U.S. patent number 3,758,595 [Application Number 05/113,079] was granted by the patent office on 1973-09-11 for detergent.
This patent grant is currently assigned to Lever Brothers Company. Invention is credited to Henry Lamaire, Vincent Lamberti.
United States Patent |
3,758,595 |
Lamberti , et al. |
September 11, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
DETERGENT
Abstract
This specification relates to a detergent. More particularly, it
is concerned with a detergent which is a sulfur analog of a
polyolether or polyolpolyether.
Inventors: |
Lamberti; Vincent (Upper Saddle
River, NJ), Lamaire; Henry (Fairfield, CT) |
Assignee: |
Lever Brothers Company (New
York, NY)
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Family
ID: |
27381276 |
Appl.
No.: |
05/113,079 |
Filed: |
February 5, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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764362 |
Aug 7, 1968 |
3562337 |
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502299 |
Oct 22, 1965 |
3427248 |
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Current U.S.
Class: |
568/37; 510/492;
510/493; 510/235; 568/39 |
Current CPC
Class: |
A61Q
17/005 (20130101); C11D 1/72 (20130101); C11D
1/75 (20130101); C11D 1/755 (20130101); A61K
8/46 (20130101); C11D 1/002 (20130101) |
Current International
Class: |
C11D
1/00 (20060101); B21D 51/46 (20060101); B21D
51/38 (20060101); C11D 1/72 (20060101); C11D
1/75 (20060101); C11D 1/755 (20060101); C07c
149/14 () |
Field of
Search: |
;260/67A,69R |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Gotts; Lewis
Assistant Examiner: Phillips; D. R.
Parent Case Text
This application is a continuation-in-part of application Ser. No.
764,362, filed Aug. 7, 1968, now issued as U.S. Pat. No. 3,562,337
which in turn is a divisional of application Ser. No. 502,299 filed
Oct. 22, 1965, now issued as U.S. Pat. No. 3,427,248.
Claims
What is claimed is:
1. A detergent which is 2-hydroxydodecyl 2'-hydroxyethyl
sulfide.
2. A detergent which is 2-hydroxy-C.sub.11 --C.sub.14 alkyl
2'-hydroxyethyl sulfide.
3. A detergent which is 2-hydroxydodecyl 2'-hydroxyethyl sulfoxide.
Description
In the past a straight chain or branched chain alcohol has been
reacted with ethylene oxide to form ethoxylates, such as
n-tetradecyl alcohol-7 moles ethylene oxide, dodecyl alcohol-10
moles ethylene oxide and Sterox AJ (tridecyl alcohol-about 9.5
moles ethylene oxide). These ethoxylates have detergent
properties.
It has now been discovered that certain thioether analogs of
polyolethers and polyolpolyethers, known also as sulfides, are
surface active agents, e.g., detergent actives, dishwashing
detergents, lime-soap dispersants and suds-boosters for other
detergent actives. The compounds of the invention also have
anti-microbial activity and are nontoxic, mild towards skin and
completely biodegradable.
These new nonionic detergents have the following generic structure:
##SPC1##
Wherein R is an aliphatic hydrocarbon group having six to 14 carbon
atoms; Z is oxygen, sulfur or sulfoxide but at least one Z is
sulfur or sulfoxide; a is 1 or 2, b is 0 or 1; m is 0 or 1; n is 0
or 1; m + n in all occurrences is 1; and R' is H, CH.sub.2 OH or
CH.sub.3. Subgeneric structures within the generic structure are as
follows: ##SPC2##
Wherein R is an aliphatic saturated hydrocarbon group having five
to 15 carbon atoms; Z is sulfur or sulfoxide; a is 1 or 2; m is 0
or 1; n is 0 or 1; m+n in all occurrences is 1; and R' is H,
CH.sub.2 OH or CH.sub.3. ##SPC3##
wherein R is an aliphatic saturated hydrocarbon group having six to
14 carbon atoms; Z is oxygen, sulfur or sulfoxide but at least one
Z is sulfur or sulfoxide; a is 1 or 2; m is 0 or 1; n is 0 or 1; m
+ n in all occurrences is 1; and R' is H, CH.sub.2 OH or CH.sub.3.
As used herein, these structures are intended to include isomeric
compounds.
Any known method may be employed to prepare the aforementioned
sulfur analogs of polyolethers and polyolpolyethers. One method is
to react a long chain epoxide or long chain glycidyl ether with
hydroxy alkyl mercaptans, such as, 2-mercapto-ethanol,
3-mercapto-1,2-propanediol, 1-mercapto-2-propanol,
3-mercapto-1-propanol, 4-mercapto-1,2,butanediol and
4-mercapto-2-butanol, in the presence of a basic catalyst, e.g.,
NaOCH.sub.3. The reaction can also be carried out without a
catalyst, but in such cases, longer reaction times are required. In
accordance with this method, the compounds of the invention are the
reaction products of: ##SPC4##
With:
HZ--(CH.sub.2).sub.a CH(OH)R' (V)
wherein R, a, b and R' are as defined heretofore and Z is oxygen or
sulfur but at least one Z is sulfur. The thioether reaction product
can be oxidized, for example with t-butyl hydroperoxide in
methanol, to form the corresponding sulfoxide. It is also possible
to react either a long-chain diol containing sulfur or a monoalkyl
thioether of glycerol with one molar proportion of ethylene oxide.
