U.S. patent number 3,755,203 [Application Number 05/138,606] was granted by the patent office on 1973-08-28 for detergent slurry compositions.
This patent grant is currently assigned to Jefferson Chemical Company, Inc.. Invention is credited to Floyd Edward Bentley, Harold George Waddill.
United States Patent |
3,755,203 |
Bentley , et al. |
August 28, 1973 |
DETERGENT SLURRY COMPOSITIONS
Abstract
A novel detergent slurry composition, also known as a crutcher
slurry, comprising alpha-olefin sulfonates is provided by
incorporating significant amounts of sulfonated vinylidene-olefins
whereby the resulting composition is characterized by reduced
viscosity.
Inventors: |
Bentley; Floyd Edward (Austin,
TX), Waddill; Harold George (Austin, TX) |
Assignee: |
Jefferson Chemical Company,
Inc. (Houston, TX)
|
Family
ID: |
26795523 |
Appl.
No.: |
05/138,606 |
Filed: |
April 29, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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99081 |
Dec 17, 1970 |
|
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Current U.S.
Class: |
510/418; 510/479;
510/498 |
Current CPC
Class: |
C11D
1/143 (20130101) |
Current International
Class: |
C11D
1/14 (20060101); C11D 1/02 (20060101); C11d
001/14 (); C11d 003/065 () |
Field of
Search: |
;252/536,555,537,556
;260/513R |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Rosdol; Leon D.
Assistant Examiner: Willis; P. E.
Parent Case Text
This is a continuation-in-part of U. S. Pat. application Ser. No.
99,081; filed Dec. 17, 1970, now abandoned; Floyd Edward Bentley
and Harold George Waddill, inventors; entitled "Detergent Slurry
Compositions."
Claims
We claim:
1. A process for reducing the viscosity of a crutcher slurry
containing from about 50 percent to about 70 percent by weight
solids, wherein said solids comprise a wash-active material and
detergent builders and the remainder water, wherein about 5 to 45
wt. % of the stated solids is wash-active material and wherein the
stated wash-active material is from about 25% to 75% by weight
sulfonated alpha-olefin containing about 12 to 24 carbon atoms per
molecule comprising incorporating a viscosity reducing agent
consisting of sulfonated vinylidene-olefins containing about 12 to
20 carbon atoms per molecule into said slurry to reduce the
viscosity thereof in an amount to provide about 75% to 25% by
weight sulfonated vinylidene-olefins based on the total weight of
the stated wash-active material.
2. The process according to claim 1 wherein said wash-active
material comprises more than 50 percent by weight sulfonated
vinylidene-olefins and less than 50 wt. % sulfonated
alpha-olefins.
3. The process according to claim 2 wherein about 15 to 65 percent
by weight of the stated solids comprise a detergent builder
selected from sodium tripolyphosphate, sodium citrate, sodium
carbonate, sodium oxydiacetate, or admixtures thereof.
4. The process according to claim 3 wherein the stated solids level
is from about 60 to 65 wt. % and wherein the stated crutcher slurry
has a viscosity of 40,000 cps. or below.
Description
This invention relates to a method for reducing the viscosity of
detergent slurries containing alpha-olefin sulfonates by means of
using sulfonated vinylidene-olefins. This invention further relates
to compositions of detergent slurries containing sulfonated
alpha-olefins and sulfonated vinylidene olefins.
Built detergent compositions are well known and have traditionally
been prepared by forming a finished deter-gent slurry containing
wash-active ingredients and various additives and by spray-drying
the slurry to form powdered detergents.
The detergent slurry composition, also known as a crutcher slurry,
contains in addition to wash-active components detergent builders
or other additives which are typically employed as detergent aids.
The use of additives and the like to improve the overall
performance or aesthetic appeal of the formulations is widely
employed. Thus, in a typical process, after the built detergent
slurry is well blended, the slurry is dried in a conventional spray
dryer via conventional techniques. Spray drying is, of course, an
old art and is typically disclosed in U. S. Pat. No. 1,652,900.
In spray drying a built detergent slurry it is advantageous from a
productivity standpoint to have as high a solids content in the
crutcher slurry as can be feasibly handled. A few percent increase
in the solids level of the slurry adds up to a significant monetary
savings in the overall process of producing spray dried detergents.
The crutcher slurry, however, at the very least must be a pumpable
mixture. It is generally preferred by the industry that crutcher
slurries prepared for spray drying have a viscosity of about 40,000
cps. or below.
