
alpha-olefinic moiety consisting of carbon and hydrogen and
containing one terminal methyl and one terminal olefinic
methylene;
(C) C9-C2o vinylidene monoolefins R1BR2 wherein B is an acyclic
vinylidene olefin moiety consisting of carbon and hydrogen
and containing two terminal methyls and one internal olefinic
methylene;
(D) C9-CZo primary alcohols Rl QRZ wherein Q is an acyclic
aliphatic primary terminal alcohol moiety consisting of carbon,
hydrogen and oxygen and containing one terminal methyl;
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(E) C9-C2o primary alcohols R1ZR2 wherein Z is an acyclic
aliphatic primary nonterminal alcohol moiety consisting of
carbon, hydrogen and oxygen and containing two terminal
methyls; and
(F) mixtures thereof;
wherein in any of (A)-(F), said RI is C1 to C3 alkyl and said R2 is
selected from H and C1 to C3 alkyl; and
(b) from about 0.1 % to about 85%, by weight of alkylating mixture of C9-
CZO linear alkylating agent selected from C9-CZO linear aliphatic olefins,
C9-C2o linear aliphatic alcohols and mixtures thereof;
wherein said alkylating mixture contains said branched alkylating agents
having
at least two different carbon numbers in said C9-CZO range, and has a mean
carbon
content of from about 9.0 to about 15.0 carbon atoms; and wherein said
components (a) and (b) are at a weight ratio of at least about 15:85;
(ii) from about 0.1 to about 8% of a co-surfactant composition selected from
the
group consisting of alkyl polyhydroxy fatty acid amide, alkyl amidopropyl
dimethyl amine and mixtures thereof; and
(iii) from about 30% to about 95%, of an aqueous liquid carrier;
wherein said composition is further characterized by a 2/3-phenyl index of
from about
275 to about 10,000.
Specifically, the fifth embodiment of the present invention comprises an
aqueous
based heavy duty laundry detergent composition comprising:
(i) from about 0.01% to about 95% by weight of composition of a modified
alkylbenzene sulfonate surfactant mixture comprising:
(a) from about 60% to about 95% by weight of surfactant mixture, a
mixture of branched alkylbenzene sulfonates having formula (n:
O
RI R2
\ L~
A [Mq~]b
S03
a
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(I)
wherein L is an acyclic aliphatic moiety consisting of carbon and
hydrogen, said L having two methyl termini and said L having no
substituents other than A, RI and R2; and wherein said mixture of
branched alkylbenzene sulfonates contains two or more of said branched
alkylbenzene sulfonates differing in molecular weight of the anion of said
formula (I) and wherein said mixture of branched alkylbenzene sulfonates
has
- a sum of carbon atoms in Rl, L and RZ of from 9 to 15;
- an average aliphatic carbon content of from about 10.0 to about 14.0
carbon atoms; M is a cation or cation mixture having a valence q; a and b
are integers selected such that said branched alkylbenzene sulfonates are
electroneutral; Rl is C1-C3 alkyl; R2 is selected from H and C1-C3 alkyl; A
is a benzene moiety; and
(b) from about 5% to about 40% by weight of surfactant mixture, of a
mixture of nonbranched alkylbenzene sulfonates having formula (II):
O
Y
I
[Mq~~b
3
a
wherein a, b, M, A and q are as defined hereinbefore and Y is an
unsubstituted linear aliphatic moiety consisting of carbon and hydrogen
having two methyl termini, and wherein said Y has a sum of carbon atoms
of from 9 to 15, preferably from 10 to 14, and said Y has an average
aliphatic carbon content of from about 10.0 to about 14.0; and
wherein said modified alkylbenzene sulfonate surfactant mixture is further
characterized by a 2/3-phenyl index of from about 275 to about 10,000 and
wherein said modified alkylbenzene sulfonate surfactant mixture has a 2-methyl-
2-phenyl index of less than about 0.3;
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(ii) from about 0.1 to about 8% of a co-surfactant composition selected from
the
group consisting of alkyl polyhydroxy fatty acid amide, alkyl amidopropyl
dimethyl amine and mixtures thereof;
(iii) from about 30% to about 95%, of an aqueous liquid Garner; and
(iv) from about 0.00001 % to about 99.9% of composition of a surfactant
selected
from the group consisting of anionic surfactants other than those of (i),
nonionic surfactants, zwitterionic surfactants, cationic surfactants,
amphoteric
surfactant and mixtures thereof;
wherein said composition is further characterized by a 2/3-phenyl index of
from about
275 to about 10,000; provided that when said composition comprises any
alkylbenzene
sulfonate surfactant other than said modified alkylbenzene sulfonate
surfactant mixture,
said composition is further characterized by an overall 2/3-phenyl index of at
least about
200, wherein said overall 2/3-phenyl index is determined by measuring 2/3-
phenyl index,
as defined herein, on a blend of said modified alkylbenzene sulfonate
surfactant mixture
and said any other alkylbenzene sulfonate to be added to said composition,
said blend,
for purposes of measurement, being prepared from aliquots of said modified
alkylbenzene sulfonate surfactant mixture and said other alkylbenzene
sulfonate not yet
exposed to any other of the components of said composition; and further
provided that
when said composition comprises any alkylbenzene sulfonate surfactant other
than said
modified alkylbenzene sulfonate surfactant mixture, said composition is
further
characterized by an overall 2-methyl-2-phenyl index of less than about 0.3,
wherein said
overall 2-methyl-2-phenyl index is to be determined by measuring 2-methyl-2-
phenyl
index, as defined herein, on a blend of said modified alkylbenzene sulfonate
surfactant
mixture and any other alkylbenzene sulfonate to be added to said composition,
said
blend, for purposes of measurement, being prepared from aliquots of said
modified
alkylbenzene sulfonate surfactant mixture and said other alkylbenzene
sulfonate not yet
exposed to any other of the components of said composition.
The detergent compositions defined herein also comprise from about 1 % to 80%
by
weight of the composition of additional detergent ingredients such as
builders, enzymes,
colorants, bleaching agents, bleach activators, colored speckles, organic
detergent
builders, inorganic alkalinity sources and mixtures thereof.
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The above mentioned embodiments and other aspects of the present invention are
more fully described and exemplified in the detailed description hereinafter.
All percentages, ratios and proportions herein are by weight, unless otherwise
specified. All temperatures are in degrees Celsius (oC) unless otherwise
specified. All
documents cited are in relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
The aqueous liquid detergent compositions of this invention comprise a
modified
alkylbenzene sulfonate surfactant mixture. The essential and optional
components of the
modified alkylbenzene sulfonate surfactant mixture and other optional
materials of the
aqueous liquid detergent compositions herein, as well as composition form,
preparation
and use, are described in greater detail as follows: (All concentrations and
ratios are on a
weight basis unless otherwise specified.) The invention, on the other hand, is
not
intended to encompass any wholly conventional liquid detergent compositions,
such as
those based exclusively on linear alkylbenzene sulfonates made by any process,
or
exclusively on known unacceptably branched alkylbenzene sulfonates such as ABS
or
TPBS.
It is preferred that when the detergent compositions of the present invention
comprise any alkylbenzene sulfonate surfactant other than said modified
alkylbenzene
sulfonate surfactant mixture (for example as a result of blending into the
detergent
composition one or more commercial, especially linear, typically linear Clo-
Ci4,
alkylbenzene sulfonate surfactants), said composition is further characterized
by an
overall 2/3-phenyl index of at least about 200, preferably at least about 250,
more
preferably at least about 350, more preferably still, at least about 500,
wherein said
overall 2/3-phenyl index is determined by measuring 2/3-phenyl index, as
defined herein,
on a blend of said modified alkylbenzene sulfonate surfactant mixture and said
any other
alkylbenzene sulfonate to be added to said composition, said blend, for
purposes of
measurement, being prepared from aliquots of said modified alkylbenzene
sulfonate
surfactant mixture and said other alkylbenzene sulfonate not yet exposed to
any other of
the components of said composition; and further provided that when said
composition
comprises any alkylbenzene sulfonate surfactant other than said modified
alkylbenzene
sulfonate surfactant mixture (for example as a result of blending into the
composition one
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14
or more commercial, especially linear, typically linear Clo-C14, alkylbenzene
sulfonate
surfactants), said composition is further characterized by an overall 2-methyl-
2-phenyl
index of less than about 0.3, preferably from 0 to 0.2, more preferably no
more than
about 0.1, more preferably still, no more than about 0.05, wherein said
overall 2-methyl-
2-phenyl index is to be determined by measuring 2-methyl-2-phenyl index, as
defined
herein, on a blend of said modified alkylbenzene sulfonate surfactant mixture
and any
other alkylbenzene sulfonate to be added to said composition, said blend, for
purposes of
measurement, being prepared from aliquots of said modified alkylbenzene
sulfonate
surfactant mixture and said other alkylbenzene sulfonate not yet exposed to
any other of
the components of said composition. These provisions may appear somewhat
unusual,
however they are consistent with the spirit and scope of the present
invention, which
encompasses a number of economical but less preferred approaches in terms of
overall
cleaning performance, such as blending of the modified alkylbenzene sulfonate
surfactants with conventional linear alkylbenzene sulfonate surfactants either
during
synthesis or during formulation into the detergent composition. Moreover, as
is well
known to practitioners of detergent analysis, a number of detergent adjuncts
(paramagnetic materials and sometimes even water) are capable of interfering
with
methods for determining the parameters of alkylbenzene sulfonate surfactant
mixtures as
described hereinafter. Hence wherever possible, analysis should be conducted
on dry
materials before mixing them into the compositions.
Moreover, the invention encompasses the addition of useful hydrotrope
precursors and/or hydrotropes, such as CI-Cg alkylbenzenes, more typically
toluenes,
cumenes, xylenes, naphthalenes, or the sulfonated derivatives of any such
materials,
minor amounts of any other materials, such as tribranched alkylbenzene
sulfonate
surfactants, dialkylbenzenes and their derivatives, dialkyl tetralins, wetting
agents,
processing aids, and the like. It will be understood that, with the exception
of
hydrotropes, it will not be usual practice in the present invention to include
any such
materials. Likewise it will be understood that such materials, if and when
they interfere
with analytical methods, will not be included in samples of compositions used
for
analytical purposes.
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A preferred modified alkylbenzene sulfonate surfactant mixture according to
first
embodiment of the present invention has M selected from H, Na, K and mixtures
thereof,
said a=1, said b=1, said q=1, and said modified alkylbenzene sulfonate
surfactant mixture
has a 2-methyl-2-phenyl index of less than about 0.3, preferably less than
about 0.2, more
preferably from 0 to about 0.1.
Such a modified alkylbenzene sulfonate surfactant mixture according can be
made as the product of a process using as catalyst a zeolite selected from
mordenite,
offretite and H-ZSM-12 in at least partially acidic form, preferably an acidic
mordenite
(in general certain forms of zeolite beta can be used as an alternative but
are not
preferred). Embodiments described in terms of their making, as well as
suitable catalysts,
are all further detailed hereinafter.
Another preferred detergent composition according to the first embodiment of
the
invention wherein said modified alkylbenzene sulfonate surfactant mixture
consists
essentially of said mixture of (a) and (b), wherein said 2-methyl-2-phenyl
index of said
modified alkylbenzene sulfonate surfactant mixture is less than about 0.1, and
said
average aliphatic carbon content is from about 11.5 to about 12.5 carbon
atoms; said Rl
is methyl; said RZ is selected from H and methyl provided that in at least
about 0.7 mole
fraction of said branched alkylbenzene sulfonates RZ is H; and wherein said
sum of
carbon atoms in Rl, L and R2 is from 10 to 14; and further wherein in said
mixture of
nonbranched alkylbenzene sulfonates, said Y has a sum of carbon atoms of from
10 to 14
carbon atoms, said average aliphatic carbon content of said nonbranched
alkylbenzene
sulfonates is from about 11.5 to about 12.5 carbon atoms, and said M is a
monovalent
cation or cation mixture selected from H, Na and mixtures thereof.
Definitions:
Methyl termini The terms "methyl termini" and/or "terminal methyl" mean the
carbon
atoms which are the terminal carbon atoms in alkyl moieties, that is L, and/or
Y of
formula (~ and formula (In respectively are always bonded to three hydrogen
atoms.
That is, they will form a CH3- group. To better explain this, the structure
below shows
the two terminal methyl groups in an alkylbenzene sulfonate.
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terminal
methyl terminal
methyl
CH
CH3
The term "AB" herein when used without further qualification is an
abbreviation for
"alkylbenzene" of the so-called "hard" or nonbiodegradable type which on
sulfonation
forms "ABS". The term "LAB" herein is an abbreviation for "linear
alkylbenzene" of the
current commercial, more biodegradable type, which on sulfonation forms linear
alkylbenzene sulfonate, or "LAS". The term "MLAS" herein is an abbreviation
for the
modified alkylbenzene sulfonate mixtures of the invention.
Impurities: The surfactant mixtures herein are preferably substantially free
from
impurities selected from tribranched impurities, dialkyl tetralin impurities
and mixtures
thereof. By "substantially free" it is meant that the amounts of such
impurities are
insufficient to contribute positively or negatively to the cleaning
effectiveness of the
composition. Typically there is less than about 5%, preferably less than about
1%, more
preferably about 0.1 % or less of the impurity, that is typically no one of
the impurities is
practically detectable.
Illustrative Structures
The better to illustrate the possible complexity of modified alkylbenzene
sulfonate surfactant mixtures of the 'invention and the resulting detergent
compositions,
structures (a) to (v) below are illustrative of some of the many preferred
compounds of
formula (I). These are only a few of hundreds of possible preferred structures
that make
up the bulk of the composition, and should not be taken as limiting of the
invention.
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CHI CH~
~3 CH3
S03M
(a) (b)
H3
v v v ~ ~3 CH3
/ CH3
S03M
(c) (d)
CH3 CH3
S03M
(e) (
CH3 CH3
S03M
(g) (h)
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CHI
CH3 CH3
S03M S03M
) ~)
CHI
CH3 ~3
S03M
~k) ~1)
CHI
CH3 CH3
S03M
Vim) Vin)
CHI
CH3 CH3
S03M
(°) (p)
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CH;
CH3 CH3
(q) (r)
CH3 CH3
S03M
(s) (t)
~3
(u) (v)
Structures (w) and (x) nonlimitingly illustrate less preferred compounds of
Formula (I) which can be present, at lower levels than the above-illustrated
preferred
types of stuctures, in the modified alkylbenzene sulfonate surfactant mixtures
of the
invention and the resulting detergent compositions.
H ~3
S03M
(x)
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Structures (y), (z), and (aa) nonlimitingly illustrate compounds broadly
within
Formula (I) that are not preferred but which can be present in the modified
alkylbenzene
sulfonate surfactant mixtures of the invention and the resulting detergent
compositions.
CHI CH3
CH3 H3C CH3
M03S
S03M
(Y) (z)
CHI
CH3
3
S03M
(aa) fib)
Structure (bb) is illustrative of a tri-branched structure not within Formula
(I), but that
can be present as an impurity.
Preferably the modified alkylbenzene sulfonate surfactant mixtures herein are
the
product of sulfonating a modified alkylbenzene, (other than well known
tetrapropylene or
AB types) wherein the modified alkylbenzene is produced by alkylating benzene
with a
branched olefin, other than tetrapropylene, and more particularly the lightly
branched
types described in more detail hereinafter, over an acidic mordenite-type
catalyst or other
suitable catalyst as defined elsewhere herein.
In certain cases, said modified alkylbenzene sulfonate surfactant mixtures
herein
can also be prepared by blending. Thus, the invention includes a detergent
composition
using a modified alkylbenzene sulfonate surfactant mixture according to the
first
embodiment wherein said modified alkylbenzene sulfonate surfactant mixture is
prepared
by a process comprising a step selected from: (i) blending a mixture of
branched and
linear alkylbenzene sulfonate surfactants having a 2/3-phenyl index of 500 to
700 with an
alkylbenzene sulfonate surfactant mixture having a 2/3-phenyl index of 75 to
160 and (ii)
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blending a mixture of branched and linear alkylbenzenes having a 2/3-phenyl
index of
500 to 700 with an alkylbenzene mixture having a 2/3-phenyl index of 75 to 160
and
sulfonating said blend. However when a modified alkylbenzene sulfonate
surfactant
mixture is prepared in this fashion, the resulting surfactant mixture will
have a 2/3-
phenyl index of from about 275 to about 10,000.
In outline, modified alkylbenzene sulfonate surfactant mixtures herein can be
made by the steps of:
(I) alkylating benzene with an alkylating mixture;
(II) sulfonating the product of (I); and (optionally but very preferably)
(III) neutralizing the product of (II).
Provided that suitable alkylation catalysts and process conditions as taught
herein
are used, the product of step (I) is a modified alkylbenzene mixture in
accordance with
the invention. Provided that sulfonation is conducted under conditions
generally known
and reapplicable from LAS manufacture, see for example the literature
references cited
herein, the product of step (II) is a modified alkylbenzene sulfonic acid
mixture in
accordance with the invention. Provided that neutralization step (III) is
conducted as
generally taught herein, the product of step (11~ is a modified alkylbenzene
sulfonate
surfactant mixture in accordance with the invention. Since neutralization can
be
incomplete, mixtures of the acid and neutralized forms of the present modified
alkylbenzene sulfonate systems in all proportions, e.g., from about 1000:1 to
1:1000 by
weight, are also part of the present invention. Overall, the greatest
criticalities are in step
Preferred modified alkylbenzene sulfonate surfactant mixtures herein comprise
the product of a process comprising the steps of: (I) alkylating benzene with
an alkylating
mixture; (II) sulfonating the product of (I); and (optionally but very
preferably) (III)
neutralizing the product of (II); wherein said alkylating mixture comprises:
(a) from
about 1% to about 99.9%, by weight of branched C9-CZO (preferably C9-C15, more
preferably Clo-C14) monoolefms, said branched monoolefins having structures
identical
with those of the branched monoolefins formed by dehydrogenating branched
paraffins
of formula R1LR2 wherein L is an acyclic aliphatic moiety consisting of carbon
and
hydrogen and containing two terminal methyls; RI is Ci to C3 alkyl; and RZ is
selected
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from H and C1 to C3 alkyl; and (b) from about 0.1% to about 85%, by weight of
C9-CZo
(preferably C9-CIS, more preferably CIO-C14) linear aliphatic olefins; wherein
said
alkylating mixture contains said branched C9-C2o monoolefins having at least
two
different carbon numbers in said C9-CZO range, and has a mean carbon content
of from
about 9.0 to about 15.0 carbon atoms (preferably from about 10.0 to about
14.0, more
preferably from about 11.0 to about 13.0, more preferably still from about
11.5 to about
12.5); and wherein said components (a) and (b) are at a weight ratio of at
least about
15:85 (preferably having branched component (a) in excess of linear component
(b), for
example 51 % or more by weight of (a) and 49% or less of (b), more preferably
60% to
95% by weight of (a) and 5% to 40% of (b), more preferably still 65% to 90% by
weight
of (a) and 10% to 35% of (b), more preferably still 70% to 85% by weight of
(a) and 15%
to 30% of (b) wherein these percentages by weight exclude any other materials,
for
example diluent hydrocarbons, that may be present in the process).
