United States Patent (19) (11) 4,223,163

Guilloty 45) Sep. 16, 1980

(54 PROCESS FOR MAKING ETHOXYLATED FOREIGN PATENT DOCUMENTS
FATTY ALCOHOLS WITH NARROW
POLYETHOXY CHAN DISTRIBUTION 1240062 5/1967 Fed. Rep. of Germany ....... 260/615 B
1300540 8/1969 Fed. Rep. of Germany ....... 260/615 B
75 Inventor: Haydée R. Guilloty, Cincinnati, Ohio
Primary Examiner-Howard T. Mars
73) Assignee: The Procter & Gamble Company, Attorney, Agent, or Firm-Robert B. Aylor; Richard C.
Cincinnati, Ohio Witte; Thomas H. O'Flaherty
21 Appl. No.: 749,653 (57) ABSTRACT
(22 Filed: Dec. 10, 1976 Improved process for making alcohol polyethoxylates
51) Int. Cl. .............................................. CO7C 41/02 with narrow polyethoxy chain distributions using ap
52U.S. Cl. .................................... 568/618; 252/170; proximately equimolar ratios of alcohol and alkali metal
252/559; 562/587 or alkali metal hydride catalyst. The products are useful
58 Field of Search ....................... 260/615 B, 615 R; in making improved carboxyalkylated alkyl polyether
568/618 surfactants having specific narrow ranges of ethoxyla
tion and containing less than about 6% fatty alcohol.
(56) References Cited Detergent compositions containing said alkyl carbox
U.S. PATENT DOCUMENTS yalkylated polyether surfactants and having less than
2,623,875 12/1952 Schlosser et al............. 260/615 B X
about 6% fatty alcohol by weight of said alkyl carbox
2,782,240 2/1957 Hefner et al. ................ 260/615 B X yalkylated polyether surfactants. Processes of making
2,841,479 7/1958 Hefner et al. ................ 260/615 B X said alkyl carboxyalkylated polyether surfactants.
2,872,432 2/1959 Metzger ...... . 260/615 B X
3,778,479 12/1973 Morrisroe et al. ............... 260/615 B 5 Claims, No Drawings
 4,223,163
1. 2
DETALED DESCRIPTION OF THE
PROCESS FOR MAKENGETHOXYLATED FATTY INVENTION
ALCOHOLS WITH NARROW POLYETHOXY
CHAN DISTRIBUTION The carboxyalkylated alkyl polyether surfactants of
5 this invention contain an alkyl chain having from about
BACKGROUND OF THE INVENTION 8 to about 18 carbon atoms. The alkyl chain can be
This invention relates to alkyl carboxyalkylated poly derived from fatty alcohols, olefins, etc. Normally, and
preferably, the alkyl chain will be a mixture of alkyl
ether surfactants of the type disclosed in U.S. Pat. Nos. chains, preferably having a narrow distribution. How
2,183,853; 2,653,972; 3,003,954; 3,038,862; 3,741,911; 10 ever, pure alkyl chains can be used. The alkyl chain is
and 3,941,710; British Pat. Nos. 456,517 and 1,169,496; desirably a straight saturated alkyl chain, but it may also
Canadian Pat. No. 912,395; French Pat. Nos. 2,014,084 be a branched and/or unsaturated alkyl chain.
and 2,042,793; Netherland patent applications . Suitable alcohol precursors of the carboxyalkylated
7,201,735-Q and 7,406,336; and Japanese patent applica alkyl polyether surfactants of this invention are primary
tions 96,579/71 and 99,331/71 (both in the name of Kao 15 aliphatic alcohols containing from about 8 to about 18
Soap Company, Ltd.) all of said patents and said patent carbon atoms and containing not more than about 70%
applications being incorporated herein by reference. by weight of the alcohol of 2-alkyl branched material.