By this process, however, a mixture of products is obtained
containing large proportions of unreacted starting diol or
thioether, with some mono-ethoxylated compound with which this
invention is concerned, and with some poly-ethoxylated compounds
such as those represented by the formula
R--S--CH.sub.2 --CH(OH)CH.sub.2 O(CH.sub.2 CH.sub.2 O).sub.x H
wherein x is greater than 1.
If a long-chain sulfur-containing epoxyalkane is a reactant, it may
be obtained by any suitable method. For example, long chain
mercaptans can be reacted with epichlorohydrin to form
3-alkylthio-2-hydroxy-1-chloropropanes which, in turn, are reacted
with strong aqueous sodium hydroxide to produce alkyl glycidyl
thioethers. Similarly, if a long-chain sulfur-containing diol is a
reactant, it may be obtained by any suitable method such as the
reaction of hydrogen sulfide with long chain epoxides.
The following short-chain polyhydroxy reactants among others are
within the scope of the above structure I:
Short-chain polyhydroxy reactant (Structure V)
a R' Name Structure 1 H ethylene glycol HOCH.sub.2 CH.sub.2 OH 1
CH.sub.2 OH glycerol HOCH.sub.2 CH(OH)CH.sub.2 OH 1 CH.sub.3
1,2-propanediol HOCH.sub.2 CHOHCH.sub.3 1 H 2-mercapto ethanol
HSCH.sub.2 CH.sub.2 OH 1 CH.sub.2 OH 3-mercapto-1,2- propanediol
HSCH.sub.2 CH(OH)CH.sub.2 OH 1 CH.sub.3 1-mercapto-2- propanol
HSCH.sub.2 CHOHCH.sub.3 2 H 1,3-propanediol HO--CH.sub.2 --CH.sub.2
--CH.sub.2 OH 2 CH.sub.2 OH 1,2,4-butane- triol HOCH.sub.2 CH.sub.2
OH(OH)CH.sub.2 OH 2 CH.sub.3 1,3-butylene glycol HOCH.sub.2
CH.sub.2 CH(OH)CH.sub.3 2 H 3mercapto-1- propanol HSCH.sub.2
CH.sub.2 CH.sub.2 OH 2 CH.sub.2 OH 4-mercapto-1, 2-butanediol
HSCH.sub.2 CH.sub.2 CH(OH)CH.sub.2 OH 2 CH.sub.3 4-mercapto-2-
butanol HSCH.sub.2 CH.sub.2 CH(OH)CH.sub.3
preferred types of compounds in this invention, among others,
include sulfides having the following structures: ##SPC5##
wherein R in structures VI to XVII is an aliphatic saturated
hydrocarbon group having five to 15 carbon atoms. The corresponding
sulfoxides for structures VI to XVII are also suitable for the
present invention.
Suitable specific compounds of this invention, among others,
include sulfides such as 2-hydroxyundecyl 2'-hydroxyethyl sulfide;
2hydroxydodecyl 2'-hydroxyethyl sulfide; 2hydroxy-C.sub.11
-C.sub.14 alkyl 2'-hydroxyethyl sulfide; 2-hydroxydodecyl
2',3'-dihydroxypropyl suflide; 2-hydroxydodecyl 2'-hydroxypropyl
sulfide; (2-hydroxy-3-decyl)propyl 2'-hydroxyethyl sulfide;
(2-hydroxy-3-dodecyl)propyl 2',3'-dihydroxypropyl sulfide;
(2-hydroxy-3-decyl)propyl 2'-hydroxypropyl sulfide;
(2-hydroxy-3-dodecylthio)propyl 2'-hydroxyethyl ether;
(2-hydroxy-3-tetradecylthio)propyl 2',3'-dihydroxypropyl ether;
(2-hydroxy-3-dodecylthio)propyl 2'-hydroxypropyl ether;
(2-hydroxy-3-dodecylthio)propyl 2'-hydroxyethyl sulfide;
(2-hydroxy-3-tetradecylthio)propyl 2',3'-dihydroxypropyl sulfide;
(2-hydroxy-3-dodecylthio)propyl 2'-hydroxypropyl sulfide; and
corresponding sulfoxides thereof.