Also encompassed herein are modified alkylbenzene sulfonate surfactant
mixtures consisting essentially of the product of a process comprising the
steps, in
sequence, o~ (n alkylating benzene with an alkylating mixture; (I)7
sulfonating the
product of (n; and ()~ neutralizing the product of (I~; wherein said
alkylating mixture
comprises: (a) from about 1% to about 99.9%, by weight of a branched
alkylating agent
selected from: (A) C9-C2o (preferably C9-CIS, more preferably CIO-C14)
internal
monoolefins RILR2 wherein L is an acyclic olefinic moiety consisting of carbon
and
hydrogen and containing two terminal methyls; (B) C9-C2o (preferably C9-CIS,
more
preferably CIO-C14) alpha monoolefins RIARZ wherein A is an acyclic alpha-
olefinic
moiety consisting of carbon and hydrogen and containing one terminal methyl
and one
terminal olefinic methylene; (C) C9-C2o (preferably C9-CIS, more preferably
CIO-CIa)
vinylidene monoolefins RIBR2 wherein B is an acyclic vinylidene olefin moiety
consisting of carbon and hydrogen and containing two terminal methyls and one
internal
olefinic methylene; (D) C9-CZO (preferably C9-CIS, more preferably CIO-C14)
primary
alcohols RIQRZ wherein Q is an acyclic aliphatic primary terminal alcohol
moiety
consisting of carbon, hydrogen and oxygen and containing one terminal methyl;
(E) C9-
C2o (preferably C9-CIS, more preferably CIO-C14) primary alcohols RIZRZ
wherein Z is an
acyclic aliphatic primary nonterminal alcohol moiety consisting of carbon,
hydrogen and
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oxygen and containing two terminal methyls; and (F) mixtures thereof; wherein
in any of
(A)-(F), said Rl is C1 to C3 alkyl and said R2 is selected from H and CI to C3
alkyl; and
(b) from about 0.1% to about 85%, by weight Of C9-C2o (preferably C9-C15, more
preferably Clo-Cia) linear alkylating agent selected from C9-C2o (preferably
C9-C15, more
preferably Clo-Cia) linear aliphatic olefins, C9-C2o (preferably C9-C15, more
preferably
Clo-C14) linear aliphatic alcohols and mixtures thereof; wherein said
alkylating mixture
contains said branched alkylating agents having at least two different carbon
numbers in
said C9-CZO (preferably C9-C15, more preferably Coo-CI4) range, and has a mean
carbon
content of from about 9.0 to about 15.0 carbon atoms (preferably from about
10.0 to
about 14.0, more preferably from about 11.0 to about 13.0, more preferably
still from
about 11.5 to about 12.5); and wherein said components (a) and (b) are at a
weight ratio
of at least about 15:85 (preferably having branched component (a) in excess of
linear
component (b), for example 51 % or more by weight of (a) and 49% or less of
(b), more
preferably 60% to 95% by weight of (a) and S% to 40% of (b), more preferably
still 65%
to 90% by weight of (a) and 10% to 35% of (b), more preferably still 70% to
85% by
weight of (a) and 15% to 30% of (b) wherein these percentages by weight
exclude any
other materials, for example diluent hydrocarbons, that may be present in the
process).
In more highly preferred embodiments, the invention encompasses a modified
alkylbenzene sulfonate surfactant mixture prepared in accordance with the
above-
outlined steps wherein said alkylating mixture consists essentially of (a)
from about
0.5% to about 47.5%, by weight of said branched alkylating agent selected
from: (G) C9-
C14 internal monoolefins R1LR2 wherein L is an acyclic olefinic moiety
consisting of
carbon and hydrogen and containing two terminal methyls; (H) C9-CI4 alpha
monoolefins
R1AR2 wherein A is an acyclic alpha-olefinic moiety consisting of carbon and
hydrogen
and containing one terminal methyl and one terminal olefinic methylene; and
(J)
mixtures thereof; wherein in any of (G)-(H), said Rl is methyl, and said RZ is
H or methyl
provided that in at least about 0.7 mole fraction of the total of said
monoolefins, RZ is H;
and (b) from about 0.1% to about 25%, by weight Of C9-C14 linear aliphatic
olefins; and
(c) from about 50% to about 98.9%, by weight of Garner materials selected from
paraffins and inert nonparaffinic solvents;
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wherein said alkylating mixture contains said branched alkylating agents
having at least
two different carbon numbers in said C9-C14 range, and has a mean carbon
content of
from about 11.5 to about 12.5 carbon atoms; and wherein said components (a)
and (b) are
at a weight ratio of from about 51:49 to about 90:10.
Other modified alkylbenzene sulfonate surfactant mixtures herein are made by
the
above-outlined processes wherein in step (I), said alkylation is performed in
the presence
of an alkylation catalyst, said alkylation catalyst is an intermediate acidity
solid porous
alkylation catalyst, and step (II) comprises removal of components other than
monoalkylbenzene prior to contacting the product of step (I) with sulfonating
agent.
Also encompassed is the modified alkylbenzene sulfonate surfactant mixture
according to the above-defined processes wherein said alkylation catalyst is
other than a
member selected from the group consisting of HF, A1C13, sulfuric acid and
mixtures
thereof. Such is the case when the alkylation catalyst is selected from the
group
consisting of non-fluoridated acidic mordenite-type catalyst, fluoridated
acidic
mordenite-type catalyst and mixtures thereof. Catalysts are described in more
detail
hereinafter.
The processes are tolerant of variation, for example conventional steps can be
added before, in parallel with, or after the outlined steps (I), (II) and
(111). This is
especially the case for accomodating the use of hydrotropes or their
precursors. Thus the
invention encompasses a modified alkylbenzene sulfonate surfactant mixture
according
to the above-outlined processes wherein a hydrotrope, hydrotrope precursor, or
mixtures
thereof is added after step (I); or the hydrotrope, hydrotrope precursor or
mixtures thereof
is added during or after step (II) and prior to step (III);
or a hydrotrope can be added during or after step (111).
Sulfonation and Workup or Neutralization (Steps II / IIn
In general, sulfonation of the modified alkylbenzenes in the instant process
can
be accomplished using any of the well-known sulfonation systems, including
those
described in "Detergent Manufacture Including Zeolite Builders and other New
Materials", Ed. Sittig., Noyes Data Corp., 1979, as well as in Vol. 56 in
"Surfactant
Science" series, Marcel Dekker, New York, 1996, including in particular
Chapter 2
entitled "Alkylarylsulfonates: History, Manufacture, Analysis and
Environmental
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Properties", pages 39-108 which includes 297 literature references. This work
provides
access to a great deal of literature describing various processes and process
steps, not
only sulfonation but also dehydrogenation, alkylation, alkylbenzene
distillation and the
like. Common sulfonation systems useful herein include sulfuric acid,
chlorosulfonic
acid, oleum, sulfur trioxide and the like. Sulfur trioxide/air is especially
preferred.
Details of sulfonation using a suitable air/sulfur trioxide mixture are
provided in US
3,427,342, Chemithon. Sulfonation processes are further extensively described
in
"Sulfonation Technology in the Detergent Industry", W.H. de Groot, Kluwer
Academic
Publishers, Boston, 1991.
Any convenient workup steps may be used in the present process. Common
practice is to neutralize after sulfonation with any suitable alkali. Thus the
neutralization
step can be conducted using alkali selected from sodium, potassium, ammonium,
magnesium and substituted ammonium alkalis and mixtures thereof. Potassium can
assist
solubility, magnesium can promote soft water performance and substituted
ammonium
can be helpful for formulating specialty variations of the instant
surfactants. The
invention encompasses any of these derivative forms of the modified
alkylbenzenesulfonate surfactants as produced by the present process and their
use in
consumer product compositions.
Alternately the acid form of the present surfactants can be added directly to
acidic
cleaning products, or can be mixed with cleaning ingredients and then
neutralized.
The hydrotropes or hydrotrope precursors useful herein can in general be
selected
from any suitable hydrotrope or hydrotrope precursor, including lower alkyl
(C1-C8)
aromatics and their sulfonic acids and sulfonate salts, but are more typically
based on a
sulfonic acid or sodium sulfonate salt of toluene, cumene, xylene, napthalene
or mixtures
thereof. The hydrotrope precursors are selected from any suitable hydrotrope
precursor,
typically toluene, cumene, xylene, napthalene or mixtures thereof. A
hydrotrope
precursor is a compound that during step (III), namely the sulfonation step,
is converted
into a hydrotrope.
In terms of process conditions for alkylation, the invention encompasses a
modified alkylbenzene sulfonate.surfactant mixture wherein in step (I) said
alkylation is
performed at a temperature of from about 125°C to about 230°C
(preferably from about
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175°C to about 215°C) and at a pressure of from about 50 psig to
about 1000 psig
(preferably from about 100 psig to about 250 psig). Preferably in step (I)
said alkylation
is performed at a temperature of from about 175°C to about
215°C, at a pressure of from
about 100 psig to about 250 psig. and a time of from about 0.01 hour to about
18 hours
(preferably, as rapidly as possible, more typically from about 0.1 hour to
about 5 hours).
If desired such alkylation may be conducted in one or more stages. Different
stages of the
process can be conducted in different manufacturing facilities. Typically in
practice, LAB
manufacturers will conduct step (I), with detergent manufacturers conducting
step (III).
Step (II) is typically conducted by either, or can even be conducted by third
party
manufacturers. .
In general it is found preferable in step (I) to couple together the use of
relatively
low temperatures (e.g., 175°C to about 215°C) with reaction
times of medium duration (1
hour to about 8 hours) in the above-indicated ranges.
It is possible even to "target" for desirably low 2-methyl-2-phenyl index in
the
present inventive compositions by selecting a relatively low reaction
temperature, e.g.,
about 190°C, and to monitor the progress of the reaction by any
convenient means (e.g.,
sampling and NMR analysis) to assure adequate completion while minimizing 2-
methyl-
2-phenyl index.
Moreover, it is contemplated that the alkylation "step" (I) herein can be
"staged"
so that two or more reactors operating under different conditions in the
defined ranges
may be useful. By operating a plurality of such reactors, it is possible to
allow for
material with less preferred 2-methyl-2-phenyl index to be initially formed
and,
surprisingly, to convert such material into material with a more preferred 2-
methyl-2-
phenyl index.
In terms of sulfonating agent selection, the invention encompasses a modified
alkylbenzene sulfonate surfactant mixture wherein step (II) is performed using
a
sulfonating agent selected from the group consisting of sulfur trioxide,
sulfur trioxide/air
mixtures, and sulfuric acid (including oleum). Chlorosulfonic acid or other
known
sulfonating agents, while less commercially relevant, are also useful and are
included for
use in the invention.
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Although in general, neutralization step (111) can be carned out with any
suitable
alkali, the invention includes a modified alkylbenzene sulfonate surfactant
mixture
wherein said step (III) is performed using a basic salt, said basic salt
having a cation
selected from the group consisting of alkali metal, alkaline earth metal,
ammonium,
substituted ammonium, and mixtures thereof and an anion selected from
hydroxide,
oxide, carbonate, silicate, phosphate, and mixtures thereof. Preferred basic
salt is selected
from the group consisting of sodium hydroxide, sodium silicate, potassium
hydroxide,
potassium silicate, magnesium hydroxide, ammonium hydroxide, and mixtures
thereof.
Alkylation Catalyst
To secure the modified alkylbenzene sulfonate surfactant mixtures of the
invention, the present invention uses a particularly defined alkylation
catalyst. Said
alkylation catalyst is an intermediate acidity solid porous alkylation
catalyst defined in
detail hereinafter. Particularly preferred alkylation catalysts comprise at
least partially
dealuminized acidic fluoridated mordenites, at least partially dealuminized
acidic
nonfluoridated mordenites, and mixtures thereof.
Numerous alkylation catalysts are unsuitable for making the present modified
alkylbenzene mixtures and modified alkylbenzene sulfonate surfactant mixtures.
Unsuitable alkylation catalysts include any of: sulfuric acid, aluminum
chloride, and HF.
Also unsuitable are non-acidic calcium mordenite, and many others. Other
catalysts, such
as the DETAL~ process catalysts of UOP are also unsuitable, at least in their
current
commercial executions. Indeed no alkylation catalyst currently used for
alkylation in the
commercial production of detergent C 10-C 14 linear alkylbenzene sulfonates
for use in
laundry products are suitable.
In contrast, suitable alkylation catalysts herein are selected from shape-
selective
moderately acidic alkylation catalysts, preferably zeolitic. The zeolite
catalyst used for
the alkylation step (I) is preferably selected from the group consisting of
mordenite,
HZSM-12, and offretite, any of these being in at least partially acidic form.
Mixtures can
be used and the catalysts can be combined with binders etc. as described
hereinafter.
More preferably, the zeolite is substantially in acid form and is contained in
a catalyst
pellet comprising a conventional binder and further wherein said catalyst
pellet
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comprises at least about 1 %, more preferably at least 5%, more typically from
50% to
about 90%, of said zeolite.
More generally, a suitable alkylation catalyst is typically at least partially
crystalline, more preferably substantially crystalline not including binders
or other
materials used to form catalyst pellets, aggregates or composites. Moreover
the catalyst
is typically at least partially acidic. Fully exchanged Ca-form mordenite, for
example,
is unsuitable whereas H-form mordenite is suitable.
The pores characterizing the zeolites useful in the present alkylation process
may be substantially circular, uniform pores of about 6.2 Angstrom, or
preferably may
be somewhat elliptical, such as in mordenite. It should be understood that, in
any case,
the zeolites used as catalysts in the alkylation step of the present process
have a major
pore dimension intermediate between that of the large pore zeolites, such as
the X and
Y zeolites, and the relatively small pore size zeolites ZSM-5 and ZSM-11, and
preferably between about 6 Angstrom and about 7 Angstrom. Indeed ZSM-5 has
been
tried and found inoperable in the present invention. The pore size dimensions
and
crystal structures of certain zeolites are specified in ATLAS OF ZEOLITE
STRUCTURE TYPES by W. M. Meier and D. H. Olson, published by the Structure
Commission of the International Zeolite Association (1978 and more recent
editions)
and distributed by Polycrystal Book Service, Pittsburgh, Pa.
The zeolites useful in the alkylation step of the instant process generally
have at
least 10 percent of the cationic sites thereof occupied by ions other than
alkali or
alkaline-earth metals. Typical but non-limiting replacing ions include
ammonium,
hydrogen, rare earth, zinc, copper and aluminum. Of this group, particular
preference is
accorded ammonium, hydrogen, rare earth or combinations thereof. In a
preferred
embodiment, the zeolites are converted to the predominantly hydrogen form,
generally by
replacement of the alkali metal or other ion originally present with hydrogen
ion
precursors, e.g., ammonium ions, which upon calcination yield the hydrogen
form. This
exchange is conveniently carried out by contact of the zeolite with an
ammonium salt
solution, e.g., ammonium chloride, utilizing well known ion exchange
techniques. In
certain preferred embodiments, the extent of replacement is such as to produce
a zeolite
material in which at least 50 percent of the cationic sites are occupied by
hydrogen ions.
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The zeolites may be subjected to various chemical treatments, including
alumina
extraction (dealumination) and combination with one or more metal components,
particularly the metals of Groups IIB, III, IV, VI, VII and VIII. It is also
contemplated
that the zeolites may, in some instances, desirably be subjected to thermal
treatment,
including steaming or calcination in air, hydrogen or an inert gas, e.g.
nitrogen or helium.
A suitable modifying treatment entails steaming of the zeolite by contact with
an
atmosphere containing from about 5 to about 100% steam at a temperature of
from about
250°C to 1000°C. Steaming may last for a period of between about
0.25 and about 100
hours and may be conducted at pressures ranging from sub-atmospheric to
several
hundred atmospheres.
In practicing the desired alkylation step of the instant process, it may be
useful to
incorporate the above-described intermediate pore size crystalline zeolites in
another
material, e.g., a binder or matrix resistant to the temperature and other
conditions
employed in the process. Such matrix materials include synthetic or naturally
occurring
substances as well as inorganic materials such as clay, silica, and/or metal
oxides. Matrix
materials can be in the form of gels including mixtures of silica and metal
oxides. The
latter may be either naturally occurnng or in the form of gels or gelatinous
precipitates.
Naturally occurring clays which can be composited with the zeolite include
those of the
montmorillonite and kaolin families, which families include the sub-bentonites
and the
kaolins commonly known as Dixie, McNamee-Georgia and Florida clays or others
in
which the main mineral constituent is halloysite, kaolinite, dickite, nacrite
or anauxite.
Such clays can be used in the raw state as originally mined or initially
subjected to
calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the intermediate pore size zeolites
employed herein may be compounded with a porous matrix material, such as
alumina,
silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-
beryllia, and silica-
titania, as well as ternary combinations, such as silica-alumina-thoria,
silica-alumina-
zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix may
be in the
form of a cogel. The relative proportions of finely divided zeolite and
inorganic oxide gel
matrix may vary widely, with the zeolite content ranging from between about 1
to about
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99% by weight and more usually in the range of about 5 to about 80% by weight
of the
composite.
A group of zeolites which includes some useful for the alkylation step herein
have a silica:alumina ratio of at least 2:1, preferably at least 10:1 more
preferably at least
20:1. The silica:alumina ratios referred to in this specification are the
structural or
framework ratios, that is, the ratio for the Si04 to the A104 tetrahedra. In
practice,
silica:alumina ratios as determined by various physical and chemical methods
are
acceptable for use herein. It should be understood that such methods may
acceptably give
some variation. For example, a gross chemical analysis may include aluminum
which is
present in the form of cations associated with the acidic sites on the
zeolite, thereby
giving a somewhat low experimentally determined silica:alumina ratio.
Similarly, if the
ratio is determined by thermogravimetric analysis (TGA) of ammonia desorption,
a
somewhat low ammonia titration may be obtained if cationic aluminum prevents
exchange of the ammonium ions onto the acidic sites. These disparities are
well known
in the art. They can be troublesome when certain treatments, such as the
dealuminization
methods described below which result in the presence of ionic aluminum free of
the
zeolite structure, are employed. Due care should therefore be taken to ensure
that the
framework silica:alumina ratio is correctly determined to the extent
acceptable to a
practitioner of the art.
When the zeolites have been prepared in the presence of organic canons they
are
typically catalytically inactive, commonly because the intracrystalline free
space is
occupied by organic cations from the forming solution. They may be activated
by heating
in an inert atmosphere at 540°C for one hour, for example, followed by
base exchange
with ammonium salts followed by calcination at 540°C in air. The
presence of organic
cations in the forming solution may not be absolutely essential to the
formation of the
zeolite; but it does appear to favor the formation of this special type of
zeolite. Some
natural zeolites may sometimes be converted to zeolites of the desired type by
various
activation procedures and other treatments such as base exchange, steaming,
alumina
extraction and calcination. The zeolites preferably have a crystal framework
density, in
the dry hydrogen form, not substantially below about 1.6 g/cm3. The dry
density for
known structures may be calculated from the number of silicon plus aluminum
atoms per
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31
1000 cubic Angstroms, as given, e.g., on page 19 of the article on Zeolite
Structure by W.
M. Meier included in "Proceedings of the Conference on Molecular Sieves,
London,
April 1967", published by the Society of Chemical Industry, London, 1968.