Such carboxy alkylated alkyl polyether surfactants Other suitable primary aliphatic alcohols are the linear
are typically prepared from alkyl polyether nonionic primary alcohols obtained from the hydrogenation of
surfactants having a distribution of analogs of varying 20 vegetable or animal fatty acids such as coconut, palm
oxyethylene chain length including a level of unethox kernel, and tallow fatty acids or by ethylene build up
ylated alcohol. It has been discovered that these fatty reactions and subsequent hydrolysis as in the Ziegler
alcohols are acceptable if they are carboxyalkylated, type processes. Preferred alcohols are n-octyl, n-nonyl,
but are a detriment if they are not reacted. However, it n-decyl, u-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl,
is known that the fatty alcohol is the least reactive spe 25 n-pentadecyl, n-hexadecyl, n-heptadecyl, and n-octade
cies in the normal process of, e.g., carboxymethylation. cyl. Other suitable alcohol precursors include primary
It is therefore an object of this invention to provide alcohols having a proportion of branching on the beta
carboxyalkylated alkyl polyether surfactants having a or 2-carbon atom wherein the alkyl branch contains
low level of fatty alcohol. from 1 to 4 carbon atoms. In such alcohols at least 30%
It is a further object of this invention to provide pro 30 of the alcohol of each specific chain length is desirably
cesses for producing said carboxyalkylated alkyl poly linear and the branching preferably comprises about
ether surfactants having a low level of fatty alcohol. 50% of methyl groups with smaller amounts of ethyl,
It is a further object of this invention to provide de propyl and butyl groups. These alcohols are conve
tergent compositions containing said carboxyalkylated niently produced by reaction of linear olefins having
from about 11 to about 17 carbon atoms with carbon
alkyl polyether surfactants and having a low level of 35 monoxide and hydrogen. Both linear and branched
fatty alcohol. chain alcohols are formed by these processes and the
It is a further object to provide processes for prepar mixtures can either be used as such or can be separated
ing alkyl polyether precursors which are nonionic sur into individual components and then recombined to
factants having narrow ranges of ethoxylation and low give the desired blend.
fatty alcohol contents. Typical processes for producing "Oxo' halides
It is a still further object to provide a process for which are then used to prepare alcohols are disclosed in
preparing said alkyl polyethers without a solvent. U.S. Pat. Nos. 2,564,456 and 2,587,858 and the direct
SUMMARY OF THE INVENTION hydroformylation of olefins to give alcohols is disclosed
45 in U.S. Pat. Nos. 2,504,682 and 1,581,988. All of these
In accordance with this invention, a carboxyalk patents are specifically incorporated herein by refer
ylated alkyl polyether surfactant is provided having the eCe.
formula The equivalent secondary alcohols can also be used.
It will be apparent that using a single chain length olefin
50 as starting material, a corresponding single chain length
wherein R is an alkyl group containing from about 8 to alcohol will result, but it is generally more economic to
utilize mixtures of olefins having a spread of carbon
about 18 carbon atoms; x is a number averaging from chain length around the desired mean. This will, of
about 1 to about 12; y is 1 or 2, preferably 1; and M is course, provide a mixture of alcohols having the same
selected from the group consisting of hydrogen; so 55 distribution of chain lengths around the mean.
dium; potassium; ammonium; mono-, di- and tri Primary aliphatic alcohols derived from vegetable
ethanolammonium; mono-, di- and tri-alkylammonium; oils and fats and from other petroleum feed stocks hav
magnesium and calcium cations and mixtures thereof. ing alkyl or alkylene groups as part of their structure
Said carboxyalkylated alkyl polyether surfactant com will also contain a range of chain lengths. Since the
prises at least two homologs having polyoxyethylene 60 range of chain lengths is C8-C20 and beyond, it is there
chains of different lengths in which each homolog is fore normal practice to separate the product from such
from about 0% to about 70% by weight of the mixture; feed stocks into different chain length ranges which are
said surfactant contains less than about 6%, preferably chosen with reference to their ultimate use.
less than about 4%, of free fatty alcohol; and the distri As mentioned previously, commercially available
bution of the polyethoxy analogs is such that at least 65 alcohol precursors normally comprise mixtures of alco
about 40% by weight of the surfactant has polyethoxy hols while materials suitable for the purposes of the
chains within-1 ethoxy groups of the average ethoxy present invention desirably have a relatively narrow
group content. distribution of chain lengths.
 3
4,223,163
4.
The polyoxyethylene portion of the surfactant desir Carboxyalkylation can also be achieved by oxidation
ably contains a relatively narrow distribution of the of an alkyl polyoxyethylene nonionic surfactant. How
homologous chain lengths. "Narrow distribution' ever, reacting alkali metal salts of chloroacetic or chlo
means that at least 40% by weight of the surfactant, ropropionic acids with the fatty alcohol polyoxyethyl
preferably 55% or greater, contains polyethoxy groups ene surfactant in alkaline medium to effect a coupling is
which are within about one ethoxy group of the aver preferred for completeness. Preferably, the carboxy
age. A more preferred distribution for C12-14 alcohols is alkyl group is a carboxy methyl group. If carboxyalky
55% within one ethoxy group and for C16-18 alcohols, lation is around 94% complete, there will, of course, be
45%. However, it is highly desirable that no more than no more than 6% residual alcohol and/or alkyl ethoxy
70% of the polyoxyethylene groups have the same 10 lates.