It is also well known that the use of alpha-olefin sulfonates
comprising from about eight to 24 carbon atoms per molecule,
especially those comprising from about 12 to 22 carbon atoms per
molecule, are enjoying wide acceptance as detergent ingredients
because of their biodegradability and detergent effectiveness.
Unfortunately, however, it has been found that built crutcher
slurries formed from the stated alpha-olefin sulfo-nates are very
viscous which makes their industrial utilization difficult and at a
65 percent by weight solids level they are actually often
impossible to handle.
Accordingly, it is an objective of the present invention to provide
an improved detergent crutcher slurry containing alpha-olefin
sulfonates characterized by a high solids level and a reduced
viscosity.
It has now been discovered that the viscosity of a crutcher slurry
comprising sulfonated alpha-olefins can be surprisingly reduced by
incorporating into the slurry significant quantities of sulfonated
vinylidene-olefins. The incorporation of the vinylidene-olefin
sulfonates provides a slurry that is high in solids level and
easily handled thereby enabling more efficient preparation of
spray-dried detergents.
The FIGURE is a graphic illustration representative of the
synergistic effects obtained according to our invention as
explained in Example I which follows.
The incorporation of sulfonated vinylidene-olefins not only
provides a vastly improved slurry, its use enables preparation of
very effective detergents.
We have found that the incorporation of sulfonated
vinylidene-olefins or a replacement of significant amounts of
sulfonated alpha-olefins by sulfonated vinylidene-olefins gave a
surprising drop in the viscosity of aqueous built detergent
slurries which was not predictable from the viscosities of the
crutcher slurries containing the stated individual components. The
viscosity-reducing effect obtained according to this invention is
therefore synergistic.
Thus, the detergent slurry composition consists of about 50 to
about 70 wt. % solids, the remainder being water, the solids
portion of the slurry contains about 5 to 45 wt. % preferably 10 to
25 wt. % of active ingredient, i.e., wash-active materials and 95
to 55 wt. %, preferably 90 to 75 wt. %, detergent builders or other
additives. The active ingredient portion, in accordance with this
invention, comprises about 25 to 75 wt. %, preferably about 30 to
70 wt. %, sulfonated alpha-olefins and about 75 to 25 wt. %,
preferably 70 to 30 wt. %, sulfonated vinylidene-olefins. In the
most preferred embodiment, the active ingredient portion comprises
greater than 50 wt. % sulfonated vinylidene-olefins and less than
50 wt. % sulfonated alpha-olefins. The active ingredient portion of
the built detergent slurry can include additional wash-active
materials if desired such as anionic or nonionic surface-active
wash-active materials in addition to the sulfonated alpha-olefins
and the sulfonated vinylidene-olefins.
Due to their reduced viscosity the crutcher slurries formulated
according to this invention are particularly suitable for the
incorporation of other wash-active materials and additives
customarily employed in making washing and cleansing agents.
The compositions of this invention thus comprise a crutcher slurry
containing about 50 to 70 percent by weight solids, preferably 60
to 65 percent by weight, the remainder water. The stated solids
portion comprises about 5 to 45, preferably about 10 to 25 wt. %
wash-active material wherein the wash-active material comprises
about 25 to 75 wt. % sulfonated alpha-olefins and about 75 to 25
wt. % sulfonated vinylidene-olefins. Accordingly, the stated solids
portion comprises about 95 to 55 wt. %, preferably about 90 to 75
wt. % detergent builders and other additives as herein
discussed.
The sulfonated vinylidene-olefins, and admixtures thereof, which
serve to reduce the viscosity of crutcher slurries containing
alpha-olefin sulfonates are employed in the form of salts. The
cation or salt portion is preferably sodium, potassium, ammonium,
or an organic base such as mono-, di-, or triethanolamine. Mixtures
of the stated salts can, of course, be employed.
The sulfonated vinylidene-olefins are obtained by conventional
sulfonation of vinylidene-olefins which can be characterized by the
following representative formula: ##SPC1##
wherein R.sub.1 and R.sub.2, taken individually, represent a
C.sub.4 to C.sub.10 alkyl and wherein the total carbon atoms per
molecule are about 12 to 20.