Reference is
made to this paper for a discussion of the crystal framework density. A
further discussion
of crystal framework density, together with values for some typical zeolites,
is given in
U.S. Pat. No. 4,016,218, to which reference is made. When synthesized in the
alkali
metal form, the zeolite is conveniently converted to the hydrogen (acidic)
form, generally
via intermediate formation of the ammonium form by ammonium ion exchange and
calcination of the ammonium form to yield the hydrogen form. It has been found
that
although the hydrogen form of the zeolite catalyzes the reaction successfully,
the zeolite
may also be partly in the alkali metal form and/or the form of other metal
salts.
EP 466,558 describes an acidic mordenite type alkylation catalyst also of
possible
use herein having overall Si/Al atomic ratio of 15-85 (15-60), Na weight
content is less
than 1000 ppm (preferably less than 250 ppm), and there is a low or zero
content of
extra-network A1 species; the elementary mesh volume as defined in EP 466,558
is
below 2,760 nm3.
US 5,057,472 is likewise useful for preparing alkylation catalysts herein and
relates to concurrent dealumination and ion-exchange of an acid-stable Na ion-
containing
zeolite, preferably mordenite, effected by contact of the zeolite with a 0.5-3
(preferably 1-
2.5) M HN03 solution containing sufficient NH4N03 to fully exchange the Na+
ions for
NH4+ and H+ ions. The resulting zeolites can have a SiOZ:A1203 ratio of 15:1
to 26:1,
preferably 17:1 to 23:1, and are preferably calcined to at least partially
convert the
NH4+/H+ form to the H+ form. Optionally, though not necessarily particularly
desirable in
the present invention, the catalyst can contain a Group VIII metal (and
optionally also an
inorganic oxide) together with the calcined zeolite of '472.
Another acidic mordenite catalyst useful for the alkylation step herein is
disclosed
in US 4,861,935 which relates to a hydrogen form of mordenite incorporated
with
alumina, the composition having a surface area of at least 580 m2 /g. Other
acidic
mordenite catalysts useful for the alkylation step herein include those
described in US
5,243,116 and US 5,198,595. Yet another alkylation catalyst useful herein is
described in
US 5,175,135 which is an acid mordenite zeolite having a silica/alumina molar
ratio of
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32
at least 50:1, a Symmetry Index of at least 1.0 as determined by X-ray
diffraction
analysis, and a porosity such that the total pore volume is in the range from
about 0.18
cc/g to about 0.45 cc/g and the ratio of the combined meso- and macropore-
volume to
the total pore volume is from about 0.25 to about 0.75.
Particularly preferred alkylation catalysts herein include the acidic
mordenite
catalysts ZeocatTM FM-8/25H available from Zeochem; CBV 90 A available from
Zeolyst International, and LZM-8 available from UOP Chemical Catalysts as well
as
fluoridated versions of the above commercial catalysts. Fluoridated mordenites
can be
prepared by a number of ways. A method of providing a particularly useful
fluoridated
mordenite is described in US 5,777,187. The invention encompasses preferred
embodiments in which the mordenites are fluoridated, but also has other
preferred
embodiments in which the mordenites are non-fluoridated.
Most generally, any alkylation catalyst may be used herein provided that the
alkylation catalyst can (a) accommodate branched olefins as described
elsewhere herein
into the smallest pore diameter of said catalyst and (b) selectively alkylate
benzene with
said branched olefins and optionally mixtures thereof with nonbranched
olefins.
Acceptable selectivity is in accordance with a 2/3-Phenyl index of about 275
to about
10,000 as defined herein.
In other terms, the catalyst selections herein are made in part with the
intention of
minimizing internal alkylbenzene formation (e.g., 4-phenyl, S-phenyl ...) The
formulators contributing to the present invention have unexpectedly discovered
that
control of internal alkylbenzene sulfonate isomers in the present inventive
surfactant
mixtures in conjunction with introduction of limited methyl branching is very
helpful for
improving their performance. The present invention connects this discovery to
discoveries of the synthesis chemists in the present invention, who have
determined how
to control internal isomer content while providing limited methyl branching in
the
modified alkylbenzene sulfonate surfactant mixtures in accordance with the
formulators'
prescriptions.
The extent to which internal isomer content needs to be controlled can vary
depending on the consumer product application and on whether outright best
performance or a balance of performance and cost is required. In absolute
terms, the
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amount of internal isomer such as internal alkylbenzene isomer is preferably
always kept
below 25% by weight, but for best results, from 0 to 10%, preferably less than
about S%
by weight. "Internal alkylbenzene" isomers as defined herein include
alkylbenzenes
having phenyl attachment to an aliphatic chain in the 4,5,6 or 7 position.
Without intending to be limited by theory, there are two reasons for which it
is
believed that the prefered alkylation catalysts are the above-described shape
selective
zeolitic type catalysts, especially mordenites. The first reason is to provide
the selectivity
of formation of preferred compounds such as branched and nonbranched 2-phenyl
and 3-
phenylalkylbenzenes. This selectivity is measured by the 2/3-phenyl index. The
second
reason is to control the amount of quaternary alkylbenzenes and thus
quaternary
alkylbenzenesulfonates.
Results with alkylation catalysts such as HF can give quite high levels of
quaternary alkylbenzenes as shown in the literature (see J. Org. Chem. Vol 37,
No. 25,
1972). This contrasts with the surprising discovery as part of the present
invention that
one can attain low levels of quaternary alkylbenzenes in catalyzed reactions
of benzene
with branched olefins, as characterized by 2-methyl-2-phenyl index. Even when
the
olefins used are substantially dibranched, as illustrated herein, a low 2-
methyl-2-phenyl
index of less than 0.1 can surprisingly be obtained.
Numerous variations of the present detergent compositions are useful. Such
variations include:
~ the detergent composition which is substantially free from alkylbenzene
sulfonate surfactants other than said modified alkylbenzene sulfonate
surfactant mixture;
~ the detergent composition which comprises, at least about 0.1%, preferably
no
more than about 10%, more preferably no more than about 5%, more
preferably still, no more than about 1 % by weight of composition, of a
commercial Coo-C~4 linear alkylbenzene sulfonate surfactant;
~ the detergent composition which comprises, at least about 0.1 %, preferably
no
more than about 10%, more preferably no more than about 5%, more
preferably still, no more than about 1 % by weight of composition, of a
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commercial highly branched alkylbenzene sulfonate surfactant. (e.g., TPBS or
tetrapropylbenzene sulfonate);
~ the detergent composition which comprises, a nonionic surfactant at a level
of
from about 0.5% to about 25% by weight of composition, and wherein said
nonionic surfactant is a polyalkoxylated alcohol in capped or non-capped
form having: - a hydrophobic group selected from linear Clo-Ci6 alkyl, mid-
chain C 1-C3 branched C l o-C i 6 alkyl, guerbet branched C l o-C i 6 alkyl,
and
mixtures thereof and - a hydrophilic group selected from 1-15 ethoxylates, 1-
15 propoxylates 1-15 butoxylates and mixtures thereof, in capped or
uncapped form. (when uncapped, there is also present a terminal primary -OH
moiety and when capped, there is also present a terminal moiety of the form -
OR wherein R is a C1-C6 hydrocarbyl moiety, optionally comprising a
primary or, preferably when present, a secondary alcohol.);
~ the detergent composition which comprises, an alkyl sulfate surfactant at a
level of from about 0.5% to about 25% by weight of composition, wherein
said alkyl sulfate surfactant has a hydrophobic group selected from linear Cio-
C18 alkyl, mid-chain C1-C3 branched Clo-CI8 alkyl, guerbet branched Clo-Cia
alkyl, and mixtures thereof and a cation selected from Na, K and mixtures
thereof;
~ the detergent composition which comprises, an alkyl(polyalkoxy)sulfate
surfactant at a level of from about 0.5% to about 25% by weight composition,
wherein said alkyl(polyalkoxy)sulfate surfactant has - a hydrophobic group
selected from linear Clo-Ci6 alkyl, mid-chain C1-C3 branched Clo-Cib alkyl,
guerbet branched Clo-Ci6 alkyl, and mixtures thereof and - a
(polyalkoxy)sulfate hydrophilic group selected from 1-15 polyethoxysulfate,
1-15 polypropoxysulfate, 1-15 polybutoxysulfate, 1-15 mixed
poly(ethoxy/propoxy/butoxy)sulfates, and mixtures thereof, in capped or
uncapped form; and - a cation selected from Na, K and mixtures thereof;
Further the present invention includes a detergent composition comprising
(preferably consisting essentially of): (i) from about 0.01 % to about 95%, by
weight of
composition, (preferably from about 0.5% to about 50%, more preferably from
about 1%,
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preferably at least 2%, more preferably at least 4%, more preferably at least
6%, more
preferably still at least 8% to about 35%) of modified alkylbenzene sulfonate
surfactant
mixture according to the invention; (ii) from about 0.00001 % to about 99.9%
by weight
of composition (preferably from about 5% to about 98%, more preferably from
about
SO% to about 95%) of a conventional hand dishwasing adjunct; and (iii) from
about
0.00001% to about 99.9% by weight of composition (preferably from about 0.1%
to
about 50%, more preferably from about 0.2% to about 40%, even more preferably
form
abour 0.5% to about 30%), of a surfactant selected from the group consisting
of anionic
surfactants other than said modified alkylbenzene sulfonate surfactant
mixture, nonionic,
cationic, amphoteric, zwitterionic and mixtures thereof; provided that when
said
detergent composition comprises any other alkylbenzene sulfonate than the
alkylbenzene
sulfonate of said modified alkylbenzene sulfonate surfactant mixture, said
modified
alkylbenzene sulfonate surfactant mixture and said other alkylbenzene
sulfonate, as a
mixture, have an overall 2/3-phenyl index of from about 275 to about 10,000
(preferably
from about 350 to about 1200, more preferably from about 500 to about 700).
Thus the invention includes a 2/3-phenyl surfactant mixture consisting
essentially
of: from 1% (preferably at least about 5%, more preferably at least about 10
%) to about
60% (in one mode preferably less than about 50%, more preferably less than
about 40
%), by weight of surfactant system of a first alkylbenzene sulfonate
surfactant, wherein
said first alkylbenzene sulfonate surfactant is a modified alkylbenzene
sulfonate
surfactant mixture according to the first embodiment; and from 40% (in one
mode
preferably at least about 50%, more preferably at least about 60 %) to about
99%
(preferably less than about 95%, more preferably less than about 90%), by
weight of
surfactant system of a second alkylbenzene sulfonate surfactant, wherein said
second
alkylbenzene sulfonate surfactant is an alkylbenzene sulfonate surfactant
mixture other
than said modified alkylbenzene sulfonate surfactant mixture according to the
first
embodiment, and wherein said second alkylbenzene sulfonate surfactant has a
2/3-phenyl
index of from about 75 to about 160 (typically said second alkylbenzene
sulfonate
surfactant is a commercial Clo-C~4 linear alkylbenzene sulfonate surfactant,
e.g., DETAL
~ process LAS or HF process LAS though in general any commercial linear (LAS)
or
branched (ABS, TPBS) type can be used); provided that said medium 2/3-phenyl
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surfactant mixture has a 2/3-phenyl index of from about 160 to about 275
(preferably
from about 170 to about 265, more preferably from about 180 to about 255). (of
course it
is equally possible within the spirit and scope of the invention to prepare
any blend of the
modified alkylbenzene sulfonate surfactant mixture of the invention with any
known
commercial linear or branched alkylbenzene sulfonate surfactant.
Processes for preparing a medium 2/3-phenyl surfactant mixture include those
comprising a step selected from: (i) blending said first alkylbenzene
sulfonate surfactant
and said second alkylbenzene sulfonate surfactant; and (ii) blending the
nonsulfonated
precursor of said first alkylbenzene sulfonate surfactant and the
nonsulfonated precursor
of said second alkylbenzene sulfonate surfactant and sulfonating said blend.
Preparative Examples
Example 1
Mixture of 4-methyl-4-nonanol, 5-methyl-5-decanol,
6-methyl-6-undecanol and 6-methyl-6-dodecanol
(A starting-material for branched olefins)
A mixture of 4.65 g of 2-pentanone, 20.7 g of 2-hexanone, 51.0 g of 2-
heptanone, 36.7 g
of 2-octanone and 72.6 g of diethyl ether is added to an addition funnel. The
ketone
mixture is then added dropwise over a period of 2.25 hours to a nitrogen
blanketed
stirred three neck 2 L round bottom flask, fitted with a reflux condenser and
containing
600 mL of 2.0 M n-pentylmagnesium bromide in diethyl ether and an additional
400 mL
of diethyl ether. After the addition is complete the reaction mixture is
stirred an
additional 2.5 hours at 20°C. The reaction mixture is then added to lkg
of cracked ice
with stirnng. To this mixture is added 393.3 g of 30% sulphuric acid solution.
The
aqueous acid layer is drained and the remaining ether layer is washed twice
with 750 mL
of water. The ether layer is then evaporated under vacuum to yield 176.1 g of
a mixture
of 4-methyl-4-nonanol, 5-methyl-S-decanol, 6-methyl-6-undecanol and 6-methyl-6-
dodecanol.
Example 2
Substantially Mono Methyl Branched Olefin Mixture
With Randomized Branching
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(A branched olefin mixture which is an alkylating agent for preparing modified
alkylbenzenes in accordance with the invention)
a) A 174.9 g sample of the mono methyl branched alcohol mixture of Example 1
is added
to a nitrogen blanketed stirred three neck round bottom 500 mL flask, fitted
with a Dean
Stark trap and a reflux condenser along with 35.8 g of a shape selective
zeolite catalyst
(acidic mordenite catalyst ZeocatTM FM-8/25H). With mixing, the mixture is
then heated
to about 110-155°C and water and some olefin is collected over a period
of 4-5 hours in
the Dean Stark trap. The conversion of the alcohol mixture of example 1 to a
substantially non-randomized methyl branched olefin mixture is now complete.
The
substantially non-randomized methyl branched olefin mixture remaining in the
flask
along with the substantially non-randomized methyl branched olefin mixture
collected in
the dean stark trap is recombined and filtered to remove catalyst. The solid
filter cake is
washed twice with 100 mL portions of hexane. The hexane filtrate is evaporated
under
vacuum and the resulting product is combined with the first filtrate to give
148.2 g of a
substantially non-randomized methyl branched olefin mixture.
b) The olefin mixture of Example 2a is combined with 36g of a shape selective
zeolite
catalyst (acidic mordenite catalyst ZeocatTM FM-8/25H) and reacted according
to
example 2a with the following changes. The reaction temperature is raised to
190-200°C
for a period of about 1-2 hours to randomize the specific branch positions in
the olefin
mixture. The substantially mono methyl branched olefin mixture with randomized
branching remaining in the flask along with the substantially mono methyl
branched
olefin mixture with randomized branching collected in the dean stark trap are
recombined
and filtered to remove catalyst. The solid filter cake is washed twice with
100 mL
portions of hexane. The hexane filtrate is evaporated under vacuum and the
resulting
product is combined with the first filtrate to give 147.5 g of a substantially
mono methyl
branched olefin mixture with randomized branching.
EXAMPLE 3
Substantially Mono Methyl Branched Alkylbenzene Mixture
With a 2/3-Phenyl Index of about S50 and a 2-Methyl-2-Phenyl Index of about
0.02
(A modified alkylbenzene mixture in accordance with the invention)
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147 g of the substantially mono methyl branched olefin mixture of example 2
and 36 g of
a shape selective zeolite catalyst (acidic mordenite catalyst ZeocatTM FM-
8/25H) are
added to a 2 gallon stainless steel, stirred autoclave. Residual olefin and
catalyst in the
container are washed into the autoclave with 300 mL of n-hexane and the
autoclave is
sealed. From outside the autoclave cell, 2000 g of benzene (contained in a
isolated
vessel and added by way of an isolated pumping system inside the isolated
autoclave
cell) is added to the autoclave. The autoclave is purged twice with 250 psig
N2, and then
charged to 60 psig N2. The mixture is stirred and heated to about 200°C
for about 4-5
hours. The autoclave is cooled to about 20°C overnight. The valve is
opened leading
from the autoclave to the benzene condenser and collection tank. The autoclave
is heated
to about 120°C with continuous collection of benzene. No more benzene
is collected by
the time the reactor reaches 120°C. The reactor is then cooled to
40°C and 750 g of n-
hexane is pumped into the autoclave with mixing. The autoclave is then drained
to
remove the reaction mixture. The reaction mixture is filtered to remove
catalyst and the
n-hexane is removed under vacuum. The product is distilled under vacuum (1-S
mm of
Hg). The substantially mono methyl branched alkylbenzene mixture with a 2/3-
Phenyl
index of about SSO and a 2-methyl-2-phenyl index of about 0.02 is collected
from 76°C -
130°C (167 g).
EXAMPLE 4
Substantially Mono Methyl Branched Alkylbenzenesulfonic Acid Mixture
with a 2/3-Phenyl Index of about 550 and a 2-Methyl-2-Phenyl Index of about
0.02
(A modified alkylbenzene sulfonic acid mixture in accordance with the
invention)
The product of example 3 is sulfonated with a molar equivalent of
chlorosulfonic acid
using methylene chloride as solvent. The methylene chloride is removed to give
210 g of
a substantially mono methyl branched alkylbenzenesulfonic acid mixture with a
2/3-
Phenyl index of about 550 and a 2-methyl-2-phenyl index of about 0.02
EXAMPLE 5
Substantially Mono Methyl Branched Alkylbenzene sulfonate, Sodium Salt
Mixture with a 2/3-Phenyl index of about 550
(A modified alkylbenzene sulfonate surfactant mixture in accordance with the
invention)
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The product of example 4 is neutralized with a molar equivalent of sodium
methoxide in
methanol and the methanol is evaporated to give 225 g of a substantially mono
methyl
branched alkylbenzene sulfonate, sodium salt mixture with a 2/3-Phenyl index
of about
550 and a 2-methyl-2-phenyl index of about 0.02.
EXAMPLE 6
Substantially Linear Alkylbenzene Mixture
With a 2/3-Phenyl Index of About 550 and a 2-Methyl-2-Phenyl Index of about
0.02
(An alkylbenzene mixture to be used as a component of modified alkylbenzenes)
A mixture of chain lengths of substantially linear alkylbenzenes with a 2/3-
Phenyl index
of about 550 and a 2-methyl-2-phenyl index of about 0.02 is prepared using a
shape
zeolite catalyst (acidic mordenite catalyst ZeocatTM FM-8/25H). A mixture of
15.1 g of
Neodene (R)10, 136.6 g of Neodene(R)1112, 89.5 g of Neodene(R)12 and 109.1 g
of 1-
tridecene is added to a 2 gallon stainless steel, stirred autoclave along with
70 g of a
shape selective catalyst (acidic mordenite catalyst ZeocatTM FM-8/25H).