length since to provide very pure materials for deter In summary, the desired low level of fatty alcohol
gent compositions is economically unfeasible. Narrow and narrow distribution can be achieved either by re
distributions can be obtained by using acid catalyzed moval of the fatty alcohol from the fatty alcohol poly
ethoxylation processes and by distillation or steam strip oxyethylene nonionic surfactant prior to carboxyalkyla
ping of the fatty alcohol polyethoxylate prior to, or 15 tion; extraction or distillation of the fatty alcohols etc.
following, carboxyalkylation. However, acid catalysis after carboxyalkylation; utilizing a fatty alcohol poly
gives rise to undesirable by-products such as low molec oxyethylene nonionic surfactant which does not contain
ular weight polyethylene glycols, olefins, decomposi excessive fatty alcohols etc. because of the process by
tion products, etc. and the preferred method for prepa which the nonionic surfactant is prepared; or by carbox
ration is the one described hereinafter. 20 yalkylation to a completeness greater than 94%. The
The preferred process of preparing the preferred resulting alkyl polyether carboxylate surfactants have
alcohol polyethoxylates having narrow distributions of improved performance with respect to removal of body
polyethoxylate chain lengths involves utilizing an essen soil, grease and oil and particulate soil.
tially 1:1 molar ratio of alkali metal or alkali metal hy Detergent Compositions
dride catalyst and fatty alcohol in the ethoxylation step. 25 The carboxyalkylated alkyl polyether surfactants of
Suitable alkaline catalysts include sodium and potassium this invention can be used to formulate desirable deter
hydrides and the sodium and potassium metals them gent compositions which are neutral or alkaline during
selves. The ratio of the catalyst to the fatty alcohol on use. Such detergent compositions will normally contain
a molar basis can be from about 0.9 to about 1.5, prefera 30 from about 2% to about 50% of said carboxyalkylated
bly from about 1.0 to about 1.2 to avoid or minimize alkyl polyether surfactants, preferably from about 10%
ester formation in the subsequent optional carboxyalky to about 40% and most preferably from about 15% to
lation step. about 30%. Since the carboxyalkylated alkyl polyether
A non-reactive solvent may be added to improve the surfactants of this invention are deliberately prepared so
fluidity of the reaction mix and is essential if the catalyst 35 as to contain low levels of fatty alcohol, it is, of course,
and the alcohol are mixed together for a long time be required that the detergent compositions also contain a
fore the addition of the ethylene oxide. This is required very low level of fatty alcohols so as to meet the limits
because the alkali metal fatty alcohol alkoxides are set forth with respect to the carboxyalkylated alkyl
solids at all conceivable reaction temperatures, e.g., polyether surfactant. The detergent composition of this
from room temperature to about 200° C., preferably invention can also contain additional surfactants, deter
from about 100 C. to about 150 C.
In an even more preferred process, the catalyst is gency builders, and minor ingredients as follows.
added to the fatty alcohol first and before the complete Surfactants
displacement of the hydrogen from the OH group on Optional surfactants include additional anionic sur
the alcohol can occur and while the mixture is still fluid, 45 factants of conventional types, nonionic surfactants,
ethylene oxide is added to start the ethoxylation reac Zwitterionic surfactants, ampholytic surfactants, and
tion. This process optimizes the distribution of the cationic surfactants. These optional surfactants are typi
ethoxylates while maintaining a fluid reaction mixture cally present at a level from 0% to about 40%, prefera
without the need for adding a solvent. In effect, the bly from about 1% to about 20%, and most preferably
alcohol acts as the solvent for the initial part of the 50 from about 2% to about 10%. Specific surfactants and
reaction and the alkoxide of the fatty alcohol polyethox mixtures that can be used in the compositions of the
ylated is fluid and acts as a solvent for the last part of the present invention are disclosed in U.S. Pat. Nos.
reaction. Preferably the ethoxylation reaction is started 3,664,961; 3,954,632; 3,936,537; 3,932,316; 3,929,678;
from about 1 to about 5 minutes after the mixing of the 3,925,262; 3,915,903; 3,862,058; 3,755,429; and
fatty alcohol and the catalyst, and after the alkoxide 55 3,729,431; all of said patents being incorporated herein
formation is from about 0% to about 75% complete. by reference.