Vinylidene-olefins can be prepared, for example, by dimerizing
C.sub.6 to C.sub.10 alpha-olefins, or admixtures thereof, such as
in the presence of aluminum alkyl, such as triethylaluminum as
described in U. S. Pat. No. 2,695,327. Exemplary vinylidene-olefins
are 2-hexyl-decene-1, 2-octyldecene-1, 2-octyl-dodecene-1, and the
like.
The sulfonated alpha-olefin component and admixtures thereof, as
hereinbefore stated, contain about 12 to 22 carbon atoms per
molecule. A conventional source for the alphaolefin can be by the
conversion of ethylene via a combined growth-displacement reaction
using the Ziegler-type polymerization catalyst. The resultant
alpha-olefin mixture, like the vinylidene-olefins, can be
fractionated and the olefin fraction desired, ranging from about
C.sub.12 to C.sub.22, recovered and subsequently sulfonated.
The sulfonation process for the vinylidene and alpha-olefins is by
conventional methods such as described in U. S. Pat No. 3,169,142.
The vinylidene and a phaolefins can be cosulfonated if desired, as
a mixture, or admixed following individual sulfonation.
The alpha- and vinylidene-olefin sulfonates employed according to
this invention need not be entirely pure. They can, accordingly, be
prepared from olefin feeds that contain small amounts, e.g., not
more than 10 wt. % of internal olefins, paraffins, diolefins,
olefins containing carbon atoms per molecule greater than C.sub.22
or less than C.sub.12, mixtures thereof, and the like. Sulfonation
with sulfur trioxide is the preferred method. The use of other
sulfonating agents can be employed if desired. It is generally
preferred when cosulfonating to employ a falling film reactor
wherein sulfonation is accomplished by using vaporized or gaseous
SO.sub.3 which has been diluted to about 2 to 5 percent by volume
concentration with inert gas at a temperature of about 20.degree.C.
to 80.degree.C., preferably from about 25.degree.C. to
75.degree.C., using a mol ratio of sulfur trioxide to olefin from
about 1.0:1.0 to 1.6:1.0, preferably 1.10:1.0 to 1.4:1.0, at either
atmospheric or superatmospheric pressures. The conventional
sulfonation step can be followed by an aging step of from about 0
to 24 hours at a temperature of about 25.degree. to 50.degree.C.
The acidic slurry from the cosulfonation reaction is then
neutralized with a strong base and diluted with water to the
desired solids level. A strong base is added in an amount
equivalent to the sulfonic acid, sultones, plus free sulfur
trioxide in the reactor effluent, generally using about a 2 to 5
percent excess. Following neutralization, the slurry is saponified
by heating to temperatures from about 100.degree. to 200.degree.C.,
preferably about 125.degree. to 160.degree.C., for about 1/2 to 4
hours either at atmospheric pressure or superatmospheric
pressure.
The preparation of the crutcher slurry is by conventional methods.
The sulfonated vinylidene-olefin can be added to the sulfonated
alpha-olefin as the slurry as directly produced from the
sulfonation reaction. If the components were cosulfonated, the
builders or other additives and active ingredients can be merely
incorporated therewith, and the solids content of the resultant
slurry adjusted by the addition of water. If desired, of course,
the sulfonates can be further refined prior to preparation of the
crutcher slurry.
The builders or other additives can be incorporated such as by
their introduction during neutralization or after saponification if
desired. In order to prevent precipitates from forming, such as
insoluble silicates, it is preferred that the additives and other
builders be incorporated subsequent to neutralization. The built
detergent slurry, after it is well blended, is passed to a
conventional spray tower and spray dried according to conventional
techniques in batch or continuous processes. The crutcher slurry if
prepared according to our invention is characterized by a high
solids level and a reduced viscosity enabling easy handling and
high productivity in producing detergents.
Some typical detergent builders or other additives usefully
employed in practicing this invention are representatively
disclosed herein. They include inorganic detergent builders,
organic builders and/or chelate formers, foam stabilizers,
anti-redeposition agents, hydrotropes, buffering agents, and the
like. Preferably, detergent builders comprising sodium
tripolyphosphate, sodium citrate, sodium carbonate, disodium
oxydiacetate, or admixtures thereof, are employed in amounts
sufficient to comprise about 15 to 65 wt. % of the total weight of
the stated solids portion.
Inorganic compounds can be included in the built detergent
composition to augment the detersive portion of the composition and
representatively include such compounds as the alkali metal
carbonates, such as potassium carbonate; borates, such as potassium
tetraborate; silicates, such as sodium silicate. Phosphates, such
as pyro, poly-, meta-, or orthophosphates are suitable. Sodium
pyrophosphate, and the like, is exemplary.