Neodene is a
trade name for olefins from Shell Chemical Company. Residual olefin and
catalyst in the
container are washed into the autoclave with 200 mL of n-hexane and the
autoclave is
sealed. From outside the autoclave cell, 2500 benzene (contained in a isolated
vessel
and added by way of an isolated pumping system inside the isolated autoclave
cell) is
added to the autoclave. The autoclave is purged twice with 250 psig N2, and
then
charged to 60 psig N2. The mixture is stirred and heated to about 200-
205°C for about 4-
hours then cooled to 70-80°C. The valve is opened leading from the
autoclave to the
benzene condenser and collection tank. The autoclave is heated to about
120°C with
continuous collection of benzene in collection tank. No more benzene is
collected by the
time the reactor reaches 120°C. The reactor is then cooled to
40°C and 1 kg of n-hexane
is pumped into the autoclave with mixing. The autoclave is then drained to
remove the
reaction mixture. The reaction mixture is filtered to remove catalyst and the
n-hexane is
evaporated under low vacuum. The product is then distilled under high vacuum
(1-5 mm
of Hg). The substantially linear alkylbenzene mixture with a 2/3-Phenyl index
of about
550 and a 2-methyl-2-phenyl index of about 0.02 is collected from 85°C -
150°C (426.2
g)~
EXAMPLE 7
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Substantially Linear Alkylbenzenesulfonic Acid Mixture
With a 2/3-Phenyl Index of About 550 and a 2-Methyl-2-Phenyl Index of About
0.02
(An alkylbenzene sulfonic acid mixture to be used as a component of modified
alkylbenzene sulfonic acid mixtures in accordance with the invention)
422.45 g of the product of example 6 is sulfonated with a molar equivalent of
chlorosulfonic acid using methylene chloride as solvent. The methylene
chloride is
removed to give 574 g of a substantially linear alkylbenzenesulfonic acid
mixture with a
2/3-Phenyl index of about S50 and a 2-methyl-2-phenyl index of about 0.02.
EXAMPLE 8
Substantially Linear Alkylbenzene sulfonate, Sodium Salt Mixture
With a 2/3-Phenyl Index of About 550 and a 2-Methyl-2-Phenyl Index of About
0.02.
(An alkylbenzene sulfonate surfactant mixture to be used as a component of
modified
alkylbenzene sulfonate surfactant mixtures in accordance with the invention)
The substantially linear alkylbenzenesulfonic acid mixture of example 7 is
neutralized
with a molar equivalent of sodium methoxide in methanol and the methanol is
evaporated to give 613 g of the substantially linear alkylbenzene sulfonate,
sodium salt
mixture with a 2/3-Phenyl index of about 550 and a 2-methyl-2-phenyl index of
about
0.02.
EXAMPLE 9
6,10-Dimethyl-2-undecanol
(A starting-material for branched olefins)
To a glass autoclave liner is added 299 g of geranylacetone, 3.8 g of 5%
rutheniumon
carbon and 150 ml of methanol. The glass liner is sealed inside a 3 L,
stainless steel,
rocking autoclave and the autoclave purged once with 250 psig NZ, once with
250 psig
HZ and then charged with 1000 psig H2. With mixing, the reaction mixture is
heated. At
about 75°C, the reaction initiates and begins consuming H2 and
exotherms to 170-180°C.
In 10-15 minutes, the temperature has dropped to 100-110°C and the
pressure dropped to
500 psig. The autoclave is boosted to 1000 psig with H2 and mixed at 100-
110°C for an
additional 1 hour and 40 minutes with the reaction consuming an additional 160
psig HZ
but at which time no more HZ consumption is observed. Upon cooling the
autoclave to
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40°C, the reaction mixture removed, filtered to remove catalyst and
concentrated by
evaporation of methanol under vacuum to yield 297.75 g of 6,10-dimethyl-2-
undecanol.
EXAMPLE 10
5,7-Dimethyl-2-decanol
(A starting-material for branched olefins)
To a glass autoclave liner is added 249 g of 5,7-dimethyl-3,5,9-decatrien-2-
one, 2.2 g of
5% rutheniumon carbon and 200 ml of methanol. The glass liner is sealed inside
a 3 L,
stainless steel, rocking autoclave and the autoclave purged once with 250 psig
NZ, once
with 250 psig H2 and then charged with 500 psig HZ. With mixing, the reaction
mixture
is heated. At about 75°C, the reaction initiates and begins consuming
HZ and exotherms
to 170°C. In 10 minutes, the temperature has dropped to 115-
120°C and the pressure
dropped to 270 psig. The autoclave is boosted to 1000 psig with H2, mixed at
110-115°C
for an additional 7 hours and 15 minutes then cooled to 30°C. The
reaction mixture is
removed from autoclave, filtered to remove catalyst and concentrated by
evaporation of
methanol under vacuum to yield 225.8 g of 5,7-dimethyl-2-decanol.
EXAMPLE 11
4, 8-Dimethyl-2-nonanol
(A starting-material for branched olefins)
A mixture of 671.2 g of citral and 185.6 g of diethyl ether is added to an
addition funnel.
The citral mixture is then added dropwise over a five hour period to a
nitrogen blanketed,
stirred, 5 L, 3-neck, round bottom flask equipped with a reflux condenser
containing 1.6
L of 3.0 M methylmagnesium bromide solution and an additional 740 ml of
diethyl ether.
The reaction flask is situated in an ice water bath to control exotherm and
subsequent
ether reflux. After addition is complete, the ice water bath is removed and
the reaction
allowed to mix for an additional 2 hours at 20-25°C at which point the
reaction mixture is
added to 3.5 Kg of cracked ice with good mixing. To this mixture is added 1570
g of
30% sulfuric acid solution. The aqueous acid layer is drained and the
remaining ether
layer washed twice with 2 L of water. The ether layer is concentrated by
evaporation of
the ether under vacuum to yield 720.6 g of 4,8-dimethyl-3,7-nonadien-2-ol. To
a glass
autoclave liner is added 249.8 g of the 4,8-dimethyl-3,7-nonadien-2-ol, 5.8 g
of 5%
palladium on activated carbon and 200 ml of n-hexane. The glass liner is
sealed inside a
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3 L, stainless steel, rocking autoclave and the autoclave purged twice with
250 psig N2,
once with 250 psig H2 and then charged with 100 psig H2. Upon mixing, the
reaction
initiates and begins consuming H2 and exotherms to 75°C. The autoclave
is heated to
80°C, boosted to 500 psig with H2, mixed for 3 hours and then cooled to
30°C. The
reaction mixture is removed from autoclave, filtered to remove catalyst and
concentrated
by evaporation of n-hexane under vacuum to yield 242 g of 4,8-dimethyl-2-
nonanol.
EXAMPLE 12
Substantially Dimethyl Branched Olefin Mixture With Randomized Branching
(A branched olefin mixture which is an alkylating agent for preparing modified
alkylbenzenes in accordance with the invention)
To a nitrogen blanketed, 2 L, 3-neck round bottom flask equipped with
thermometer,
mechanical stirrer and a Dean-Stark trap with reflux condenser is added 225 g
of 4,8-
dimethyl-2-nonanol (example 11), 450 g of 5,7-dimethyl-2-decanol (example 10),
225 g
of 6,10-dimethyl-2-undecanol (example 9) and 180 g of a shape selective
zeolite catalyst
(acidic mordenite catalyst Zeocat~ FM-8/25H). With mixing, the mixture is
heated
(135-160°C) to the point water and some olefin is driven off and
collected in Dean-Stark
trap at a moderate rate. After a few hours, the rate of water collection slows
and the
temperature rises to 180-195°C where the reaction is allowed to mix for
an additional 2-4
hours.
The dimethyl branched olefin mixture remaining in the flask along with the
dimethyl
branched olefin mixture that distilled over are recombined and filtered to
remove the
catalyst. The catalyst filter cake is slurned with 500 ml of hexane and vacuum
filtered.
The catalyst filter cake is washed twice with 100 ml of hexane and the
filtrate
concentrated by evaporation of the hexane under vacuum. The resulting product
is
combined with the first filtrate to give 820 g of dimethyl branched olefin
mixture with
randomized branching.
EXAMPLE 13
Substantially Dimethyl Branched Alkylbenzene Mixture With Randomized Branching
and
2/3-Phenyl Index of About 600 and 2-Methyl-2-Phenyl Index of About 0.04
(A modified alkylbenzene mixture in accordance with the invention)
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820 g of the dimethyl branched olefin mixture of example 12 and 160 g of a
shape
selective zeolite catalyst (acidic mordenite catalyst ZeocatTM FM-8/25H) is
added to a 2
gallon stainless steel, stirred autoclave and the autoclave is sealed. The
autoclave is
purged twice with 80 psig N2 and then charged to 60 psig N2. From outside the
autoclave cell, 3000 g of benzene (contained in a isolated vessel and added by
way of an
isolated pumping system inside the isolated autoclave cell) is added to the
autoclave.
The mixture is stirred and heated to 205°C to about 210°C. The
reaction is continued for
about 10 minutes at which time the product mixture is sampled. The 10 minute
sample is
filtered to remove catalyst and vacuum pulled on the mixture to remove any
residual
traces of benzene. The sample is distilled under vacuum (1-5 mm of Hg). The
dimethyl
branched alkylbenzene mixture with randomized branching and 2/3-Phenyl index
of
about 600 and a 2-methyl-2-phenyl index of about 0.26 is collected from
90°C - 140°C.
The reaction is continued at 205°C to about 210°C for about 8
hours. The autoclave is
cooled to about 30°C overnight. The valve is opened leading from the
autoclave to the
benzene condenser and collection tank. The autoclave is heated to about
120°C with
continuous collection of benzene. No more benzene is collected by the time the
reactor
reaches 120°C and the reactor is then cooled to 40°C. The
autoclave is then drained to
remove the reaction mixture. The reaction mixture is filtered to remove
catalyst and
vacuum pulled on the mixture to remove any residual traces of benzene. The
product is
distilled under vacuum (1-5 mm of Hg). The dimethyl branched alkylbenzene
mixture
with randomized branching and 2/3-Phenyl index of about 600 and a 2-methyl-2-
phenyl
index of about 0.04 is collected from 90°C - 140°C.
EXAMPLE 14
Substantially Dimethyl Branched Alkylbenzenesulfonic Acid Mixture
With Randomized Branching and a 2/3-Phenyl Index of about 600 and a 2-Methyl-2-
Phenyl Index of About 0.04
(A modified alkylbenzene sulfonic acid mixture in accordance with the
invention)
The dimethyl branched alkylbenzene product of example 13 is sulfonated with a
molar
equivalent of chlorosulfonic acid using methylene chloride as solvent with HCl
evolved
as a side product. The resulting sulfonic acid product is concentrated by
evaporation of
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methylene chloride under vacuum. The substantially dimethyl branched
alkylbenzenesulfonic acid mixture has a 2/3 Phenyl Index of about 2/3-Phenyl
index of
about 600 and a 2-methyl-2-phenyl index of about 0.04.
EXAMPLE 1 S
Substantially Dimethyl Branched Alkylbenzenesulfonic Acid, Sodium Salt Mixture
with
Randomized Branching and 2/3-Phenyl Index of about 600 and a 2-Methyl-2-Phenyl
Index of About 0.04
(A modified alkylbenzene sulfonate surfactant mixture in accordance with the
invention)
The dimethyl branched alkylbenzenesulfonic acid mixture of example 14 is
neutralized
with a molar equivalent of sodium methoxide in methanol and the methanol is
evaporated to give solid dimethyl branched alkylbenzene sulfonate, sodium salt
mixture
with randomized branching and a 2/3-Phenyl index of about 600 and a 2-methyl-2-
phenyl
index of about 0.04.
EXAMPLE 16
Modified alkylbenzene sulfonate surfactant mixtures according to the invention
(Medium 2/3-phenyl type)
Blends are prepared o~
I) Modified alkylbenzene sulfonate surfactant mixture in accordance with the
invention
having a 2/3-Phenyl index of about 550 (according to Example 5)
II) Commercial C11.7 (average) linear alkylbenzene sulfonate surfactant (HF
type) sodium
salt having a 2/3-Phenyl index of about 100
In the table below, percentages are by weight:
A B C
I 25% 15% 38%
II 75% 85% 62%
Each of the above blends has a 2/3-phenyl index in the range from about 160 to
about
275.
EXAMPLE 17
Modified alkylbenzene sulfonate surfactant mixtures according to the invention
(Medium 2/3-phenyl type)
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Blends are prepared of:
I) Modified alkylbenzene sulfonate surfactant mixture in accordance with the
invention
having a 2/3-Phenyl index of about 550 (according to Example 5)
II] Commercial C1.7 (average) linear alkylbenzene sulfonate surfactant (DETAL
~ type)
sodium salt having a 2/3-Phenyl index of about 150
In the table below, percentages are by weight:
A B C
I 25% 15% 10%
II 75% 85% 90%
Each of the above blends has a 2/3-phenyl index in the range from about 160 to
about
275.
EXAMPLE 18
Modified alkylbenzene sulfonic acid mixtures according to the invention
(Medium 2/3-phenyl type)
Blends are prepared of
I) Modified alkylbenzene sulfonic acid surfactant mixture in accordance with
the
invention having a 2/3-Phenyl index of about S50 (according to Example 4)
II) Commercial C11,7 (average) linear alkylbenzene sulfonic acid (HF type)
having a 2/3-
Phenyl index of about 100.
In the table below, percentages are by weight:
A B C
I 25% 15% 38%
II 75% 85% 62%
Each of the above blends has a 2/3-phenyl index in the range from about 160 to
about
275.
EXAMPLE 19
Modified alkylbenzene sulfonic acid mixtures according to the invention
(Medium 2/3-phenyl type)
Blends are prepared of:
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I) Modified alkylbenzene sulfonic acid mixture in accordance with the
invention having a
2/3-Phenyl index of about 550 (according to Example 4)
II) Commercial C11.7 (average) linear alkylbenzene sulfonic acid (DETAL ~
type) having
a 2/3-Phenyl index of about 150.
In the table below, percentages are by weight:
A B C
I 25% 15% 10%
II 75% 85% 90%
Each of the above blends has a 2/3-phenyl index in the range from about 160 to
about
275.
EXAMPLE 20
Modified alkylbenzene mixtures according to the invention
(Medium 2/3-phenyl type)
Blends are prepared of
I) Modified alkylbenzene mixture in accordance with the invention having a 2/3-
Phenyl
index of about 550 (according to Example 3)
II) Commercial C11_~ (average) linear alkylbenzene (HF type) having a 2/3-
Phenyl index
of about 100.
In the table below, percentages are by weight:
A B C
I 25% 15% 38%
II 75% 85% 62%
Each of the above blends has a 2/3-phenyl index in the range from about 160 to
about
275.
EXAMPLE 21
Modified alkylbenzene mixtures according to the invention
(Medium 2/3-phenyl type)
Blends are prepared of:
I) Modified alkylbenzene mixture in accordance with the invention having a 2/3-
Phenyl
index of about 550 (according to Example 3)
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In Commercial C~1,~ (average) linear alkylbenzene (DETAL ~ type) having a 2/3-
Phenyl
index of about 150.
In the table below, percentages are by weight:
A B C
I 25% 15% 10%
II 75% 85% 90%
Each of the above blends has a 2/3-phenyl index in the range from about 160 to
about
275.
EXAMPLE 22
Modified Alkylbenzene Mixture according to the invention
With a 2/3-Phenyl Index of about 550 and a 2-Methyl-2-Phenyl Index of about
0.02
110.25 g of the substantially mono methyl branched olefin mixture of example
2, 36.75 g
a nonbranched olefin mixture (decene : undecene : dodecene : tridecene ratio
of 2 : 9
20 : 18) and 36 g of a shape selective zeolite catalyst (acidic mordenite
catalyst ZeocatTM
FM-8/25H) are added to a 2 gallon stainless steel, stirred autoclave. Residual
olefin and
catalyst in the container are washed into the autoclave with 300 mL of n-
hexane and the
autoclave is sealed. From outside the autoclave cell, 2000 g of benzene
(contained in a
isolated vessel and added by way of an isolated pumping system inside the
isolated
autoclave cell) is added to the autoclave. The autoclave is purged twice with
250 psig
N2, and then charged to 60 psig N2. The mixture is stirred and heated to about
200°C
for about 4-5 hours. The autoclave is cooled to about 20°C overnight.
The valve is
opened leading from the autoclave to the benzene condenser and collection
tank. The
autoclave is heated to about 120°C with continuous collection of
benzene. No more
benzene is collected by the time the reactor reaches 120°C. The reactor
is then cooled to
40°C and 750 g of n-hexane is pumped into the autoclave with mixing.
The autoclave is
then drained to remove the reaction mixture. The reaction mixture is filtered
to remove
catalyst and the n-hexane is removed under vacuum. The product is distilled
under
vacuum (1-5 mm of Hg). A modified alkylbenzene mixture with a 2/3-Phenyl index
of
about 550 and a 2-methyl-2-phenyl index of about 0.02 is collected from
76°C - 130°C
( 167 g).
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EXAMPLE 23
Modified Alkylbenzenesulfonic Acid Mixture according to the invention
(Branched and Nonbranched Alkylbenzenesulfonic Acid Mixture)
with a 2/3-Phenyl Index of about 550 and a 2-Methyl-2-Phenyl Index of about
0.02
The modified alkylbenzene mixture of example 22 is sulfonated with a molar
equivalent
of chlorosulfonic acid using methylene chloride as solvent. The methylene
chloride is
removed to give 210 g of a modified alkylbenzenesulfonic acid mixture with a
2/3-
Phenyl index of about 550 and a 2-methyl-2-phenyl index of about 0.02.
EXAMPLE 24
Modified Alkylbenzenesulfonate, Sodium Salt Mixture According to the invention
(Branched and Nonbranched Alkylbenzenesulfonate, Sodium Salt Mixture)
with a 2/3-Phenyl Index of about 550 and a 2-Methyl-2-Phenyl Index of about
0.02
The modified alkylbenzenesulfonic acid of example 23 is neutralized with a
molar
equivalent of sodium methoxide in methanol and the methanol is evaporated to
give 225
g of a modified alkylbenzenesulfonate, sodium salt mixture with a 2/3-Phenyl
index of
about 550 and a 2-methyl-2-phenyl index of about 0.02.
Methods for Determining Compositional Parameters (2/3-phenyl index 2-methyl-2-
phenyl index) of Mixed Alkylbenzene/ Alkylbenzenesulfonate/
Alkylbenzenesulfonic
Acid Systems.
It is well known in the art to determine compositional parameters of
conventional linear
alkylbenzenes and/or highly branched alkylbenzenesulfonates (TPBS, ABS). See,
for
example Surfactant Science Series, Volume 40, Chapter 7 and Surfactant Science
Series,
Volume 73, Chapter 7. Typically this is done by GC and/or GC-mass spectroscopy
for
the alkylbenzenes and HPLC for the alkylbenzenesulfonates or sulfonic acids;
13C nmr is
also commonly used. Another common practice is desulfonation. This permits GC
and/or
GC-mass spectroscopy to be used, since desulfonation converts the sulfonates
or sulfonic
acids to the alkylbenzenes which are tractable by such methods.
In general, the present invention provides unique and relatively complex
mixtures
of alkylbenzenes, and similarly complex surfactant mixtures of
alkylbenzenesulfonates
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and/or alkylbenzenesulfonic acids. Compositional parameters of such
compositions can
be determined using variations and combinations of the art-known methods.