The product of the above reaction has a distribution Alkyl ether sulfates of value in compositions of the
of polyethoxy homologs in which there is from about 0 present invention are disclosed in Belgian Pat. Nos.
to about 70% of each of the homologs and has a "nar 807,262 and 807,263 issued on May 13, 1974 and specifi
row distribution' as defined hereinbefore. These alkali 60 cally incorporated herein by reference.
metal alkyl polyethoxides can be reacted with an acid to Other useful detergent compounds herein include the
generate highly desirable nonionic surfactants. But pref. water-soluble salts of esters of o-sulfonated fatty acids
erably the alkyl polyethoxides are reacted with e.g., containing from about 6 to 20 carbon atoms in the fatty
alkali metal salts of chloroacetic acid or bromoacetic acid group and from about 1 to 10 carbon atoms in the
acid or the corresponding alkali metal salts of chloro 65 ester group; water-soluble salts of 2-acyloxy-alkane-1-
and bromo-propionic acids to generate the desirable sulfonic acids containing from about 2 to 9 carbon
carboxymethyl and carboxyethyl alkyl polyethoxylates atoms in the acyl group and from about 9 to about 23
of this invention. carbon atoms in the alkane moiety and 3-alkyloxy al
 4,223,163
5 6
kane sulfonates containing from about 1 to 3 carbon amples of these and other phosphorus builder com
atoms in the alkyl group and from about 8 to 20 carbon pounds are disclosed in U.S. Pat. Nos. 3, 159,581;
atoms in the alkane moiety. 3,213,030; 3,422,021; 3,422,137; 3,400, 176; and
Alkane sulfonates useful in the present invention are 3,400,148, incorporated herein by reference.
usually mixed secondary alkyl sulfonates having from Non-phosphorus-containing builder salts such as the
10 to 20 carbon atoms in the alkyl chain. Preferably at alkali metal carbonates, bicarbonates and silicates are
least 80% and most preferably at least 90% by weight of also useful herein.
the alkyl group lies in the C10-17 chain length range. Water soluble, organic builders are also useful herein.
Alkane sulfonates are preferably prepared by treating a For example, the alkali metal, ammonium and substi
selected paraffin material of the desired chain length 10 tuted ammonium polyacetates, carboxylates, polycar
distribution with sulfur dioxide and oxygen to give a boxylates and polyhydroxy-sulfonates are useful build
secondary sulfonic acid, which is then neutralized with ers in the present compositions and processes. Specific
a suitable base. An alternative process utilizes chlorine examples of the polyacetate and polycarboxylate
and sulfur dioxide in the presence of UV light to give builder salts include sodium, potassium, lithium, ammo
sulfuryl chlorides which are then hydrolyzed and neu 15 nium and substituted ammonium salts of ethylenedi
tralized to form the secondary alkyl sulfonates. aminetetraacetic acid, nitrilotriacetic acid, oxydisuc
Specific preferred detergents for use herein include: cinic acid, mellitic acid, benzene polycarboxylic acids,
sodium linear C10-C18 alkylbenzene sulfonate; trietha and citric acid.
nolamine C10-C18 alkyl benzene sulfonate; sodium tal Preferred examples of polycarboxylate builders are
low alkyl sulfate, sodium coconut alkyl glyceryl ether 20 set forth in U.S. Pat. No. 3,308,067, Diehl, incorporated
sulfonate; the sodium salt of a sulfated condensation herein by reference. Examples of such materials include
product of a tallow alcohol with from about 1 to about the water-soluble salts of homo- and co-polymers of
3 moles of ethylene oxide; 3-(N,N-dimethyl-N- aliphatic carboxylic acids such as maleic acid, itaconic
coconutalkylammonio)-2-hydroxypropane-1-sulfonate; acid, measconic acid, fumaric acid, aconitic acid, citra
3-(N,N-dimethyl-N-coconut-alkylammonio)-propane 25 conic acid and methylenemalonic acid.
1-sulfonate; 6-(N-dodecyl-benzyl-N,N-dimethylam Additional preferred builders herein include the
monio) hexanoate; and the water-soluble sodium and water-soluble salts, especially the sodium and potassium
potassium salts of higher fatty acids containing 8 to 24 salts, of carboxymethyloxymalonate, carboxymethylox
carbon atoms. ysuccinate, cis-cyclohexanehexacarboxylate, cis
It is to be recognized that any of the foregoing deter 30 cyclopentanetetracarboxylate and phloroglucinol tri
gents can be used separately herein or as mixtures. sulfonate. -

Detergency Builders A further class of detergency builder materials useful

in the present invention are insoluble sodium aluminosil
The detergent compositions of this invention can icates, particularly those disclosed in Belgian Pat. No.