Organic builders and/or chelate formers can also be used with the
aforestated inorganic alkaline builders and include such materials
as the alkali metal salts of phytic acid; alkali metal, ammonium or
substituted ammonium aminopolycarboxylate, such as sodium and
potassium N-(2-hydroxyethyl)ethylenediamine triacetates, sodium and
potassium nitrilotriacetates and sodium potassium and
triethanolammonium-N-(2-hydroxyethyl)nitrilodiacetates. Mixed salts
of these polycarboxylates are also suitable. Other valuable
polycarboxylate builder compounds are the sodium and potassium
salts of polymaleate, polyacrylate and polymethacrylate. Other
organic builders such as the polyphosphonates such as sodium and
potassium salts of ethane-1-1,1-diphosphonate, sodium and potassium
salts of methylene diphosphonate, sodium and potassium salts of
ethylene diphosphonate, and sodium and potassium salts of
ethane-1,1,2-triphosphonate are exemplary. Alkali metal salts of
ethane-2-carboxy-1,1-diphosphonic acid, hydroxymethanediphosphonic
acid, carbonyl diphosphonic acid, ethane-1-hydroxy,
1,1,2-triphosphonic acid, and the like, are also
representative.
Foam stabilizers can also be employed as additives such as the
alkanol amides of fatty acids such as the isopropanol amide of
lauric acid and the ethanol amide of lauric acid, water-soluble
alkaline salts of N-alkylimino-diacetic acid, and the like.
Anti-redeposition agents and organic high-molecular colloidal
substances such as water-soluble derivatives of cellulose and
starch exemplified by sodium carboxymethyl cellulose are also
suitable.
Various hydrotropes can be added if desired to improve the
compatibility of the various ingredients employed. Hydrotropes such
as benzene sulfonate, xylene sulfonate, toluene sulfonate or their
salts such as ethanolammonium, diethanolammonium, and
triethanolammonium and especially as the alkali metal potassium or
sodium salts are suitable.
Various miscellaneous agents such as buffering agents,
anticorrosion agents, water softeners, wetting agents, optical
brighteners, chemical bleaching agents, resin stabilizers, dyes and
pigments, germicides and antibacterial agents, and the like, as is
customary, can be suitably employed.
In addition to the aforestated additives and builders that are
suitable for incorporation with the sulfonated alphaolefin and
sulfonated vinylidene-olefin components of this invention, various
other wash-active cleaning agents can be suitably incorporated in
the crutcher slurry.
Exemplary wash-active materials include anionic, nonionic,
ampholytic and Zwitterionic detergent components. The alkali soaps
of fatty acids can be suitably employed as well as the synthetic
nonsoap detergent materials. Exemplary wash-active materials are
disclosed in U. S. Pat. Nos. 3,159,581 and 3,213,030.
All of the aforementioned U. S. patents are hereby incorporated by
reference thereto.
Illustrative of the foregoing discussion and description and not to
be interpreted as a limitation on the scope thereof or on the
materials herein employed, the following examples are presented to
illustrate the viscosity-reducing effect of the vinylidene-olefin
sulfonates in typical built detergent slurries, commonly known as
crutcher slurries.
EXAMPLE I
Crutcher slurries were formulated using the following typical
detergent formulation:
Wt. % Active ingredient 12.00 Sodium tripolyphosphate 48.20 Sodium
silicate 8.42 Sodium carboxymethyl celulose 1.20 Sodium sulfate
28.90 Sodium xylene sulfonate 1.28
The ingredients were well blended with water to form a 65 wt. %
solids slurry and the viscosity of each slurry at 60.degree.C. was
measured on the Brookfield viscometer. The composition and
concentration of active ingredient as well as the results are
reported in Table 1 and graphically depicted in the figure.
TABLE 1
Run No. Active Ingredient, Wt. % 1 2 4 3 5 Alpha-olefin
sulfonate.sup.(1) 100 0 3070 50 Vinylidene-olefin sulfonate.sup.(2)
0 100 7030 50 Viscosity cps. at 60.degree.C. 2,000, 120, 15,1, 11,
000 000 40000 200 (1) 41 wt. % C.sub.16, 33 wt. % C.sub.18, 26 wt.
% C.sub.20 - sodium salt. (2) 22.5 wt. % C.sub.16, 57.5 wt. %
C.sub.18, 19.4 wt. % C.sub.20 - sodium salt.