The sequence of methods to be used depends on the composition to be
characterized as follows:
Composition Sequence of Methods (Methods separated
by commas
to be characterized are run in sequence, others can be run
in parallel)
Alkylbenzene mixturesGC, NMR1 NMR 2
Alkylbenzene mixturesGC, DIS, GC, NMRl NMR 2
with impurities*
AlkylbenzenesulfonicOption 1: HPLC, NMR3 NMR 4
acid
mixtures Option 2: HPLC, DE, NMR1 NMR 2
AlkylbenzenesulfonateOption 1: HPLC, AC, NMR3 NMR 4
salt mixtures Option 2: HPLC, DE, NMRl NMR 2
AlkylbenzenesulfonicOption 1: HPLC, HPLC-P, HPLC, NMR3 NMR
acid 4
mixtures Option 2: HPLC, DE, DIS, GC, NMRl NMR
2
with impurities*
AlkylbenzenesulfonateOption 1: HPLC, HPLC-P, HPLC, AC, NMR3
NMR 4
salt mixtures Option 2: HPLC, DE, DIS, GC, NMRl NMR
2
with impurities*
'~ l ypicaliy preferred when the material contains more than about 10%
impurities such as
dialkylbenzenes, olefins, paraffins, hydrotropes, dialkylbenzenesulfonates,
etc.
GC
Equipment:
~ Hewlett Packard Gas Chromatograph HP5890 Series II equipped with a
split/splitless
inj ector and FID
~ J&W Scientific capillary column DB-1HT, 30 meter, 0.25mm id, O.lum film
thickness
cat# 1221131
~ Restek Red lite Septa 1 lmm cat# 22306
~ Restek 4mm Gooseneck inlet sleeve with a carbofrit cat# 20799-209.5
~ O-ring for inlet liner Hewlett Packard cat# 5180-4182
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~ J.T.Baker HPLC grade Methylene Chloride cat# 9315-33, or equivalent
~ 2m1 GC autosampler vials with crimp tops, or equivalent
Sample Preparation:
~ Weigh 4-S mg of sample into a 2 ml GC autosampler vial
~ Add 1 ml J.T. Baker HPLC grade Methylene Chloride, cat# 9315-33 to the GC
vial,
seal with llmm crimp vial teflon lined closures (caps), part # HP5181-1210
using
crimper tool, part # HP8710-0979 and mix well
~ The sample is now ready for injection into the GC
GC Parameters:
Carrier Gas: Hydrogen
Column Head Pressure: 9 psi
Flows: Column Flow @ 1 ml/min.
Split Vent @ ~3m1/min.
Septum Purge @ 1 ml/min.
Injection: HP 7673 Autosampler, 10 ul syringe, lul injection
Injector Temperature: 350 °C
Detector Temperature: 400 °C
Oven Temperature Program: initial 70 °C hold 1 min.
rate 1 °C/min.
final 180 °C hold 10 min.
Standards required for this method are 2-phenyloctane and 2-phenylpentadecane,
each
freshly distilled to a purity of greater than 98%. Run both standards using
the conditions
specified above to define the retention time for each standard. This defines a
rentention
time range which is the retention time range to be used for characterizing any
alkylbenzenes or alkylbenzene mixtures in the context of this invention (e.g.,
test
samples). Now run the test samples for which compositional parameters are to
be
determined. Test samples pass the GC test provided that greater than 90% of
the total
GC area percent is within the retention time range defined by the two
standards. Test
samples that pass the GC test can be used directly in the NMR1 and NMR2 test
methods.
Test samples that do not pass the GC test must be further purified by
distillation until the
test sample passes the GC test.
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DESULFONATION (DE)
The desulfonation method is a standard method described in "The Analysis of
Detergents and Detergent Products" by G. F. Longman on pages 197-199. Two
other
useful descriptions of this standard method are given on page 230-231 of
volume 40 of
the Surfactant Sience Series edited by T. M. Schmitt: "Analysis of
Surfactants" and on
page 272 of volume 73 of the Surfactant Science Series: "Anionic Surfactants"
edited by
John Cross. This is an alternative method to the HPLC method, described
herein, for
evaluation of the branched and nonbranched alkylbenzenesulfonic acid and/or
salt
mixtures (Modified Alkylbenzensulfonic acid and or salt Mixtures). The method
provides a means of converting the sulfonic acid and/or salt mixture into
branched and
nonbranched alkylbenzene mixtures which can then be analyzed by means of the
GC and
NMR methods NMR1 and NMR2 described herein.
HPLC
See L.R. Snyder and J.J. Kirkland, "Introduction to Modern Liquid
Chromatography",
2nd. Ed., Wiley, NY, 1979.
Apparatus
Suitable HPLC System Waters Division of Millipore or equivalent.
HPLC pump with He sparge and Waters, model 600 or equivalent
temperature control
Autosampler/injector Waters 717, or equivalent
Autosampler 48 position tray Waters or equivalent
UV detector Waters PDA 996 or equivalent
Fluorescence detector Waters 740 or equivalent
Data System/Integrator Waters 860 or equivalent
Autosampler vials and caps 4 mL capacity, Millipore #78514 and
#7851 S.
HPLC Column, X2 Supelcosil LC18, 5 pm, 4.6 mm x 25 cm,
Supelcosil #58298
Column Inlet Filter Rheodyne O.Sum x 3 mm
Rheodyne #7335
LC eluent membrane filters Millipore SJHV M47 10, disposable filter
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funnel with 0.45 ~m membrane.
Balance Sartorius or equivalent; precision ~O.OOOlg.
Vacuum Sample Clarification Kit with pumps and
filters, Waters #WAT085113.
Rea _gents
C8 LAS standard material Sodium-p-2-octylbenzene sulfonate.
C15 LAS standard material Sodium-p-2-pentadecylbenzene sulfonate.
Procedure
A. Preparation of HPLC mobile Phase
1. Mobile phase A
a) Weigh 11.690 g sodium chloride and transfer to a 2000 mL
volumetric flask. Dissolve in 200 mL HPLC grade water.
b) Add 800 mL of acetonitrile and mix. Dilute to volume after
solution comes to room temperature. This prepares a solution of
100 mM NaCI/40% ACN.
c) Filter through an LC eluent membrane filter and degas prior to use.
2. Mobile phase B - Prepare 2000 mL of 60% acetonitrile in HPLC grade
water. Filter through an LC eluent membrane filter and degas prior to use.
B. C8 and C 15 Internal Standard Solution
1. Weigh 0.050 g of a 2-phenyloctylbenzenesulfonate and O.OSOg of 2-
Phenylpentadecanesulfonate standards and quantitatively transfer to a 100
mL volumetric flask.
2. Dissolve with 30 mL ACN and dilute to volume with HPLC grade water.
This prepares ca. 1500 ppm solution of the mixed standard.
C. Sample Solutions
1. Wash Solutions - Transfer 250 ~,L of the standard solution to a 1 mL
autosampler vial and add 750 ~L of the wash solution. Cap and place in
the autosampler tray.
2. Alkylbenzenesulfonic acid or Alkylbenzenesulfonate - Weigh 0.10 g of
the alkylbenzenesulfonic acid or salt and quantitatively transfer to a 100
mL volumetric flask. Dissolve with 30 mL ACN and dilute to volume
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with HPLC grade water. Transfer 250 ~L of the standard solution to a 1
mL autosampler vial and add 750 pL of the sample solution. Cap and
place in the autosampler tray. If solution is excessively turbid, filter
through 0.45 um membrane before transferring to auto-sampler vial. Cap
and place in the auto-sampler tray.
D. HPLC System
1. Prime HPLC pump with mobile phase. Install column and column inlet
filter and equilibrate with eluent (0.3 mL/min for at least 1 hr.).
2. Run samples using the following HPLC conditions:
Mobile phase A 100 mM NaCI/40% ACN
Mobile phase B 40% H20/60% ACN
time 0 min. 100% Mobile phase A 0% Mobile Phase B
time 75 min. 5% Mobile phase A 95% Mobile Phase B
time 98 min. 5% Mobile phase A 95% Mobile Phase B
time 110 min. 100% Mobile phase A 0% Mobile Phase B
time 120 min. 100% Mobile phase A 0% Mobile Phase B
Note: A gradient delay time of 5-10 minutes may be needed depending on dead
volume of HPLC system.
Flow rate 1.2 mL/min.
Temperature 25°C
He sparge rate 50 mL/hr.
UV detector 225 nm
Fluorescence detector 7~ = 225 nm, ~, =295 nm with
sensitivity at 10 x.
Run time 120 min.
Injection volume 10 ~L
Replicate injections 2
Data rate 0.45 MB/Hr.
Resolution 4.8nm
3. The column should be washed with 100% water followed by 100%
acetonitrile and stored in 80/20 ACN/water.
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The HPLC elution time of the 2-phenyloctylbenzenesulfonate defines the lower
limit and the elution time of the 2-phenylpentadecanesulfonate standard
defines the upper
limit of the HPLC analysis relating to the alkylbenzenesulfonic acid/salt
mixture of the
invention. If 90% of the alkylbenzenesulfonic acid/salt mixture components
have
retention times within the range of the above standards then the sample can be
further
defined by methods NMR 3 and NMR 4.
If the alkylbenzenesulfonic acid/salt mixture contains 10% or more of
components outside the retention limits defined by the standards then the
mixture should
be further purified by method HPLC-P or by DE, DIS methods.
HPLC Preparative (HPLC-P)
Alkylbenzenesulfonic acids and/or the salts which contain substantial
impurities (10% or
greater) are purified by preparative HPLC. See L.R. Snyder and J.J. Kirkland,
"Introduction to Modern Liquid Chromatography", 2nd. Ed., Wiley, NY, 1979.
This is
routine to one skilled in the art. A sufficient quantity should be purified to
meet the
requirements of the NMR 3 and NMR 4.
Preuarative LC method using Mega Bond Elut Sep Pak~ (HPLC-P)
Alkylbenzenesulfonic acids and/or the salts which contain substantial
impurities (10% or
greater) can also be purified by an LC method (also defined herein as HPLC-P).
This procedure is actually preferred over HPLC column prep purification.
As much as 500 mg of unpurified MLAS salts can be loaded onto a lOg(60m1) Mega
Bond Elut Sep Pak~ and with optimized chromatography the purified MLAS salt
can be
isolated and ready for freeze drying within 2 hours. A 100 mg sample of
Modified
alkylbenzenesulfonate salt can be loaded onto a Sg(20m1) Bond Elut Sep Pak and
ready
within the same amount of time.
A. Instrumentation
HPLC: Waters Model 600E gradient pump, Model 717 Autosampler, Water's
Millennium PDA, Millenium Data Manager (v. 2.15)
Mega Bond Elut: C18 bonded phase, Varian Sg or lOg, PN:1225-6023, 1225-6031
with adaptors
HPLC Columns: Supelcosil LC-18 (X2), 250x4.6mm, Smm; #58298
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Analytical Balance: Mettler Model AE240, capable of weighing samples to
~O.Olmg
B. Accessories
Volumetrics: glass, lOmL
Graduated Cylinder: 1L
HPLC Autosampler Vials: 4mL glass vials with Teflon caps and glass low volume
inserts and pipette capable of accurately delivering 1, 2, and SmL volumes
C. Reagents and Chemicals
Water (DI-H20): Distilled, deionized water from a Millipore, Milli-Q system or
equivalent
Acetonitrile (CH3CN): HPLC grade from Baker or equivalent Sodium Chloride
Crystal
Baker Analyzed or equivalent
D. HPLC Conditions
Aqueous Phase Preparation:
A: To 600mL of DI-H20 contained in a 1L graduated cylinder, add 5.845
of sodium chloride. Mix well and add 400 ml ACN. Mix well.
B: To 400m1 of DI-Hz0 contained in a 1L graduated cylinder, add 600m1
ACN and mix well.
Reservoir A: 60/40, H20/CAN with salt and Reservoir B: 40/60,
H20/ACN
Run Conditions: Gradient: 100% A for 75 min. S%A/ 95% B for 98 min. 5%A/95% B
for 1 lOmin. 100%A for 125min.
Column Temperature Not Thermostatted (i.e., room temp.)
HPLC Flow Rate 1.2mL/min
Injection Volume IOmL
Run Time 125 minutes
UV Detection 225nm
Conc. >4mg/ml
SEP PAK EQUILIBRATION (BOND ELUT, SG)
1. Pass 10 ml of a solution containing 25/75 H20/ACN onto the sep pak by
applying
positive pressure with a 10 cc syringe at a rate of ~ 40 drops/min. Do not
allow the
sep pak to go dry.
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2. Immediately pass l Oml (x3) of a solution containing 70/30 H20/ACN in the
same
manner as #l. Do not allow the sep pak to go dry. Maintain a level of solution
(~lmm) at the head of the sep pals.
3. The sep pak is now ready for sample loading. MLAS
SAMPLE LOADING/ SEPARATION AND ISOLATION
4. Weigh <200 mg of sample into a 1 dram vial and add 2 ml of 70/30 H20/ACN.
Sonicate and mix well.
5. Load sample onto Bond Elut and with positive pressure from a 10 cc syringe
begin
separation. Rinse vial with 1 ml (x2) portions of the 70/30 solution and load
onto sep
pak. Maintain ~lmm of solution at the head of the sep pak.
6. Pass 10 ml of 70/30 onto the Bond Elut with positive pressure from a 10 cc
syringe at
a rate of ~40 drops/min.
7. 4. Repeat this with 3 ml and 4 ml and collect effluent if interested in
impurities.
MLAS ISOLATION AND COLLECTION
1. Pass 10 ml of solution containing 25/75 H20/ACN with positive pressure from
a 10
cc syringe and collect effluent. Repeat this with another 10 ml and again with
5 ml.
The isolated MLAS is now ready for freeze drying and subsequent
characterization.
2. Rotovap until ACN is removed and freeze dry the remaining H20. Sample is
now
ready for chromatography.
Note: When incorporating the Mega Bond Elut Sep Pak (10 g version) up to 500
mg
of sample can be loaded onto the sep pak and with solution volume adjustments,
the
effluent can be ready for freeze drying within 2 hours.
SEP PAK EQUILIBRATION (BOND ELUT, lOG)
1. Pass 20 ml of a solution containing 25/75 HZO/ACN onto the sep pak using
laboratory air or regulated cylinder air at a rate which will allow ~ 40
drops/min. You
can not use positive pressure from a syringe because it is not sufficient to
move the
solution thru the sep pak. Do not allow the sep pak to go dry.
2. Immediately pass 20m1 (x2) and an additional 10 ml of a solution containing
70/30
H20/ACN in the same manner as #1. Do not allow the sep pak to go dry. Maintain
a
level of solution (~lmm)at the head of the sep pak.
3. The sep pak is now ready for sample loading.
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MLAS SAMPLE LOADING/SEPARATION AND ISOLATION
1. Weigh <500 mg of sample into a 2 dram vial and add 5 ml of 70/30 H20/ACN.
Sonicate and mix well.
2. Load sample onto Bond Elut and with positive pressure from an air source
begin
separation. Rinse vial with 2 ml (x2) portions of the 70/30 solution and put
onto the
sep pak. Maintain ~lmm of solution at the head of the sep pak.
3. Pass 20 ml of 70/30 onto the Bond Elut with positive pressure from an air
source at a
rate of ~40 drops/min. Repeat this with 6 ml and 8 ml and collect effluent if
interested in impurities.
MLAS ISOLATION AND COLLECTION
1. Pass 20 ml of solution containing 25/75 H20/ACN with positive pressure from
an air
source and collect effluent.
2. Repeat this with another 20 ml and again with 10 ml. This isolated fraction
contains
the pure MLAS.
3. The isolated MLAS is now ready for freeze drying and subsequent
characterization.
4. Rotovap until ACN is removed and freeze dry the remaining H20.Sample is now
ready for chromatography.
Note: Adjustments in organic modifier concentration may be necessary for
optimum
separation and isolation.
DISTILLATION (DIS)
A 5 liter, 3-necked round bottom flask with 24/40 joints is equipped with a
magnetic stir
bar. A few boiling chips (Hengar Granules, catalog #136-C) are added to the
flask. A
91/2 inch long vigreux condenser with a 24/40 joint is placed in the center
neck of the
flask. A water cooled condenser is attached to the top of the vigreux
condenser which is
fitted with a calibrated thermometer. A vacuum receiving flask is attached to
the end of
the condenser. A glass stopper is placed in one side arm of the 5 liter flask
and a
calibrated thermometer in the other. The flask and the vigreux condenser are
wrapped
with aluminum foil. To the 5 liter flask, is added 2270 g of an alkylbenzene
mixture
which contains 10% or more impurities as defined by the GC method. A vacuum
line
leading from a vacuum pump is attached to the receiving flask. The
alkylbenzene
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mixture in the 5 liter flask is stirred and vacuum is applied to the system.
Once the
maximum vacuum is reached (at least 1 inch of Hg pressure by gauge or less),
the
alkylbenzene mixture is heated by means of an electric heating mantle. The
distillate is
collected in two fractions. Fraction A is collected from about 25°C to
about 90°C as
measured by the calibrated thermometer at the top of the vigreux column.
Fraction B is
collected from about 90°C to about 155°C as measured by the
calibrated thermometer at
the top of the vigreux column. Fraction A and pot residues (high boiling) are
discarded.
Fraction B (1881 g) contains the alkylbenzene mixture of interest. The method
can be
scaled according to the practitioner's needs provided that sufficient quantity
of the
alkylbenzene mixture remains after distillation for evaluation by NMR methods
NMR1
and NMR2.
ACIDIFICATION SAC)
Salts of alkylbenzenesulfonic acids are acidified by common means such as
reaction in a
solvent with HCl or sulfuric acid or by use of an acidic resin such as
Amberlyst 15.
Acificication is routine to one skilled in the art. After acidifying remove
all solvents,
especially any moisture, so that the samples are anhydrous and solvent-free.
Note: For all of the below NMR test methods, the chemical shifts of the NMR
spectrum
are externally referenced to CDC13, i.e. chloroform.
NMR1
isC-NMR 2/3-Phenyl Index for Alkylbenzene Mixtures
A 400 mg sample of an alkylbenzene mixture is dissolved in 1 ml of anhydrous
deuterated chloroform containing 1 % v/v TMS as reference and placed in a
standard
NMR tube. The 13C NMR is run on the sample on a 300 MHz NMR spectrometer using
a 20 second recycle time, a 40° i3C pulse width and gated heteronuclear
decoupling. At
least 2000 scans are recorded. The region of the 13C NMR spectrum between
about
145.00 ppm to about 150.00 ppm is integrated. The 2/3-Phenyl index of an
alkylbenzene
mixture is defined by the following equation:
2/3-Phenyl Index = (Integral from about 147.65 ppm to about 148.05
ppm)/(Integral
from about 145.70 ppm to about 146.15 ppm) x 100
NMR2
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13C-NMR 2-Methyl-2-Phenyl Index
A 400 mg sample of an anhydrous alkylbenzene mixture is dissolved in 1 ml of
anhydrous deuterated chloroform containing 1 % v/v TMS as reference and placed
in a
standard NMR tube. The 13C NMR is run on the sample on a 300 MHz NMR
spectrometer using a 20 second recycle time, a 40° i3C pulse width and
gated
heteronuclear decoupling. At least 2000 scans are recorded. The 13C NMR
spectrum
region between about 145.00 ppm to about 150.00 ppm is integrated. The 2-
methyl-2-
phenyl index of an alkylbenzene mixture is defined by the following equation:
2-methyl-2-phenyl index - (Integral from about 149.35 ppm to about 149.80
ppm)/(Integral from about 145.00 ppm to about 150.00 ppm).