contain all manner of detergency builders commonly 35 814,874 issued Nov. 12, 1974 and incorporated herein
taught for use in detergent compositions. However, by reference. This discloses and claims detergent com
because of the superior performance characteristics of positions containing sodium aluminosilicates of the for
the alkyl polyether carboxylate surfactants of this in mula
vention, it is possible to formulate detergent composi
tions which are effective and which do not contain 40
phosphate builders or other sequestering builders. The
builders are normally employed in the present composi whereinz and y are integers of at least 6, the molar ratio
tions at concentrations of from about 0% to about 70%, of z to y is in the range from 1.0:1 to about 0.5:1 and x
preferably from about 20% to about 60%, and most is an integer from about 15 to about 264, said aluminosil
preferably from about 30% to about 50%. Useful build 45 icates having a calcium ion exchange capacity of at least
ers herein include any of the conventional inorganic and 200 mg. eq/gr. and a calcium ion exchange rate of at
organic water soluble builder salts. least about 2 grains/gallon/minute/gram. A preferred
Such inorganic detergency builders can be, for exam material is
ple, water-soluble salts of pyrophosphates, orthophos
phates, polyphosphates, phosphonates, carbonates, bi 50 Na12(AlO2)12(SiO2)12.27 H2O
carbonates and silicates. Specific examples of inorganic
phosphate builders include sodium and potassium tri Another type of detergency builder material useful in
polyphosphates, pyrophosphates and hexametaphos the present compositions and processes comprises a
phates. Detergent compositions incorporating pyro water-soluble material capable of forming a water
phosphate builders form the subject of the following 55 insoluble reaction product with water hardness cations
commonly assigned copending applications and patent in combination with a crystallization seed which is ca
that are hereby incorporated by reference, Ser. No. pable of providing growth sites for said reaction prod
618,303, Benson, Cherney and Collier, PROCESS FOR uct. Builder materials of this type are disclosed in Bel
PREPARING A PYROPHOSPHATE-SILICATE gian Pat. No. 798,856 issued Oct. 29, 1973 and incorpo
DETERGENT PRODUCT; filed Sept. 29, 1975 and 60 rated herein by reference.
Ser. No. 713,725, Hau and Cherney, DETERGENT Minor Ingredients
BUILDER AND DETERGENT COMPOSITION,
filed Aug. 12, 1976 and U.S. Pat. No. 3,939,100. The compositions herein can optionally contain all
The polyphosphonates specifically include, for exam manner of additional materials commonly found in laun
ple, the sodium and potassium salts of ethylene diphos 65 dering and cleaning compositions. Specifically, oxidiz
phonic acid, the sodium and potassium salts of ethane ing bleaches such as sodium perborate, sodium percar
1-hydroxy-1,1-diphosphonic acid and the sodium and bonate, optionally with bleach precursors such as
potassium salts of ethane-1,1,2-triphosphonic acid. Ex phthalic anhydride, tetra acetyl ethylene diamine, tetra
 4,223,163
7 8
acetyl methylene diamine or tetra acetylglycoluril may 5%-20% by weight of the composition. The balance of
be incorporated at levels of 1% to 25% of the composi such compositions normally comprise minor ingredients
tion. such as viscosity and gel control agents, perfumes,
Suds suppressors such as blends of silanated silica and brighteners, colors, pH control agents and water which
silicone fluids, C20-22 fatty acids and certain microcrys conventionally is present at a level of at least 25% by
talline waxes, e.g. Mobilwax 2305 may be employed weight.
alone or as mixtures at levels of 0.005% to 5%, prefera The following examples illustrate the preparation of
bly 0.01% to 3% and most preferably 0.1% to 1% of the the alkyl polyether carboxylate surfactants of this in
composition. vention and detergent compositions containing said
Viscosity and anticalking aids such as sodium salts of O surfactants.
lower alkyl aromatic sulphonic acids are conveniently
employed at levels of 0.5% to 5%, particularly if other EXAMPLE I
anionic surfactants are used as part of the surfactant Part A
mixture. Other useful anticaking ingredients include the A sample of carboxymethylated alkyl polyethoxylate
alkali metal salts of sulphosuccinic acid and benzene 15
surfactant was synthesized by reacting an alkyl polye
sulphonic acid. thoxylate in which the alkyl group contains primarily
Certain clays may also be present as emulsification 12 and 13 carbon atoms and the polyethoxylate portion
and processing aids in accordance with the teachings in contains an average of about 3.2 ethoxy groups per
Belgian Pat. No. 821,094, incorporated herein by refer
eCe. 20 molecule with sodium chloroacetate and 50% aqueous
Soil suspending agents such as sodium carboxy sodium hydroxide at 70-80 C. and 5-10 millimeters of
methyl cellulose and hydroxyethyl cellulose may also mercury pressure. After completion of the reaction, the
be used in amounts of 0.25% to 5% by weight. Other product was heated to about 150° C. and a stream of
suitable materials useful for this purpose include co water was added to the reactor. Heat was maintained
polymers of maleic anhydride with ethylene or methyl 25 until most of the unreacted polyethoxy compound was
vinyl ether and certain polymeric glassy metaphos removed by the steam distillation. This unreacted mate
phates. rial was collected and found to contain about 95% une
Enzymes such as the proteolytic enzymes sold under thoxylated fatty alcohols, the remainder being mono
the trade names “Alcalase' and "Esterase' (Novo In and di-ethoxy alcohols.