The compounds of the present invention may be used alone as
detergents. However, the compounds of the invention may also be
used in combination with other detergents. Examples of detergent
compounds with which the compounds of the invention may be admixed
to form superior combinations are the well-known anionic types
represented by the water-soluble and water-dispersible organic
surface-active agents having in the molecule a hydrophobic group of
about eight to about 22 carbon atoms and a hydrophilic sulfate,
sulfonate or carboxylic group having a cation which does not
insolubilize the compound. The following anionic detergents, among
others, are suitable for use with the compounds of the present
invention:
1. Alkylbenzenesulfonates, such as sodium and potassium salts
having a branched or straight chain alkyl portion of about nine to
about 15 carbon atoms.
2. Alkyl sulfates, such as the sodium and triethanol-ammonium salts
of C.sub.10 --C.sub.20 alkyl sulfuric acid, prepared by sulfating
the alcohols derived from coconut oil or tallow, or prepared
synthetically.
3. The alkali metal and ammonium salts of the sulfated ethoxylates
of a long-chain alcohol and 3 to 5 molar proportions of ethylene
oxide, for example, the ammonium salt of an ethoxylate containing
an average of 3.1 molar proportions of ethylene oxide and 1 mole of
an alcohol mixture known commercially as Alfol 1412, composed of
about 2/3 n-tetradecanol and about 1/3 n-dodecanol.
4. The compounds known as "Medialans", which are amido carboxylic
acids formed by condensing fatty acids of C.sub.8 --C.sub.22 chain
length with sarcosine, CH.sub.3 NHCH.sub.2 COOH. Generally the
alkali metal and basic nitrogen-radical salts are employed.
5. Alkanesulfonates, such as ammonium dodecane-sulfonate.
6. Alkoxyhydroxypropanesulfonates, such as the water-soluble salts
of 3-dodecyloxy-2-hydroxy-1-propane-sulfonate.
7. Soaps, the surface-active substances formed usually by the
reaction of caustic alkalies with natural glyceridic fats and oils,
generally prepared in high purity, and having the generic molecular
formula RCOONa, wherein R is a straight-chain hydrocarbon group
having from about seven to about 21 atoms.
8. Olefine sulfonates, such as dodecene sulfonate, and the
compounds described in U.S. Pat. No. 3,332,880.
The compounds of the invention are also suds-boosters for nonionic
detergents. The following nonionic detergents, among others, are
suitable for use with the compounds of the present invention.
1. The Pluronics, formed by condensing propylene oxide with
propylene glycol to a molecular weight of about 600-2500 to form a
base followed by condensing ethylene oxide to this base to the
extent of about 10 to about 90 percent, total molecule basis. U. S.
Pat. Nos. 2,674,619 and 2,677,700 describe operable nonionic
compounds.
2. Compounds formed by the simultaneous polymerization of propylene
oxide and ethylene oxide, and containing randomly positioned
oxypropylene and oxyethylene groups. These and related compounds
are described in U.S. Pat. Nos. 2,979,528, 3,036,118, 3,022,335,
3,036,130 and 3,048,548.
3. Alkyl phenols having nine to 12 carbon atoms in the alkyl
portion, (straight or branched) ethoxylated with 4-10 molar
proportions of ethylene oxide.
4. Ethoxylates of fatty alcohols having eight to 18 carbon atoms
per molecule and 5-30 molar proportions of oxyethylene groups.
In addition to being suds-boosters for the above detergents, the
compounds of this invention act as suds-boosters for ampholytic
compounds such as hydroxyalkyl methyl taurates and zwitterionic
surface-active substances, such as coco dimethyl sulfopropyl
betaine.
The compounds of this invention may interact synergistically with
all suds-producing surface-active substances to provide mixtures
having improved properties beyond those expected on the basis of
the properties of the individual components of the mixture. With
nonsoaps, the synergism may be evident in suds production or
stability. With soaps, the synergism may be evident in the form of
reduced lime-soap scum formation.
Thus, in accordance with this invention, new compounds have been
formed. The compounds of the present invention have certain
noteworthy features. For example, the synergistic suds-producing
properties of the compounds with other detergents and sudsing
agents are surprising. The antimicrobial properties of the
compounds are also surprising. Furthermore, the compounds of the
invention are nonionic surfactants with foaming characteristics
superior to both well-known anionic and nonionic detergents. The
ability to formulate a detergent based on the nonionic materials of
the invention having high foaming or dishwashing characteristics
with built-in germicidal properties and which at the same time is
biodegradable by sewage or natural water bacteria is certainly
surprising and unexpected.
The following examples are submitted to illustrate but not to limit
this invention. Unless otherwise indicated, all parts and
percentages in the specification and claims are based upon
weight.