EXAMPLE II
The above example was similarly repeated except that viscosities
were determined on crutcher slurries at various solids levels.
The identified formulation employed in Example I was used. The
viscosity results are reported in Table 2.
TABLE 2
Viscosity Data, cps. at 60.degree.C. Wt. % Solids of Crutcher
Slurry Active Ingredient, Wt. % 50% 60% 65% Alpha-olefin
sulfonate.sup.(1) 168,000 2,000,000 2,000,000 Alpha-olefin
sulfonate vinylidene-olefin sulfonate mixture.sup.(2) 400 2,050
11,000 (1) Same as reported in Table 1. (2) 44.3 wt. % alpha-olefin
sulfonate (sodium salt)-18 wt. % C.sub.16, 14.4 wt. % C.sub.18,
11.8 wt. % C.sub.20 ; 55.7 wt. % vinylidene-olefin sulfonate
(sodium salt) 17.1 wt. % C.sub.16, 29.2 wt. % C.sub.18, 9.4 wt. %
C.sub.20.
example iii
a crutcher slurry was formulated to yield the following dry powder
composition:
Wt. % Active ingredient 15.0 Sodium tripolyphosphate 40.0 Sodium
silicate 7.0 Sodium carboxylmethyl cellulose 0.5 Sodium sulfate
30.0 Water 7.5
The ingredients were blended with water to form slurries as
reported in Table 3. The viscosity of each slurry at 60.degree.C.
was measured as in previous examples and is reported in Table
3.
TABLE 3
Viscosity Data, cps. at 60.degree.C. Wt. % Solids of Crutcher
Slurry Active Ingredient, Wt. % 50% 60% 65% Alpha-olefin sulfonate
vinylidene-olefin sulfonate mixture.sup.(1) 2,000 3,600 8,640
Alpha-olefin sulfonate.sup.(2) 3,800 82,000 >1,000,000 (1) 13.10
wt. % C.sub.12, 14.00 wt. % C.sub.16, 23.80 wt. % C.sub.18 and 7.65
wt. % C.sub.20 vinylidene-ol efin sulfonates; 14.73 wt. % C.sub.16,
11.82 wt. % C.sub.18, 9.48 wt. % C.sub.20 and 5.54 wt. % C.sub.22
alpha-olefin sulfonates. (2) 13.10 wt. % C.sub.12, 28.7 wt. %
C.sub.16, 35.6 wt. % C.sub.18, 17.1 wt. % C.sub.20 and 5.5 wt. %
C.sub.22 alpha-olefin sulfonates.
The foregoing examples effectively demonstrate that the addition of
sulfonated vinylidene-olefins or the replacement of alpha-olefin
sulfonates with sulfonated vinylideneolefins produces a surprising
and significant drop in the viscosity of the aqueous crutcher
slurries and demonstrates a synergistic effect of these two
components to provide a viscosityreducing effect.
EXAMPLE IV
Crutcher slurries were formulated using the following dry powder
compositions: ##SPC2##
The various ingredients in the above formulations I to V were well
blended with water to form 60 wt. % solids slurries in formulations
I-III and 65 wt. % solids slurries in formulations IV and V. The
viscosities of each of the above-mentioned slurries were then
determined when the active ingredient employed was an all
alpha-olefin sulfonate, an all vinylidene-olefin sulfonate and
lastly wherein the active ingredient was a mixture of alpha- and
vinylidene-olefin sulfonates. The results are reported in Table 4.
##SPC3##
EXAMPLE V
Formula I of the above example was employed and the example
similarly repeated except that viscosities were determined on
crutcher slurries at various solids levels. The viscosity results
are reported in Table 5.
TABLE 5
Viscosity.sup.(1) Wt. % solids of crutcher slurry Active Ingredient
60% 65% 70% Alpha-olefin sulfonate.sup.(1) 6,800 25,000 37,500
Vinylidene-olefin sulfonate.sup.(1) (2) (2) (2)
Alpha/vinylidene-olefin sulfonate.sup.(1) 540 360 1,200.sup.(3)
The preceding examples can be repeated with similar success by
substituting the generically and specifically described reactants
and conditions of this invention with those employed in the
examples. As will be evident to those skilled in the art various
modifications of this invention can be made or followed in light of
the discussion and disclosure herein set forth without departing
from the spirit or the scope thereof.
* * * * *