dustries A/S, Denmark) Maxatase and AZ-Protease 30 Another sample was reacted to the same reaction
(Gist-Brocades NV, The Netherlands) may be incorpo completeness (i.e., about 88% of the alkyl polyethoxy
rated at levels of up to 1% by weight, preferably from late are reacted), but was not steam distilled as was the
0.25% to 0.75% by weight. Such enzymatic materials original paste sample.
may be coated or prilled to aid their stability and to The above samples were then acidified, separated
minimize the formation of dust during processing and 35 from the water-soluble salts, and then neutralized to
subsequent storage. give the following compositions.
Typical but non-limiting examples of granular com
positions in accordance with the present invention com Surfactant Steam Distilled Not Distilled
prise by weight of the composition: 2%-30%, prefera Paste Analyses A. B
bly 10%-25% and most preferably 15%-20% surfac 40
Anionic in paste 65.2% 49.3%
tant; 10%–80%, preferably 25%-70% by weight of a Unreacted nonionic 2.1% 5.5%
detergent builder salt; and 1%-50% of other optional By-product Salt 0.3% 0.8%
ingredients such as bleaches, suds suppressors, viscosity Water 32.4% 44.4%
and anti-caking aids, anti-redeposition agents, fluoresc Fatty alcohol as %
of unreacted 14% 70%
ers, enzymes, perfumes, colors, processing aids, corro 45 Fatty alcohol as %
sion control agents, and antibacterial agents. of total active 0.4% 7.0%
Typical but non-limiting liquid detergent composi % alkyl polyethoxylate w
tions embodying the present invention comprise (by within 1 ethoxy
weight of the compositions) 5%–50%, preferably group of the average 43% 38%
20%-40% and most preferably 25%-35% of an alkyl 50
polyether carboxylate surfactant; in accordance with In the above table, sample A is representative of the
the present invention and 5%-35%, preferably preferred surfactants of this invention and Sample B is
10%-30% and most preferably 10%-20% of an addi representative of the prior art.
tional surfactant which is either another anionic surfac Surfactant A and Surfactant B were tested in a prod
tant or a nonionic surfactant. In a preferred embodi 55 uct which was composed of 18% surfactant, 25% hy
ment, a source of alkalinity is included at a level suffi drated sodium Zeolite A having an average particle size
cient to raise the pH to a value of at least 7.0. For this of about 3 microns, 20% of 1.6 ratio of sodium silicate,
purpose, free base should be added in excess of that 24% sodium sulfate, and 10% sodium carbonate.
necessary to provide the cation for the anionic surfac The two detergent compositions were tested versus a
tant. Any source of free alkalinity can be employed but 60 commercial product (Tide containing about 6% phos
preferred materials are sodium and potassium hydrox phorus), the products were tested at a level equivalent
ide and alkanolamines. Usage of the latter is normally to one cup usage for the removal of body soil relative to
1%-20%, preferably 2%-15%, and most preferably the reference product. The test involves washing soiled
5%-10% by weight of the composition. Optionally cloth fabrics which are then graded by a panel of ex
builder materials such as pyrophosphates, silicates, and 65 perts as to relative cleanness. The body soil removal
the previously-described synthetic aluminosilicates, performance of the reference product (Tide) was arbi
citrates, borates, or nitrilotriacetates may be present in trarily normalized to zero, so the performance of deter
solution or dispersed and suspended at levels of gent compositions A and B is stated relative to Tide
 4,223,163
9 10
performance. A value of +2.5 units represents a com metal at 100° C. and diglyme (Bis-2-methoxyethylether)
pletely clean fabric. The results were as follows: solvent. During the reaction the temperature increased
by 15 C. and the liquid turned dark although it became
Wash Conditions Composition Composition lighter thereafter. The formation of the alkoxide turned
Hardness gragal/Temp. (F) A. B the mixture opaque. The mixture was then heated up to
2/70 +0.18 --0.32 150° C. and 3.5 moles of ethylene oxide per mole offatty
7/70 --2.20 -- 1.29 alcohol were added over a period of about 4 hours.
9/70
2/100
-- 1.17
--0.50
-0.63
--0.16
The mixture became clear and light yellow. The reac
9/100 --0.82 -0.40 10
tion was carried out under a flowing nitrogen blanket.