EXAMPLE I
Compound A, 2-hydroxydodecyl 2'-hydroxyethyl sulfide, was prepared
by stirring a mixture of 25.3 g. (0.325 moles) of 2-mercaptoethanol
and 5.4 g. (0.1 mole) of sodium methoxide under nitrogen while
adding dropwise 55.1 g. (0.324 moles) of 1,2-epoxydodecane over a
period of 25 minutes. After continued stirring on a steam bath for
85 minutes, the crude material was cooled and dissolved in hexane.
A portion therefrom was washed with water in the presence of
methanol to remove the catalyst and another portion was merely
filtered. Evaporation of the hexane in each case afforded the
desired product, 2-hydroxydodecyl 2'-hydroxyethyl sulfide.
Compound B, 2hydroxy-C.sub.11 --C.sub.14 alkyl 2'-hydroxyethyl
sulfide, was prepared in the same manner except that 1,2 epoxy
C.sub.11 --C.sub.14 alkane was used as one of the reactants.
Compound C, a sulfoxide compound, 2-hydroxydodecyl 2'-hydroxyethyl
sulfoxide, was formed by oxidizing Compound A, 2-hydroxydodecyl
2'-hydroxyethyl sulfide, with t-butyl hydroperoxide in methanol.
More specifically, a solution of 8 g. of 2-hydroxydodecyl
2'-hydroxyethyl sulfide in 38 ml. of methanol was treated with 3 g.
of t-butyl hydrogen peroxide and heated at 50.degree.C. for two
days. The solvent was evaporated and the crystals washed with
hexane.
The dishwashing properties of the compounds prepared according to
Examples A, B and C were determined by ascertaining the number of
plates washed in duplicate tests with 1.8 g. of each of the above
compounds in 6 quarts of 120 ppm water at 116.degree.F., both with
or without 0.54 g. of coconut fatty acid monoethanolamide (CMEA).
The results are shown in Table 1.
TABLE 1
Boosted with No. of Dishes Comound CMEA Washed Compound No 20-24 B
No 20 A Yes 38-42 B Yes 42 C Yes 42
This example shows that the sulfides and a corresponding sulfoxide
within the purview of the present invention have excellent
dishwashing properties.
EXAMPLE II
The compounds listed in Table 2 are other compounds that are
considered to be suitable detergents. They may be prepared by the
same procedure described in Example I by varying the reactants to
provide the required end product.
TABLE 2
2-hydroxyundecyl 2'-hydroxyethyl sulfide;
2-hydroxydodecyl 2',3'-dihydroxypropyl sulfide;
2-hydroxydodecyl 2'-hydroxypropyl sulfide;
(2-hydroxy-3-decyloxy)propyl 2'-hydroxyethyl sulfide;
(2-hydroxy-3-dodecyloxy)propyl 2',3'-dihydroxypropyl sulfide;
(2-hydroxy-3-decyloxy)propyl 2'-hydroxypropyl sulfide;
(2-hydroxy-3-dodecylthio)propyl 2'-hydroxyethyl ether;
(2-hydroxy-3-tetradecylthio)propyl 2',3'-dihydroxypropyl ether;
(2-hydroxy-3-dodecylthio)propyl 2'-hydroxypropyl ether;
(2-hydroxy-3-dodecylthio)propyl 2'-hydroxyethyl sulfide;
(2-hydroxy-3-tetradecylthio)propyl 2',3'-dihydroxy-propyl
sulfide;
(2-hydroxy-3-dodecylthio)propyl 2'-hydroxypropyl sulfide; and
corresponding sulfoxides thereof.
EXAMPLE III
The germicidal activity of several compounds described in this
invention was determined by the Streak Gradient Plate Method.
The Streak Gradient Plate Method is a modification of the gradient
plate method of Szybalski, Science 116: 46-48 (1952), for the
determination of germicide MEC (Minimum Effective Concentration)
values. This method employs streaks of several organisms per
plate.
As shown in Table 3, certain compounds of the invention have
surprisingly high antimicrobial activity and they are superior to
well-known germicides and soaps against a number of
micro-organisms.
TABLE 3
Germicidal Activity by the Gradient Streak Plate Method
Compound Minimum Effective Concentration (MEC) in ppm Sa Mc Sf Ca
An 2-hydroxydodecyl hydroxyethyl sulfide 36 51 25 34 18 2-hydroxy
C.sub.11 -C.sub.14 alkyl 2'-hydroxy- ethyl sulfide 50 111 28 100 27
Controls: Alfonic 1418-6 (Alfol 1418- 62.5% EO) >10,000 Sterox
DJ (Dodecylphenol- 10EO) >10,000 Igepon A (coconut) 1780 3550
5000 3900 1660 Soap (LTS) 1550 1880 2200 1610 455 Culture Codes: Sa
-- S.aureus Mc -- M.candidus Sf -- Strep.faecalis Ca -- C.albicans
An -- A.niger
Having set forth the general nature and specific embodiments of the
present invention, the true scope is now particularly pointed out
in the appended claims.
* * * * *