NMR3
isC-NMR 2/3-Phenyl Index for Alkylbenzenesulfonic Acid Mixtures
A 400 mg sample of an anhydrous alkylbenzenesulfonic acid mixture is dissolved
in 1 ml
of anhydrous deuterated chloroform containing 1 % v/v TMS as reference and
placed in a
standard NMR tube. The 13C NMR is run on the sample on a 300 MHz NMR
spectrometer using a 20 second recycle time, a 40° i3C pulse width and
gated
heteronuclear decoupling. At least 2000 scans are recorded. The 13C NMR
spectrum
region between about 152.50 ppm to about 156.90 ppm is integrated. The 2/3-
Phenyl
Index of an alkylbenzenesulfonic acid mixtureis defined by the following
equation:
2/3-Phenyl Index = (Integral from about 154.40 to about 154.80 ppm)/(Integral
from
about 152.70 ppm to about 153.15 ppm) x 100
NMR4
'3C-NMR 2-Methyl-2-Phenyl Index for Alkylbenzenesulfonic Acid Mixtures
A 400 mg sample of an anhydrous alkylbenzenesulfonic acid mixture is dissolved
in 1 ml
of anhydrous deuterated chloroform containing 1 % v/v TMS as reference and
placed in a
standard NMR tube. The 13C NMR is run on the sample on a 300 MHz NMR
spectrometer using a 20 second recycle time, a 40° 13C pulse width and
gated
heteronuclear decoupling. At least 2000 scans are recorded. The 13C NMR
spectrum
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region between about 152.50 ppm to about 156.90 ppm is integrated. The 2-
methyl-2-
phenyl Index for an alkylbenzenesulfonic acid mixture is defined by the
following
equation:
2-methyl-2-phenyl index - (Integral from about 156.40 ppm to about 156.65
ppm)/(Integral from about 152.50 ppm to about 156.90 ppm).
AQUEOUS BASED HEAVY DUTY LIQUID DETERGENTS
SURFACTANTS
The present invention also comprises aqueous based liquid detergent
compositions.
The aqueous liquid detergent compositions preferably comprise from about 10%
to about
98%, preferably from about 30% to about 95%, by weight of an aqueous liquid
carrier
which is preferably water. Additionally, the aqueous liquid detergent
compositions of the
present invention comprise a surfactant system which preferably contains one
or more
detersive co-surfactants in addition to the branched surfactants disclosed
above. The
additional co-surfactants can be selected from nonionic detersive surfactant,
anionic
detersive surfactant, zwitterionic detersive surfactant, amine oxide detersive
surfactant,
and mixtures thereof. The surfactant system typically comprises from about S%
to about
70%, preferably from about 1 S% to about 30%, by weight of the detergent
composition.
Anionic Surfactant
Anionic surfactants include C 11-C 1 g alkyl benzene sulfonates (LAS) and
primary,
branched-chain and random C 1 p-C20 alkyl sulfates (AS), the C 10-C 1 g
secondary (2,3)
alkyl sulfates of the formula CH3(CH2)x(CHOS03 M+) CH3 and CH3
(CH2)y(CHOS03 M+) CH2CH3 where x and (y + 1) are integers of at least about 7,
preferably at least about 9, and M is a water-solubilizing cation, especially
sodium,
unsaturated sulfates such as oleyl sulfate, the C 10-C 1 g alkyl alkoxy
sulfates ("AEXS";
especially EO 1-7 ethoxy sulfates), C 1 p-C 1 g alkyl alkoxy carboxylates
(especially the EO
1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the C10-Clg alkyl
polyglycosides
and their corresponding sulfated polyglycosides, and C 12-C 1 g alpha-
sulfonated fatty acid
esters.
Generally speaking, anionic surfactants useful herein are disclosed in U.S.
Patent
No. 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent No.
3,919,678,
Laughlin et al, issued December 30, 1975.
Useful anionic surfactants include the water-soluble salts, particularly the
alkali
metal, ammonium and alkylolammonium (e.g., monoethanolammonium or
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triethanolammonium) salts, of organic sulfuric reaction products having in
their
molecular structure an alkyl group containing from about 10 to about 20 carbon
atoms
and a sulfonic acid or sulfuric acid ester group. (Included in the term
"alkyl" is the alkyl
portion of aryl groups.) Examples of this group of synthetic surfactants are
the alkyl
sulfates, especially those obtained by sulfating the higher alcohols (Cg-C 1 g
carbon
atoms) such as those produced by reducing the glycerides of tallow or coconut
oil.
Other anionic surfactants herein are the water-soluble salts of alkyl phenol
ethylene
oxide ether sulfates containing from about 1 to about 4 units of ethylene
oxide per
molecule and from about 8 to about 12 carbon atoms in the alkyl group.
Other useful anionic surfactants herein include the water-soluble salts of
esters of a-
sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty
acid group
and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of
2-acyloxy-
alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl
group and
from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble
salts of olefin
sulfonates containing from about 12 to 24 carbon atoms; and b-alkyloxy alkane
sulfonates
containing from about 1 to 3 carbon atoms in the alkyl group and from about 8
to 20
carbon atoms in the alkane moiety.
Particularly preferred anionic surfactants herein are the alkyl polyethoxylate
sulfates
of the formula
RO(C2H40)xS03-M+
wherein R is an alkyl chain having from about 10 to about 22 carbon atoms,
saturated or
unsaturated, M is a canon which makes the compound water-soluble, especially
an alkali
metal, ammonium or substituted ammonium cation, and x averages from about 1 to
about
15.
Preferred alkyl sulfate surfactants are the non-ethoxylated C12-15 prim' ~d
secondary alkyl sulfates. Under cold water washing conditions, i.e., less than
abut 65°F
(18.3°C), it is preferred that there be a mixture of such ethoxylated
and non-ethoxylated
alkyl sulfates. Examples of fatty acids include capric, lauric, myristic,
palmitic, stearic,
arachidic, and behenic acid. Other fatty acids include palmitoleic, oleic,
linoleic,
linolenic, and ricinoleic acid.
Nonionic Surfactant
Conventional nonionic and amphoteric surfactants include C 12-C 1 g alkyl
ethoxylates (AE) including the so-called narrow peaked alkyl ethoxylates and
C6-C12
alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy).
The C 10-
C 1 g N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples
include
the C 12-C 1 g N-methylglucamides. See WO 9,206,154. Other sugar-derived
surfactants
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include the N-alkoxy polyhydroxy fatty acid amides, such as C 10-C 1 g N-(3-
methoxypropyl) glucamide. The N-propyl through N-hexyl C 12-C 1 g glucamides
can be
used for low sudsing. C10-C20 conventional soaps may also be used. If high
sudsing is
desired, the branched-chain C 1 p-C 16 soaps may be used. Examples of nonionic
surfactants are described in U.S. Patent No. 4,285,841, Barrat et al, issued
August 25,
1981.
Preferred examples of these surfactants include ethoxylated alcohols and
ethoxylated alkyl phenols of the formula R(OC2H4)nOH, wherein R is selected
from the
group consisting of aliphatic hydrocarbon radicals containing from about 8 to
about 15
carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from
about 8 to
about 12 carbon atoms, and the average value of n is from about 5 to about 15.
These
surfactants are more fully described in U.S. Patent No. 4,284,532, Leikhim et
al, issued
August 18, 1981. Particularly preferred are ethoxylated alcohols having an
average of
from about 10 to abut 1 S carbon atoms in the alcohol and an average degree of
ethoxylation of from about 6 to about 12 moles of ethylene oxide per mole of
alcohol.
Mixtures of anionic and nonionic surfactants are especially useful.
Other conventional useful surfactants are listed in standard texts, including
C 12-
C 1 g betaines and sulfobetaines (sultaines).
Amine Oxide Surfactants
The compositions herein also contain amine oxide surfactants of the formula:
R1(EO)x(PO)y(BO)zN(O)(~H2R~)2~qH2o (~
In general, it can be seen that the structure (I) provides one long-chain
moiety
Rl(EO)x(PO)y(BO)z and two short chain moieties, CH2R'. R' is preferably
selected
from hydrogen, methyl and -CH20H. In general R1 is a primary or branched
hydrocarbyl
moiety which can be saturated or unsaturated, preferably, R1 is a primary
alkyl moiety.
When x+y+z = 0, R1 is a hydrocarbyl moiety having chainlength of from about 8
to about
18. When x+y+z is different from 0, R1 may be somewhat longer, having a
chainlength
in the range C 12-C24. The general formula also encompasses amine oxides
wherein
x+y+z = 0, R1 = Cg-Clg, R' is H and q is 0-2t preferably 2. These amine oxides
are
illustrated by C 12_ 14 a~Yldimethyl amine oxide, hexadecyl dimethylamine
oxide,
octadecylamine oxide and their hydrates, especially the dihydrates as
disclosed in U.S.
Patents 5,075,501 and 5,071,594, incorporated herein by reference.
The invention also encompasses amine oxides wherein x+y+z is different from
zero,
specifically x+y+z is from about 1 to about 10, R1 is a primary alkyl group
containing 8
to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in
these
embodiments y + z is preferably 0 and x is preferably from about 1 to about 6,
more
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preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents
propyleneoxy; and BO represents butyleneoxy. Such amine oxides can be prepared
by
conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates
with
dimethylamine followed by oxidation of the ethoxylated amine with hydrogen
peroxide.
Highly preferred amine oxides herein are solids at ambient temperature, more
preferably they have melting-points in the range 30°C to 90°C.
Amine oxides suitable for
use herein are made commercially by a number of suppliers, including Akzo
Chemie,
Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-
Othmer
review article for alternate amine oxide manufacturers. Preferred commercially
available
amine oxides are the solid, dehydrate ADMOX 16 and ADMOX 18, ADMOX 12 and
especially ADMOX 14 from Ethyl Corp.
Preferred embodiments include dodecyldimethylamine oxide dehydrate,
hexadecyldimethylamine oxide dehydrate, octadecyldimethylamine oxide
dehydrate,
hexadecyltris(ethyleneoxy)dimethyl-amine oxide, tetradecyldimethylamine oxide
dehydrate, and mixtures thereof.
Whereas in certain of the preferred embodiments R' is H, there is some
latitude with
respect to having R' slightly larger than H. Specifically, the invention
further
encompasses embodiments wherein R' is CH20H, such as hexadecylbis(2-
hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-
hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
Builders
The compositions herein also optionally, but preferably, contain up to about
50%,
more preferably from about 1% to about 40%, even more preferably from about S%
to
about 30%, by weight of a detergent builder material. Lower or higher levels
of builder,
however, are not meant to be excluded. Detergent builders can optionally be
included in
the compositions herein to assist in controlling mineral hardness. Inorganic
as well as
organic builders can be used. Builders are typically used in fabric laundering
compositions to assist in the removal of particulate soils. Detergent builders
are
described in U.S. Patent No. 4,321,165, Smith et al, issued March 23, 1982.
Preferred
builders for use in liquid detergents herein are described in U.S. Patent No.
4,284,532,
Leikhim et al, issued August 18, 1981.
Examples of silicate builders are the alkali metal silicates, particularly
those having
a Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as
the layered
sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H.
P. Rieck.
NaSKS-6 is the trademark for a crystalline layered silicate marketed by
Hoechst
(commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-
6
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silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2Si05
morphology
form of layered silicate. It can be prepared by methods such as those
described in
German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered
silicate for use herein, but other such layered silicates, such as those
having the general
formula NaMSix02x+1'yH20 wherein M is sodium or hydrogen, x is a number from
1.9
to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used
herein.
Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
NaSKS-1 l,
as the alpha, beta and gamma forms. As noted above, the delta-Na2Si05 (NaSKS-6
form) is most preferred for use herein. Other silicates may also be useful
such as for
example magnesium silicate, which can serve as a stabilizing agent for oxygen
bleaches
and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as
disclosed in German Patent Application No. 2,321,001 published on November 15,
1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders can be a significant builder ingredient in liquid detergent
formulations.
Aluminosilicate builders include those having the empirical formula:
Mz(zA102)y] ~xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range from 1.0
to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These
aluminosilicates can be crystalline or amorphous in structure and can be
naturally-
occurring aluminosilicates or synthetically derived. A method for producing
aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669,
Krummel,
et al, issued October 12, 1976. Preferred synthetic crystalline
aluminosilicate ion
exchange materials useful herein are available under the designations Zeolite
A, Zeolite P
(B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the
crystalline
aluminosilicate ion exchange material has the formula:
Nal2~(A102) 12(Si02) 12] ~xH20
wherein x is from about 20 to about 30, especially about 27. This material is
known as
Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein.
Preferably, the
aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate
compounds. As used
herein, "polycarboxylate" refers to compounds having a plurality of
carboxylate groups,
preferably at least 3 carboxylates. Polycarboxylate builder can generally be
added to the
composition in acid form, but can also be added in the form of a neutralized
salt. When
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utilized in salt form, alkali metals, such as sodium, potassium, and lithium,
or
alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful
materials. One important category of polycarboxylate builders encompasses the
ether
polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent
3,128,287,
issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued
January 18, 1972.
See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on
May 5,
1987. Suitable ether polycarboxylates also include cyclic compounds,
particularly
alicyclic compounds, such as those described in U.S. Patents 3,923,679;
3,835,163;
4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers of malefic anhydride with ethylene or vinyl methyl ether, l, 3, 5-
trihydroxy
benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the
various alkali
metal, ammonium and substituted ammonium salts of polyacetic acids such as
ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as
polycarboxylates such
as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene
1,3,5-
tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium salt),
are polycarboxylate builders of particular importance for heavy duty liquid
detergent
formulations due to their availability from renewable resources and their
biodegradability.
Oxydisuccinates are also especially useful in such compositions and
combinations.
Also suitable in the detergent compositions of the present invention are the
3,3-
dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
Patent
4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders
include the CS-
C20 alkyl and alkenyl succinic acids and salts thereof. A particularly
preferred
compound of this type is dodecenylsuccinic acid. Specific examples of
succinate builders
include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-
dodecenylsuccinate
(preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the
preferred
builders of this group, and are described in European Patent Application
86200690.5/0,200,263, published November S, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield
et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March
7, 1967.
See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C 12-C 1 g monocarboxylic acids, can also be incorporated
into the
compositions alone, or in combination with the aforesaid builders, especially
citrate
and/or the succinate builders, to provide additional builder activity. Such
use of fatty
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acids will generally result in a diminution of sudsing, which should be taken
into account
by the formulator.
In situations where phosphorus-based builders can be used the various alkali
metal
phosphates such as the well-known sodium tripolyphosphates, sodium
pyrophosphate and
sodium orthophosphate can be used. Phosphonate builders such as ethane-1-
hydroxy-l,l-
diphosphonate and other known phosphonates (see, for example, U.S. Patents
3,159,581;
3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
OTHER OPTIONAL COMPOSITION COMPONENTS
In addition to the liquid and solid phase components as hereinbefore
described, the
aqueous based detergent compositions can, and preferably will, contain various
other
optional components. Such optional components may be in either liquid or solid
form.
The optional components may either dissolve in the liquid phase or may be
dispersed
within the liquid phase in the form of fine particles or droplets. Some of the
other
materials which may optionally be utilized in the compositions herein are
described in
greater detail as follows:
Optional Inorganic Detergent Builders
The detergent compositions herein may also optionally contain one or more
types of
inorganic detergent builders beyond those listed hereinbefore that also
function as
alkalinity sources. Such optional inorganic builders can include, for example,
aluminosilicates such as zeolites. Aluminosilicate zeolites, and their use as
detergent
builders are more fully discussed in Corkill et al., U.S. Patent No.
4,605,509; Issued
August 12, 1986, the disclosure of which is incorporated herein by reference.
Also
crystalline layered silicates, such as those discussed in this '509 U.S.
patent, are also
suitable for use in the detergent compositions herein. If utilized, optional
inorganic
detergent builders can comprise from about 2% to 15% by weight of the
compositions
herein.
Optional Enzymes
The detergent compositions herein may also optionally contain one or more
types of
detergent enzymes. Such enzymes can include proteases, amylases, cellulases
and
lipases. Such materials are known in the art and are commercially available.
They may
be incorporated into the aqueous liquid detergent compositions herein in the
form of
suspensions, "marumes" or "prills". Another suitable type of enzyme comprises
those in
the form of slurries of enzymes in nonionic surfactants, e.g., the enzymes
marketed by
Novo Nordisk under the tradename "SL" or the microencapsulated enzymes
marketed by
Novo Nordisk under the tradename "LDP."
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Enzymes added to the compositions herein in the form of conventional enzyme
prills are especially preferred for use herein. Such prills will generally
range in size from
about 100 to 1,000 microns, more preferably from about 200 to 800 microns and
will be
suspended throughout the non-aqueous liquid phase of the composition. Prills
in the
compositions of the present invention have been found, in comparison with
other enzyme
forms, to exhibit especially desirable enzyme stability in terms of retention
of enzymatic
activity over time. Thus, compositions which utilize enzyme prills need not
contain
conventional enzyme stabilizing such as must frequently be used when enzymes
are
incorporated into aqueous liquid detergents.
If employed, enzymes will normally be incorporated into the non-aqueous liquid
compositions herein at levels sufficient to provide up to about 10 mg by
weight, more
typically from about 0.01 mg to about 5 mg, of active enzyme per gram of the
composition. Stated otherwise, the non-aqueous liquid detergent compositions
herein
will typically comprise from about 0.001 % to 5%, preferably from about 0.01 %
to 1 % by
weight, of a commercial enzyme preparation. Protease enzymes, for example, are
usually
present in such commercial preparations at levels sufficient to provide from
0.005 to 0.1
Anson units (AU) of activity per gram of composition.
Optional Chelating_A
The detergent compositions herein may also optionally contain a chelating
agent
which serves to chelate metal ions, e.g., iron and/or manganese, within the
non-aqueous
detergent compositions herein. Such chelating agents thus serve to form
complexes with
metal impurities in the composition which would otherwise tend to deactivate
composition components such as the peroxygen bleaching agent. Useful chelating
agents
can include amino carboxylates, phosphonates, amino phosphonates,
polyfunctionally-
substituted aromatic chelating agents and mixtures thereof.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetraacetates, N-hydxoxyethyl-ethylenediaminetriacetates,
nitrilotriacetates, ethylene-diamine tetrapropionates,
triethylenetetraaminehexacetates,
diethylenetriaminepentaacetates, ethylenediaminedisuccinates and ethanol
diglycines.
The alkali metal salts of these materials are preferred.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of this invention when at least low levels of total phosphorus
are permitted
in detergent compositions, and include ethylenediaminetetrakis (methylene-
phosphonates) as DEQUEST. Preferably, these amino phosphonates do not contain
alkyl
or alkenyl groups with more than about 6 carbon atoms.
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Preferred chelating agents include hydroxy-ethyldiphosphonic acid (HEDP),
diethylene triamine penta acetic acid (DTPA), ethylenediamine disuccinic acid
(EDDS)
and dipicolinic acid (DPA) and salts thereof. The chelating agent may, of
course, also act
as a detergent builder during use of the compositions herein for fabric
laundering/bleaching. The chelating agent, if employed, can comprise from
about 0.1
to 4% by weight of the compositions herein. More preferably, the chelating
agent will
comprise from about 0.2% to 2% by weight of the detergent compositions herein.