The average molecular weight was about 352 and the
ethylene average per mole was about 3.8. The distribu
Part B tion of polyethoxy homologs was as follows:
E0-0.7%
Two samples of carboxymethylated alkyl polye E1-6.3%
thoxylate surfactants were prepared. Both were derived 15
E2-17.3%
from fatty alcohols containing approximately the same E3-22.4%
alkyl chain lengths and distributions and the polyethoxy E4-21.2%
portions of the compounds had the same average chain E5-15.6%
length, but the samples, differed in distribution of the E6-8.6%
various polyethoxy homologs. 20
E7-5.6%
The alkyl polyethoxylate feed stock was derived by E8-2.3%
reacting a C12-13 fatty alcohol with approximately three The alkyl polyethoxylate was carboxymethylated by
moles of ethylene oxide per mole of alcohol. The alkyl
polyethoxylate contained roughly 14% fatty alcohol. adding one mole of sodium chloroacetate slurried in
This alkyl polyethoxy surfactant was steam stripped 25 diglyme at 80 C. The mixture turned creamy color and
until there was only about 1% fatty alcohol present. the temperature increased approximately 10° C. The
Both of these materials were carboxylakylated giving reaction continued for about 35 minutes at which point
samples as follows: the temperature was 65° C. The heat was then turned on
to increase the temperature to 90° C. Agitation was
Composition Composition
30 stopped five minute later and the reactor was left over
A B night under nitrogen. The pH at the end of the reaction
Average number carbons in
was close to neutral. The percentage completeness was
alkyl chain 12.9 12.8 about 85.2% leaving about 9.55% of alkyl polyethoxy
Average number ethoxy groups 4.5 4.7 late surfactant present in the finished reaction mix.
Portion of alkyl polyethoxylate 35
reacted to give an anionic 72% 67% Part D
Portion of alkyl polyethoxy
material which is unreacted 28% 33% A primary fatty alcohol containing from 12 to 14
Fraction of
the alkyl polyethoxylate
carbon atoms was mixed with sodium metal pellets and
which is still an alcohol 7.5% 1.0%
before the reaction was complete, when the tempera
Estimated alcohol in final com ture was about 150 F. and prior to solidification, ethyl
position as a percent of the alkyl ene oxide gas was added in a ratio of about 3 moles of
polyethoxylate feed stock 5.3% 0.8% ethylene oxide per mole of alcohol. The reaction con
% of alkyl polyethoxylate within tinued for about four hours during which time the tem
it lethoxy group of the average 30% 45%
45
perature increased to about 185 F. The resulting mate
rial had a molecular weight of about 311 and ethylene
The above samples were performance tested in accor oxide content of about 2.54 moles of ethylene oxide per
dance with the procedures set forth hereinbefore using mole of fatty alcohol. The polyethylene oxide homolog
a formula containing 18% surfactant, 18% of the afore distribution was as follows:
mentioned zeolite A, 20%. 1.6 ratio sodium silicate, 26% E0-3.8%
sodium sulfate, and 7.7% sodium pyrophosphate. The 50
E1-15.3%
reference product in this series of tests was a commer E2-25.9%
cial Tide detergent composition containing 0% phos E3-23.8%
phorus. V
Results were as follows: E4-15.9%
55 E5-10.7%
E6-3.5%
Stripped Unstripped E7-1.2%
Wash Conditions
surfactant
body soil
surfactant
body soil
This alkyl polyethoxylate surfactant was carboxyme
Hardness gr./gal/temp. (F) removal removal thylated by the addition of 0.05 moles of sodium hy
2/70 0.31 --0.32 droxide in powder form per mole of fatty alcohol and
7/70 -- 1.31 - 0.91 1.05 moles of sodium chloroacetate per mole of fatty
9/70 - 1.47 --0.80 alcohol. The mixture which was light yellow turned
12/70 -- 1.23 --0.96 creamy. The temperature of the reaction was originally
60° C. and after one-half hour, it increased to 70° C. The
Part C
65 reaction mixture was left overnight under a nitrogen
blanket and the percentage completeness was 71% and
One mole of a primary fatty alcohol containing 12 the percent of alkyl polyethoxylate surfactant present
carbon atoms was reacted with one mole of sodium was about 20%,
 4,223,163
11 12
Part E. advantages for the higher ratios of catalyst to fatty
alcohol and for addition of the ethylene oxide shortly
Samples of the surfactant from the foregoing process after the addition of the sodium catalyst without a sol
were performance tested according to the procedure in vent being present.