Optional Thickening Viscosity Control and/or Dispersing A ents
The detergent compositions herein may also optionally contain a polymeric
material
which serves to enhance the ability of the composition to maintain its solid
particulate
components in suspension. Such materials may thus act as thickeners, viscosity
control
agents and/or dispersing agents. Such materials are frequently polymeric
polycarboxylates but can include other polymeric materials such as
polyvinylpyrrolidone
(PVP) or polyamide resins.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, malefic acid (or malefic anhydride),
fumaric acid,
itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid.
The presence in the polymeric polycarboxylates herein of monomeric segments,
containing no carboxylate radicals such as vinylmethyl ether, styrene,
ethylene, etc. is
suitable provided that such segments do not constitute more than about 40% by
weight of
the polymer.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid.
Such acrylic acid-based polymers which are useful herein are the water-soluble
salts of
polymerized acrylic acid. The average molecular weight of such polymers in the
acid
form preferably ranges from about 2,000 to 100,000, more preferably from about
2,000 to
10,000, even more preferably from about 4,000 to 7,000, and most preferably
from about
4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include,
for
example, the alkali metal, salts. Soluble polymers of this type are known
materials. Use
of polyacrylates of this type in detergent compositions has been disclosed,
for example,
Diehl, U.S. Patent 3,308,067, issued March 7, 1967. Such materials may also
perform a
builder function.
If utilized, the optional thickening, viscosity control and/or dispersing
agents should
be present in the compositions herein to the extent of from about 0.1% to 4%
by weight.
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More preferably, such materials can comprise from about 0.5% to 2% by weight
of the
detergents compositions herein.
Optional Clay Soil Removal/Anti-redeposition Agents
The compositions of the present invention can also optionally contain water-
soluble
ethoxylated amines having clay soil removal and anti-redeposition properties.
If used,
soil materials can contain from about 0.01 % to about 5% by weight of the
compositions
herein.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S.
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred
clay soil
removal-anti-redeposition agents are the cationic compounds disclosed in
European
Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other
clay soil
removal/anti-redeposition agents which can be used include the ethoxylated
amine
polymers disclosed in European Patent Application 111,984, Gosselink,
published June
27, 1984; the zwitterionic polymers disclosed in European Patent Application
112,592,
Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
Patent
4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or
anti-
redeposition agents known in the art can also be utilized in the compositions
herein.
Another type of preferred anti-redeposition agent includes the carboxy methyl
cellulose
(CMC) materials. These materials are well known in the art.
Peroxygen Bleaching Agent With Optional Bleach Activators
Peroxygen bleaching agents may be organic or inorganic in nature. Inorganic
peroxygen bleaching agents are frequently utilized in combination with a
bleach
activator.
Useful organic peroxygen bleaching agents include percarboxylic acid bleaching
agents and salts thereof. Suitable examples of this class of agents include
magnesium
monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic
acid, 4-
nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such
bleaching
agents are disclosed in U.S. Patent 4,483,781, Hartman, Issued November 20,
1984;
European Patent Application EP-A-133,354, Banks et al., Published February 20,
1985;
and U.S. Patent 4,412,934, Chung et al., Issued November 1, 1983. Highly
preferred
bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as
described in U.S. Patent 4,634,551, Issued January 6, 1987 to Burns et al.
Inorganic peroxygen bleaching agents may also be used in the detergent
compositions herein. Inorganic bleaching agents are in fact preferred. Such
inorganic
peroxygen compounds include alkali metal perborate and percarbonate materials,
most
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preferably the percarbonates. For example, sodium perborate (e.g. mono- or
tetra-
hydrate) can be used. Suitable inorganic bleaching agents can also include
sodium or
potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches,
sodium
pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Persulfate
bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
Frequently inorganic peroxygen bleaches will be coated with silicate, borate,
sulfate or
water-soluble surfactants. For example, coated percarbonate particles are
available from
various commercial sources such as FMC, Solvay Interox, Tokai Denka and
Degussa.
Inorganic peroxygen bleaching agents, e.g., the perborates, the percarbonates,
etc.,
are preferably combined with bleach activators, which lead to the in situ
production in
aqueous solution (i.e., during use of the compositions herein for fabric
launderinglbleaching) of the peroxy acid corresponding to the bleach
activator. Various
non-limiting examples of activators are disclosed in U.S. Patent 4,915,854,
Issued April
10, 1990 to Mao et al.; and U.S. Patent 4,412,934 Issued November 1, 1983 to
Chung et
al. The nonanoyloxybenzene sulfonate (HOBS) and tetraacetyl ethylene diamine
(TAED)
activators are typical. Mixtures thereof can also be used. See also the
hereinbefore
referenced U.S. 4,634,551 for other typical bleaches and activators useful
herein.
Other useful amido-derived bleach activators are those of the formulae:
R1N(RS)C(O)R2C(O)L or R1C(O)N(RS)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms,
R2 is an
alkylene containing from 1 to about 6 carbon atoms, RS is H or alkyl, aryl, or
alkaryl
containing from about 1 to about 10 carbon atoms, and L is any suitable
leaving group,
for example, oxybenzene sulfonate, -OOH, -OOM. A leaving group is any group
that is
displaced from the bleach activator as a consequence of the nucleophilic
attack on the
bleach activator by the perhydrolysis anion. A preferred leaving group is
phenol
sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)
oxybenzenesulfonate,
(6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as described in
the
hereinbefore referenced U.S. Patent 4,634,551. Such mixtures are characterized
herein as
(6-Cg-C 1 p alkamido-caproyl)oxybenzenesulfonate.
Another class of useful bleach activators comprises the benzoxazin-type
activators
disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October 30, 1990,
incorporated herein by reference. A highly preferred activator of the
benzoxazin-type is:
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71
O
i~
C,O
~C
N
Still another class of useful bleach activators includes the acyl lactam
activators,
especially acyl caprolactams and acyl valerolactams of the formulae:
O O
~I
O C-CH2-CH2 O C-CH2 CH2
R6 C-N ~ R6-~C-N
H2
\CH2-CH2~ \CH2 CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to about
12 carbon atoms. Highly preferred lactam activators include benzoyl
caprolactam,
octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl
caprolactam,
decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl
valerolactam, decanoyl valerolactam, undecenoyl valerolactam, 3,5,5-
trimethylhexanoyl
valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, Issued to
Sanderson,
October 8, 1985, incorporated herein by reference, which discloses acyl
caprolactams,
including benzoyl caprolactam, adsorbed into sodium perborate.
If peroxygen bleaching agents are used, they will generally comprise from
about
0.1% to 30% by weight of the composition. More preferably, peroxygen bleaching
agent
will comprise from about 1 % to 20% by weight of the composition. Most
preferably,
peroxygen bleaching agent will be present to the extent of from about 5% to
20% by
weight of the composition. If utilized, bleach activators can comprise from
about 0.5%
to 20%, more preferably from about 3% to 10%, by weight of the composition.
Frequently, activators are employed such that the molar ratio of bleaching
agent to
activator ranges from about 1:1 to 10:1, more preferably from about 1.5:1 to
5:1.
In addition, it has been found that bleach activators, when agglomerated with
certain acids such as citric acid, are more chemically stable.
Optional Bleach Catalysts
If desired, the bleaching compounds can be catalyzed by means of a manganese
compound. Such compounds are well known in the art and include, for example,
the
manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat.
5,244,594; U.S.
Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos.
549,271A1,
549,272A1, 544,440A2, and 544,490A1; Preferred examples of these catalysts
include
MnN2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mn~2(u-O)1(u-
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OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)2, Mn~4(u-O)6(1,4,7-
triazacyclononane)4(C104)4, Mn~Mn~4(u-O)1(u-OAc)2_(1,4,7-trimethyl-1,4,7-
triazacyclononane)2(C104)3, Mn~(1,4,7-trimethyl-1,4,7-triazacyclononane)-
(OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include
those
disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese
with
various complex ligands to enhance bleaching is also reported in the following
United
States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117;
5,274,147;
5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and
processes herein can be adjusted to provide on the order of at least one part
per ten
million of the active bleach catalyst species in the aqueous washing liquor,
and will
preferably provide from about 0.1 ppm to about 700 ppm, more preferably from
about 1
ppm to about 500 ppm, of the catalyst species in the laundry liquor.
Cobalt bleach catalysts useful herein are known, and are described, for
example,
in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inor~.
Bioinor~
Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein
are cobalt
pentaamine acetate salts having the formula [Co(NH3)SOAc] Ty, wherein "OAc"
represents an acetate moiety and "Ty' is an anion, and especially cobalt
pentaamine
acetate chloride, [Co(NH3)SOAc]C12; as well as [Co(NH3)SOAc](OAc)2;
[Co(NH3)SOAc](PF6)2; [Co~3)SOAc](504); [Co(NH3)SOAc](BF4)2; and
[Co(NH3)SOAc](N03)2 (herein "PAC").
These cobalt catalysts are readily prepared by known procedures, such as
taught
for example in the Tobe article and the references cited therein, in U.S.
Patent 4,810,410,
to Diakun et al, issued March 7,1989, J. Chem. Ed. (1989), 66 (12), 1043-45;
The
Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-
Hall;
1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inor~. Chem., 21, 2881-
2885
(1982); Inor~. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960);
and
Journal of Physical Chemistry, 56, 22-25 (1952).
As a practical matter, and not by way of limitation, the compositions and
cleaning
processes herein can be adjusted to provide on the order of at least one part
per hundred
million of the active bleach catalyst species in the aqueous washing medium,
and will
preferably provide from about 0.01 ppm to about 25 ppm, more preferably from
about
0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about S
ppm, of
the bleach catalyst species in the wash liquor. In order to obtain such levels
in the wash
liquor of an automatic washing process, typical compositions herein will
comprise from
about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%,
of
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73
bleach catalyst, especially manganese or cobalt catalysts, by weight of the
cleaning
compositions.
Optional Bri~hteners, Suds Suppressors Dyes and/or Perfumes
The detergent compositions herein may also optionally contain conventional
brighteners, suds suppressors, dyes and/or perfume materials. Such
brighteners, suds
suppressors, silicone oils, dyes and perfumes must, of course, be compatible
and non-
reactive with the other composition components in a non-aqueous environment.
If
present, brighteners suds suppressors, dyes and/or perfumes will typically
comprise from
about 0.0001 % to 2% by weight of the compositions herein.
Polymeric Soil Release A e~nt
Any polymeric soil release agent known to those skilled in the art can
optionally be
employed in the compositions and processes of this invention. Polymeric soil
release
agents are characterized by having both hydrophilic segments, to hydrophilize
the surface
of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments,
to deposit
upon hydrophobic fibers and remain adhered thereto through completion of
washing and
rinsing cycles and, thus, serve as an anchor for the hydrophilic segments.
This can enable
stains occurnng subsequent to treatment with the soil release agent to be more
easily
cleaned in later washing procedures.
Examples of polymeric soil release agents useful herein include U.S. Patent
4,721,580, issued January 26, 1988 to Gosselink; U.S. Patent 4,000,093, issued
December 28, 1976 to Nicol, et al.; European Patent Application 0 219 048,
published
April 22, 1987 by Kud, et al.; U.S. Patent 4,702,857, issued October 27, 1987
to
Gosselink; U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel.
Commercially available soil release agents include the SOKALAN type of
material, e.g.,
SOKALAN HP-22, available from BASF (West Germany). Also see U.S. Patent
3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur
issued
July 8, 1975. Examples of this polymer include the commercially available
material
ZELCON 5126 (from Dupont) and MILEASE T (from ICI). Other suitable polymeric
soil release agents include the terephthalate polyesters of U.S. Patent
4,711,730, issued
December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters
of U.S.
Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block
polyester
oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to
Gosselink.
Preferred polymeric soil release agents also include the soil release agents
of U.S. Patent
4,877,896, issued October 31, 1989 to Maldonado et al.
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If utilized, soil release agents will generally comprise from about 0.01 % to
about
10.0%, by weight, of the detergent compositions herein, typically from about
0.1% to
about 5%, preferably from about 0.2% to about 3.0%.
Chelating~ents
The detergent compositions herein may also optionally contain one or more iron
and/or manganese chelating agents. Such chelating agents can be selected from
the group
consisting of amino carboxylates, amino phosphonates, polyfunctionally-
substituted
aromatic chelating agents and mixtures therein, all as hereinafter defined.
Without
intending to be bound by theory, it is believed that the benefit of these
materials is due in
part to their exceptional ability to remove iron and manganese ions from
washing
solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents include ethylenediamine-
tetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo-triacetates,
ethylenediamine tetraproprionates, triethylenetetraaminehexacetates,
diethylenetriaminepenta.a.cetates, and ethanoldiglycines, alkali metal,
ammonium, and
substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in the
compositions of the invention when at lease low levels of total phosphorus axe
permitted
in detergent compositions, and include ethylenediaminetetrakis
(methylenephosphonates)
as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or
alkenyl
groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor
et al.
Preferred compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-
dihydroxy-3,5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate
("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233,
November
3, 1987, to Hartman and Perkins.
If utilized, these chelating agents will generally comprise from about 0.1 %
to about
10% by weight of the detergent compositions herein. More preferably, if
utilized, the
chelating agents will comprise from about 0.1 % to about 3.0% by weight of
such
compositions.
Clay Soil Removal/Anti-redeposition Agents
The compositions of the present invention can also optionally contain water-
soluble
ethoxylated amines having clay soil removal and antiredeposition properties.
Liquid
detergent compositions typically contain about 0.01% to about 5% of these
compositions.
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The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S.
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred
clay soil
removal-antiredeposition agents are the cationic compounds disclosed in
European Patent
Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay
soil
removal/antiredeposition agents which can be used include the ethoxylated
amine
polymers disclosed in European Patent Application 111,984, Gosselink,
published June
27, 1984; the zwitterionic polymers disclosed in European Patent Application
112,592,
Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
Patent
4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or
anti
redeposition agents known in the art can also be utilized in the compositions
herein.
Another type of preferred antiredeposition agent includes the carboxy methyl
cellulose
(CMC) materials. These materials are well known in the art.
Polymeric Dispersing A:~ents
Polymeric dispersing agents can advantageously be utilized at levels from
about
0.1 % to about 7%, by weight, in the compositions herein, especially in the
presence of
zeolite and/or layered silicate builders. Suitable polymeric dispersing agents
include
polymeric polycarboxylates and polyethylene glycols, although others known in
the art
can also be used. It is believed, though it is not intended to be limited by
theory, that
polymeric dispersing agents enhance overall detergent builder performance,
when used in
combination with other builders (including lower molecular weight
polycarboxylates) by
crystal growth inhibition, particulate soil release peptization, and anti-
redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, malefic acid (or malefic anhydride),
fumaric acid,
itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid.
The presence in the polymeric polycarboxylates herein or monomeric segments,
containing no carboxylate radicals such as vinylinethyl ether, styrene,
ethylene, etc. is
suitable provided that such segments do not constitute more than about 40% by
weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic
acid.
Such acrylic acid-based polymers which are useful herein are the water-soluble
salts of
polymerized acrylic acid. The average molecular weight of such polymers in the
acid
form preferably ranges from about 2,000 to 10,000, more preferably from about
4,000 to
7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of
such acrylic
acid polymers can include, for example, the alkali metal, ammonium and
substituted
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ammonium salts. Soluble polymers of this type are known materials. Use of
polyacrylates of this type in detergent compositions has been disclosed, for
example, in
Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred component of
the
dispersing/anti-redeposition agent. Such materials include the water-soluble
salts of
copolymers of acrylic acid and malefic acid. The average molecular weight of
such
copolymers in the acid form preferably ranges from about 2,000 to 100,000,
more
preferably from about 5,000 to 75,000, most preferably from about 7,000 to
65,000. The
ratio of acrylate to maleate segments in such copolymers will generally range
from about
30:1 to about l:l, more preferably from about 10:1 to 2:1. Water-soluble salts
of such
acrylic acid/maleic acid copolymers can include, for example, the alkali
metal,
ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers
of this
type are known materials which are described in European Patent Application
No. 66915,
published December 15, 1982, as well as in EP 193,360, published September 3,
1986,
which also describes such polymers comprising hydroxypropylacrylate. Still
other useful
dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such
materials
are also disclosed in EP 193,360, including, for example, the 45/45/10
terpolymer of
acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is polyethylene glycol (PEG).
PEG can exhibit dispersing agent performance as well as act as a clay soil
removal-
antiredeposition agent. Typical molecular weight ranges for these purposes
range from
about 500 to about 100,000, preferably from about 1,000 to about 50,000, more
preferably from about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used, especially
in
conjunction with zeolite builders. Dispersing agents such as polyaspartate
preferably
have a molecular weight (avg.) of about 10,000.
Dye Transfer Inhibiting A e~nts
The compositions of the present invention may also include one or more
materials
effective for inhibiting the transfer of dyes from one fabric to another
during the cleaning
process. Generally, such dye transfer inhibiting agents include polyvinyl
pyrrolidone
polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof.
If used,
these agents typically comprise from about 0.01 % to about 10% by weight of
the
composition, preferably from about 0.01% to about 5%, and more preferably from
about
0.05% to about 2%.
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More specifically, the polyamine N-oxide polymers preferred for use herein
contain
units having the following structural formula: R-Ax-P; wherein P is a
polymerizable unit
to which an N-O group can be attached or the N-O group can form part of the
polymerizable unit or the N-O group can be attached to both units; A is one of
the
following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is
aliphatic,
ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any
combination
thereof to which the nitrogen of the N-O group can be attached or the N-O
group is part
of these groups. Preferred polyamine N-oxides are those wherein R is a
heterocyclic
group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and
derivatives thereof.
The N-O group can be represented by the following general structures:
O O
W )x- ~ -~2)y~ =N-W )x
(R3)z
wherein Rl, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups
or
combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group
can be
attached or form part of any of the aforementioned groups. The amine oxide
unit of the
polyamine N-oxides has a pKa <10, preferably pKa <'7, more preferred pKa <(.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric
backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide,
polyimides,
polyacrylates and mixtures thereof. These polymers include random or block
copolymers
where one monomer type is an amine N-oxide and the other monomer type is an N-
oxide.
The amine N-oxide polymers typically have a ratio of amine to the amine N-
oxide of 10:1
to 1:1,000,000. However, the number of amine oxide groups present in the
polyamine
oxide polymer can be varied by appropriate copolymerization or by an
appropriate degree
of N-oxidation. The polyamine oxides can be obtained in almost any degree of
polymerization. Typically, the average molecular weight is within the range of
500 to
1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000.
This
preferred class of materials can be referred to as "PVNO".
The most preferred polyamine N-oxide useful in the detergent compositions
herein
is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about
50,000
and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as
a
class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has
an average
molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to
200,000,
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and most preferably from 10,000 to 20,000. (The average molecular weight range
is
determined by light scattering as described in Barth, et al., Chemical
Analysis, Vol 113.
"Modern Methods of Polymer Characterization", the disclosures of which are
incorporated herein by reference.) The PVPVI copolymers typically have a molar
ratio of
N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from
0.8:1 to
0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either
linear or
branched.
The present invention compositions also may employ a polyvinylpyrrolidone
("PVP") having an average molecular weight of from about 5,000 to about
400,000,
preferably from about 5,000 to about 200,000, and more preferably from about
5,000 to
about 50,000. PVP's are known to persons skilled in the detergent field; see,
for example,
EP-A-262,897 and EP-A-256,696, incorporated herein by reference. Compositions
containing PVP can also contain polyethylene glycol ("PEG") having an average
molecular weight from about 500 to about 100,000, preferably from about 1,000
to about
10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash
solutions
is from about 2:1 to about 50:1, and more preferably from about 3:1 to about
10:1.
The detergent compositions herein may also optionally contain from about
0.005%
to S% by weight of certain types of hydrophilic optical brighteners which also
provide a
dye transfer inhibition action. If used, the compositions herein will
preferably comprise
from about 0.01 % to 1 % by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those
having
the structural formula:
R1 R2
N H H N
N OOIj 0 C C O NOO N
ON H H NO
R2 S03M S~3M Ri
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is
selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a
cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-
triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the tradename Tinopal-UNPA-
GX by
Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical
brightener useful in the detergent compositions herein.
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When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-
anilino-6-(N-
2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic
acid
disodium salt. This particular brightener species is commercially marketed
under the
tradename Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such
as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]2,2'-
stilbenedisulfonic acid, sodium salt. This particular brightener species is
commercially
marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
The specific optical brightener species selected for use in the present
invention
provide especially effective dye transfer inhibition performance benefits when
used in
combination with the selected polymeric dye transfer inhibiting agents
hereinbefore
described. The combination of such selected polymeric materials (e.g., PVNO
and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal
SBM-
GX and/or Tinopal AMS-GX) provides significantly better dye transfer
inhibition in
aqueous wash solutions than does either of these two detergent composition
components
when used alone. Without being bound by theory, it is believed that such
brighteners
work this way because they have high affinity for fabrics in the wash solution
and
therefore deposit relatively quick on these fabrics. The extent to which
brighteners
deposit on fabrics in the wash solution can be defined by a parameter called
the
"exhaustion coefficient". The exhaustion coefficient is in general as the
ratio of a) the
brightener material deposited on fabric to b) the initial brightener
concentration in the
wash liquor. Brighteners with relatively high exhaustion coefficients are the
most
suitable for inhibiting dye transfer in the context of the present invention.
Of course, it will be appreciated that other, conventional optical brightener
types of
compounds can optionally be used in the present compositions to provide
conventional
fabric "brightness" benefits, rather than a true dye transfer inhibiting
effect. Such usage
is conventional and well-known to detergent formulations.
COMPOSITION FORM
The aqueous based heavy-duty liquid detergent compositions disclosed herein
can
contain water and other solvents as Garners. Low molecular weight primary or
secondary
alcohols exemplified by methanol, ethanol, propanol, and isopropanol are
suitable.
Monohydric alcohols are preferred for solubilizing surfactant, but polyols
such as those
containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups
(e.g.,
1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be
used. The
compositions may contain from 5% to 90%, typically 10% to SO% of such
carriers.
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The detergent compositions herein will preferably be formulated such that,
during
use in aqueous cleaning operations, the wash water will have a pH of between
about 6.5
and about 11, preferably between about 7.5 and 11. Techniques for controlling
pH at
recommended usage levels include the use of buffers, alkalis, acids, etc., and
are well
known to those skilled in the art.
COMPOSITION PREPARATION AND USE
The aqueous based heavy-duty liquid detergent compositions of the present
invention can be made by mixing and blending the desired ingredients with the
desired
sovent. In a typical process for preparing such compositions, essential and
certain
preferred optional components will be combined in a particular order and under
certain
conditions.
The compositions of this invention, prepared as hereinbefore described, can be
used
to form aqueous washing solutions for use in the laundering and bleaching of
fabrics.
Generally, an effective amount of such compositions is added to water,
preferably in a
conventional fabric laundering automatic washing machine, to form such aqueous
laundering/bleaching solutions. The aqueous washing/bleaching solution so
formed is
then contacted, preferably under agitation, with the fabrics to be laundered
and bleached
therewith.
An effective amount of the liquid detergent compositions herein added to water
to
form aqueous laundering/bleaching solutions can comprise amounts sufficient to
form
from about 500 to 7,000 ppm of composition in aqueous solution. More
preferably, from
about 800 to 3,000 ppm of the detergent compositions herein will be provided
in aqueous
washing/bleaching solution.
The following examples illustrate the preparation and performance advantages
of the
modified alkyl benzene sulfonate surfactant mixtures containing aqueous liquid
detergent
compositions of the instant invention. Such examples, however, are not
necessarily meant to
limit or otherwise define the scope of the invention herein. All parts,
percentages and ratios
used herein are expressed as percent weight unless otherwise specified. In the
following
Examples, the abbreviations for the various ingredients used for the
compositions have the
following meanings. In these Examples, the following abbreviation is used for
a modified
alkylbenzene sulfonate, sodium salt form or potassium salt form, prepared
according to any
of the preceding process examples: MLAS
ABBREVIATIONS
LAS Sodium linear alkyl benzene sulfonate
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MBASx Mid-chain branched primary alkyl (average
total carbons =
x) sulfate
MBAEXSz Mid-chain branched primary alkyl (average
total carbons =
z) ethoxylate (average EO = x) sulfate,
sodium salt
MBAEx Mid-chain branched primary alkyl (average
total carbons
= x) ethoxylate (average EO = 5)
Endolase Endoglunase enzyme of activity 3000 CEVU/g
sold by
NOVO Industries A/S
MEA Monoethanolamine
PG Propanediol
BPP Butoxy - propoxy - propanol
EtOH Ethanol
NaOH Solution of sodium hydroxide
NaTS Sodium toluene sulfonate
Citric acid Anhydrous citric acid
CxyFA C 1 x-C 1 y fatty acid
CxyEz A Clx-ly branched primary alcohol condensed
with an
average of z moles of ethylene oxide
Carbonate Anhydrous sodium carbonate with a particle
size
between 200~m and 900~,m
Citrate Tri-sodium citrate dihydrate of activity
86.4% with a
particle size distribution between 425~m
and 850 ~m
TFAA C16-18 alkyl N-methyl glucamide
LMFAA C12-14 alkyl N-methyl glucamide
APA C8-C10 amido propyl dimethyl amine
Fatty Acid (C C 12-C 14 fatty acid
12/ 14)
Fatty Acid (TPK)Topped palm kernel fatty acid
Fatty Acid (RPS)Rapeseed fatty acid
Borax Na tetraborate decahydrate
PAA Polyacrylic Acid (mw = 4500)
PEG Polyethylene glycol (mw--4600)
MES Alkyl methyl ester sulfonate
SAS Secondary alkyl sulfate
NaPS Sodium paraffin sulfonate
C45AS Sodium C 14-C 15 linear alkyl sulfate
CxyAS Sodium Clx-Cly alkyl sulfate (or other
salt if specified)
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CxyEzS Sodium Clx-Cly alkyl sulfate condensed
with z moles of ethylene oxide (or other
salt if specified)
CxyEz A Clx-ly branched primary alcohol condensed
with an
average of z moles of ethylene oxide
AQA R2.N+(CH3)x((C2H4O)yH)z with R2 = Cg - C18
x+z=3,x=Oto3,z=Oto3,y=1 to 15.
STPP Anhydrous sodium tripolyphosphate
Zeolite A Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12~ 27H20 having a primary
particle
size in the range from 0.1 to 10 micrometers
NaSKS-6 Crystalline layered silicate of formula
8 -Na2Si205
Carbonate Anhydrous sodium carbonate with a particle
size
between 200pm and 900~m
Bicarbonate Anhydrous sodium bicarbonate with a particle
size
distribution between 400pm and 1200~m
Silicate Amorphous Sodium Silicate (Si02:Na20; 2.0
ratio)
Sulfate Anhydrous sodium sulfate
PAE ethoxylated (15-18) tetraethylene pentamine
PIE ethoxylated polyethylene imine
PAEC methyl quaternized ethoxylated dihexylene
triamine
MA/AA Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 70,000.
CMC Sodium carboxymethyl cellulose
Protease Proteolytic enzyme of activity 4KNPU/g sold by
NOVO Industries A/S under the tradename Savinase
Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by
NOVO Industries A/S under the tradename Carezyme
Amylase Amylolytic enzyme of activity 60KNU/g sold by
NOVO Industries A/S under the tradename Termamyl
60T
Lipase Lipolytic enzyme of activity 100kLU/g sold by NOVO
Industries A/S under the tradename Lipolase
PB 1 Anhydrous sodium perborate bleach of nominal
formula NaB02.H202
Percarbonate Sodium Percarbonate of nominal formula
2Na2C03.3H202
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NaDCC Sodium dichloroisocyanurate
NOBS Nonanoyloxybenzene sulfonate, sodium salt
TAED Tetraacetylethylenediamine
DTPMP Diethylene triamine penta (methylene
phosphonate),
marketed by Monsanto under Trade name
bequest 2060
Photoactivated bleach Sulfonated Zinc
Phthalocyanine
bleach encapsulated in dextrin soluble
polymer
Brightener Disodium 4,4'-bis(2-sulphostyryl)biphenyl
1
Brightener Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-
2
triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP 1,1-hydroxyethane diphosphonic acid
SRP 1 Sulfobenzoyl end capped esters with oxyethylene
oxy
and terephthaloyl backbone
SRP 2 sulfonated ethoxylated terephthalate
polymer
SRP 3 methyl capped ethoxylated terephthalate
polymer
Silicone antifoamPolydimethylsiloxane foam controller
with siloxane-
oxyalkylene copolymer as dispersing agent with a ratio
of said foam controller to said dispersing agent of 10:1
to 100:1.
Isofol 16 Condea trademark for C16 (average) Guerbet alcohols
CaCl2 Calcium chloride
MgCl2 Magnesium chloride
DTPA Diethylene triamine pentaacetic acid
EXAMPLE 25
Liquid detergent compositions are made according to the follow;"
A B C D
C AE3S 2 8 7 5
MLAS 15 12 10 8
C -C alk ldimeth 1 amine oxide - - - 2
C AS 6 4 6 8
C N-meth 1 lucamide S 4 3 3
C AES 6 1 1 1
C -C fatt acid 11 4 4 3
Citric acid 1 3 3 2
DTPMP 1 1 1 0.5
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MEA 8 5 5 2
NaOH 1 2.5 1 1.5
PG 14.5 13.1 10.0 8
EtOH 1.8 4.7 5.4 1
Am lase (300KNU/ 0.1 0.1 0.1 0.1
Li ase D96/L (100KNU/ 0.15 0.15 0.15 0.15
Protease 35 1) 0.5 0.5 0.5 0.5
Endolase 0.05 0.05 0.05 0.05
Cellulase 0.09 0.09 0.09 0.09
Tere hthalate-based of er 0.5 - 0.3 0.3
Boric acid 2.4 2.8 2.8 2.4
Sodium x lene sulfonate - 3 - _
2-bu 1-octanol 1 1 1 1
Branched silicone 0.3 0.3 0.3 0.3
Water & minors U to
100%
The above liquid detergent compositions (A-D) are found to be very efficient
in
the removal of a wide range of stains and soils from fabrics under various
usage
conditions.
EXAMPLE 26
The following compositions (E to J) are heavy duty liquid laundry detergent
compositions according to the present invention.
Exam le #: E F G H I J
MLAS 17 15 7.0 7.0 12 12
C35AE3S/C25AE32.0 9.0 - - 7.0 7.0
S
C25 AE2.SS - - 12.0 12.0 - -
C24 N-Me 6.0 5.0 4.5 3.7 4.0 4.0
Glucamide
C35 E7 6.0 1.0 - - - -
C23 E9 - - 2.0 1.0 5.0 S.0
C 10 APA - 1.5 - 2.0 - 2. 5
C24 Fatt Acid 7.5 1.1 2.0 4.0 5.0 5.0
C48 Fatt Acid 3.0 3.5 - - - -
Citric Acid 1.0 3.5 3.0 3.0 3.0 3.0
Protease 34 0.6 0.6 0.9 0.9 1.2 1.2
#)
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Li ase 0.1 0.1 0.1 0.1 0.2 0.2
Amylase 0.1 0.1 0.1 0.1 - 0.1
300KMU/ )
Cellulase 0.03 0.03 0.05 0.05 0.2 0.2
Endolase 0.1 0.1 - - _ _
Bri tener 2 0.1 0.1 - - - -
Boric Acid 3.0 3.0 3.5 3.5 4.0 4.0
MEA 8.0 4.0 1.0 1.5 7.0 7.0
NaOH 1.0 4.0 3.0 2.5 1.0 1.0
PG 12.0 12.0 7.5 7.5 7.0 7.0
EtOH 1.0 1.0 3.5 3.5 6.0 6.0
Na TS - - 2.5 2.5 - -
Minors BalanceBalanceBalanceBalanceBalanceBalance
The Following Examples illustrate aqueous based liquid detergent compositions
according to the present invention.
EXAMPLE 27
Aqueous based heavy duty liquid laundry detergent compositions F to J which
comprise the mid-chain branched surfactants of the present invention are
presented
below.
In redient F G H I J
MBAE1.8S14.4 10 12 14 16 20
MLAS 10 8 6 4 0
C23E9 2 2 2 2 2
LMFAA 5 5 5 5 0
Citric acid builder3 3 3 3 5
Fatt acid builder2 2 2 2 0
PAE 1 1 1.2 1.2 0.5
PG 8 8 8 8 4.5
EtOH 4 4 4 4 2
Boric acid 3.5 3.5 3.5 3.5 2
Sodium Cumene 3 3 3 3 0
Sulfonate
H = 8.0 8.0 8.0 8.0 7.0
Enz mes, d es, balancebalancebalancebalancebalance
water
100 100 100 100 100
% % % %
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EXAMPLE 28
The following aqueous liquid laundry detergent compositions K to O are
prepared
in accord with the invention:
K L M N O
MLAS 1-7 7-12 12-17 17-22 1-35
Any combination 1 S 10 - 5 - 0 - 0 - 25
o - 15 10 S
C25 AExS*Na (x = 21
1.0
- 2.5)
C25 AS (linear to
high
2-alkyl)
C14-17 NaPS
C12-16 SAS
C18 1,4 disulfate
LAS
C12-16 MES
MBAE1.8S14.4 and
/ or
MBAS 14.4
LMFAA 0-3.5 0-3.5 0-3.5 0-3.5 0-8
C23E9orC23E6.5 0-2 0-2 0-2 0-2 0-8
APA 0.5 0.5 0.5 0.5 0.5 -
2
Citric Acid S 5 5 5 0 - 8
Fatty Acid (TPK 2 2 2 2 0 - 14
or
C12/14
EtOH 4 4 4 4 0 - 8
PG 6 6 6 6 0-10
MEA 1 1 1 1 0 - 3
NaOH 3 3 3 3 0 - 7
NaTS 2.3 2.3 2.3 2.3 0-4
Na formate 0.1 0.1 0.1 0.1 0 - 1
Borax 2.5 2.5 2.5 2.5 0 - 5
Protease 0.9 0.9 0.9 0.9 0 - 1.3
Li ase 0.06 0.06 0.06 0.06 0 - 0.3
Am lace 0.15 0.15 0.15 0.15 0 - 0.4
Cellulase 0.05 0.05 0.05 0.05 0 - 0.2
PAE 0-0.6 0-0.6 0-0.6 0-0.6 0-2.5
PIE 1.2 1.2 1.2 1.2 0 - 2.5
PAEC 0-0.4 0-0.4 0-0.4 0-0.4 0-2
SRP 2 0.2 0.2 0.2 0.2 0 - 0.5
Bri tener 1 or 2 0.1 0.15 0.15 0.15 0 - 0.5
S
Silicone antifoam 0.12 0.12 0.12 0.12 0 - 0.3
Fumed Silica 0.00150.0015 0.0015 0.0015 0-0.003
Perfume 0.3 0.3 0.3 0.3 0 - 0.6
~ ~ ~
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D a 0.0013 0.0013 0.0013 0.0013 0-0.003
Moisture/minors BalanceBalanceBalanceBalanceBalance
Product pH (10% 7.7 7.7 7.7 7.7 6 - 9.5
in DI
water
EXAMPLE 29
The following aqueous liquid laundry detergent compositions P to T are
prepared
in accord with the invention:
P Q R S T
MLAS 2 6.25 10.5 14.75 19
Any combination 17 12.75 8.5 4.25 0
of
C25E1-3S
C25 AS
C14-17 NaPS
C12-16 SAS
C18 1,4 disulfate
LAS
C12-16 MES
MBAE 1 S 14.4 and
/ or
MBAS 14.4
LMFAA 1-5.5 1-5.5 1-S.5 l-5.5 1-5.5
C23E9 4-6 4-6 4-6 4-6 4-6
0-1.5 0-1.5 0-1.5 0-1.5 0-1.5
Citric Acid 1 1 1 1 1
Fatt Acid (TPK,C12/14)7.5 7.5 7.5 7.5 7.5
Fatt Acid RPS 3.1 3.1 3.1 3.1 3.1
EtOH 0-6 0-6 0-6 0-6 0-6
PG 4-10 4-10 4-10 4-10 4-10
MEA 3-8 3-8 3-8 3-8 3-8
NaOH 1.5 1. S 1. 5 1.5 1.5
NaTS 0-2 0-2 0-2 0-2 0-2
Borax 2-2.5 2-2.5 2-2.5 2-2.5 2-2.5
CaCl2 0.02 0.02 0.02 0.02 0.02
Protease 0.3 0.3 0.3 0.3 0.3 -
-1 - 1 - 1 - 1 1
Lipase 0.05 0.05 0.05 0.05 0.05 -
- - - - 0.3
0.3 0.3 0.3 0.3
Amylase 0.05 0.05 0.05 0.05 0.05 -
- - - - 0.5
0.5 0.5 0.5 0.5
Cellulase 0.3 0.3 0.3 0.3 0.3
P~ 1.2 1.2 1.2 1.2 0 - 2.5
PAC 0-0.4 0-0.4 0-0.4 0-0.4 0-2
P~ 0.2 0.2 0.2 0.2 0.2 -
- - - 0.7 - 0.7
0.7 0.7 0.7
SRP 3 0.1 0.1 0.1 0.1 0.1 -
- - - 0.2 - 0.2
0.2 0.2 0.2
Bri tener 1 or 2 0.15 0.15 0.15 0.15 0.15
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Silicone antifoam 0.2 0.2 0.2 0.2 0.2 -
- - - - 0.25
0.25 0.25 0.25 0.25
Isofo116 0-2 0-2 0-2 0-2 0-2
Perfume 0.5 0.5 0.5 0.5 0.5
Moisture/minors Balanc BalancBalanceBalanceBalance
a a
H 10% in DI water 7.6 7.6 7.6 7.6 7.6
EXAMPLE 30
Aqueous based heavy duty liquid laundry detergent compositions which comprise
the mid-chain branched surfactants of the present invention are presented
below.
In edient A B C D E
MLAS 10 12 14 16 20
Na C25AES surfactant10 8 6 4 0
C23E09 surfactant 2 2 2 2 2
C l2alk 1 lucose 5 5 5 5 0
amide
Citric acid builder 3 3 3 3 S
Fatt acid builder 2 2 2 2 0
Tetraethylenepentamine1 1 1.2 1.2 0.5
ethox fated 15-18
Pro anediol 8 8 8 8 4.5
Ethanol 4 4 4 4 2
Boric acid 3.5 3.5 3.5 3.5 2
Sodium Cumene 3 3 3 3 0
Sulfonate
H = 8.0 8.0 8.0 8.0 7.0
Enz es, d es, water balancebalance balancebalancebalance
100% 100% 100% 100% 100%