Part A using a formula with 18% surfactant, 25% of the 5 Similar results are obtained when potassium metal
zeolite, 20% of 1.6 ratio sodium silicate, 24% sodium and sodium and lithium hydrides are substituted for the
sulfate, and 10% sodium carbonate. The results were as sodium metal and octanol, nonanol, decanol, undecanol,
follows: tridecanol, tetradecanol, pentadecanol, hexadecanol,
10
heptadecanol, octadecanol and mixtures thereof are
Stripped Unstripped substituted for the alcohols.
surfactant surfactant Part B
Wash Conditions body soil body soil
Hardness gr./gal/temp. (F) removal removal When the above fatty alcohol polyethoxylates from
2/70 -0.78 --0.45 Runs 1-8 are carboxylakylated as in Example I, superior
7/70 --0.95 -0.43 15 carboxyalkylated alkyl polyethoxylate surfactants are
9/70 --0.75 --0.25
obtained. When substituted into the detergent composi
tions of Example I on a part for part basis for the car
In the above test the reference product was a com boxyalkylated alkyl polyethoxylate surfactants, essen
mercial detergent, Tide, containing about 6% phospho tially equivalent performance is obtained.
U.S. 20
Part C
EXAMPLE II
Part A
Samples of the above surfactants 1, 2, 6 and 7 were
performance tested according to the procedure of Part
Sodium metal was used as an ethoxylation catalyst in 25 E of Example I against the unstripped surfactant. The
preparing the following polyethoxylated fatty alcohols. results were as follows:
The first two runs were with essentially pure dodecanol
and the rest were with mixtures of C12-C14 fatty alco Wash Conditions 70 F.
hols. The ratio of ethylene oxide to fatty alcohol is -- Hardness gr/gal.
given in column 1; the temperature of the initial ethoxy 30 Surfactant 2 6 9 12
lation reaction in column 2; the time of ethylene oxide Run 1 --0.33 -- 1.38 - 1.00 -
addition in column 3; the molar ratio of sodium metal to Run 2 -0.5 --0.55 --0.44 -0.61
fatty alcohol in column 4; the percent of fatty alcohol in Run 6 --0.10 --O.09 --0.37 -0.51
the product in column 5; and the poisson fatty alcohol Run 7 -0.65 -0.46 -0.10 --0.20
content in column 6. Diglyme solvent was added to the 35
first two runs, but no solvent was used for the rest. All What is claimed:
reactions were under nitrogen. Runs 12-15 were in an 1. The process of preparing fatty alcohol polyethoxy
autoclave (12-13 rocking; 14-15 stirred). lates having a narrow distribution of polyethoxylate
chain lengths in which a fatty alcohol containing from
Temp. Time % OH 40 about 8 to about 18 carbon atoms is reacted with ethyl
Run
No. EO/OH Add.
at EO
Add.
at EO
NaOH
Un-
reacted
Poisson
9%, OH
ene oxide in a ratio of ethylene oxide to fatty alcohol of
from about 1 to about 20 at a temperature which is
1
2
3.8
4.0
150 C. 45 min.
160 C. 90 min,
1.00
1.00
0.70
1.02
1.80
0.95
between room temperature and about 200° C. in the
3 3.9 110 C. at 75% 100 0.33 1.00 45 presence of an alkali metal or alkali metal hydride cata
Add. of Na lyst which is present in a molar ratio of catalyst to fatty
(1-2 min) alcohol of from about 0.9 to about 1.5 in which said
4.
5
3.5
3.5
120
10
C.
C.
1-3
1-3
min.
min.
0.75
0.90
3.89
3.83
.60
1.60
ethylene oxide is added to the mixture of fatty alcohol
6 2.5 185 C. 1-3 min. .00 3.8 5.00 and catalyst after the addition of the catalyst and before
7 4.5 190 C. 1-3 min. 1.00 0.19 0.50 the formation of the fatty alcohol alkoxide is about 75%
8 4.1 60 C. 15-20 min. 0.90 1.17 0.80 50 complete.
9
10
2.2
3.5
125
110
C.
C.
20 min.
23 min.
0.50
0.25
14.63
8.43
7.50
1.80
2. The process of claim 1 wherein the ethylene oxide
1.3 110 C. 10-15 min. 0.05 34.84 22.50 is added to the fatty alcohol within from about 1 to
12 3.2 100 C, 35 min. 1.00 3.30 2.40 about 5 minutes after the addition of the catalyst.
13
14
2.7
3.0
75
105
C.
C.
50 min.
35 min.
1.00
1.00
7.65
12.28
4.10
2.80 55
3. The process of claim 1 wherein the ratio of fatty
15 2.8 105 C. 1-3 min. 1.00 0.60 4.00
alcohol to catalyst is from about 1.0 to about 1.2.
4. The process of claim 1 wherein said alchol is a
primary alcohol.
The higher ratios of ethylene oxide to fatty alcohol 5. The process of claim 1 temperature is from about
will naturally result in lower fatty alcohol contents, 100 C. to about 150 C.
regardless of the process. However, there are clear 60 k x k

65