US 3691081 A
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United States Patent Office US. Cl. 252--89 4 Claims ABSTRACT OF THE DISCLOSURE A detergent composition primarily adapted for use as an industrial surfactant which comprises a liquid substantially biodegradable mixture or blend of an ethoxylated detergent range alcohol and an ethoxylated plasticiser range alcohol, the said mixture or blend including ethoxylates of alcohols derived by hydrofor-mylation of mlxed olefines.
The present invention concerns liquid detergent compositions primarily for use as general purpose industrial surfactants. 1
A detergent material presently extensively used in industrial cleaning and scouring operations (for example general cleaning, emulsifying, wool scouring and leather tanning) is alkyl phenol ethoxylate, for example nonyl phenol ethoxylate, containing an average of 8 to 10 moles of ethylene oxide per mole of alkyl phenol. This mate rial exhibits an excellent balance of general detergent properties but an important factor contributing to its ready acceptance by industrial users is its liquidity at'ordinary temperatures which permits easy transporation, storage, metering, and dosing. In one important respect, however, alkyl phenol ethoxylates are not wholly satisfactory;
they are doubtfully sufliciently biodegradable even when the alkyl grouping of the phenol residue is linear.
Any biodegradable detergent material or composition that is to gain acceptance on its merits as a general purpose liquid cleaning agent in, say, industrial outlets, where alkyl phenol ethoxylates are presently predominantly used should as well as displaying an acceptable balance of detergent properties, very desirably also'be a liquid at ordinary temperatures. Detergent materials that are slurries or solids may, of course, be brought into aqueous solution and be distributed and handled as. such but this is seldom as satisfactory as dealing in a liquid material of the highest possible content of active ingredient.-
The present invention provides a detergent composition primarily adapted for use as an industrial surfactant where alkyl phenol ethoxylates presently have established utility, which comprises a liquid substantially biodegradable mixture or blend of an ethoxylated higher alcohol (or mixture of higher alcohols) containing from 11 to 20, preferably 11 to 15, carbon atoms in the alcohol residue and an ethoxylated lower alcohol (or mixture of lower alcohols) containing from 6 to 10 carbon atoms in the alcohol residue, the degree of ethoxylation being the same or difierent in the two cases and in each case being to an average of from 5 to 10 moles of ethylene oxide per mole of alcohol (subject to liquidity in the mixture or blend) Patented Sept. 12, 1972 and wherein said mixture or blend including ethoxylates of alcohols derived by hydroformylation of mixed olefines.
The present compositions are to be liquid at ordinary temperatures (say 10 to 20 C.). Liquidity at 0 C. will be desirable in some cases and to achieve this test with differing mixtures or blends may be' necessary. For a higher alcohol fraction containing alcohols with 11 to 15 carbon atoms and in which, for instance, the C alcohol is a principal component so that the average carbon content is, for example, around 12, the optimum average level of ethylene oxide is around 7 moles per mole of alcohol. A lower alcohol ethoxylate fraction blended or mixed with this higher alcohol ethoxylate fraction and derived for instance from a mixture of alcohols in which the C alcohol is a principal component may very suitably also contain an average of around 7 moles of ethylene oxide per mole of alcohol. Alcohols of diflerent molecular weights tend to be ethoxylated to similar average extents under given conditions and, thus, when a mixture of condensates as aforedescribed is prepared by ethoxylating a mixture of alcohols, the level of ethoxylation of the lower alcohol fraction will be similar to that of the higher alcohol fraction. Clearly, however, a blend of condensates may also be obtainedby mixing separately formed condensates of the higher and lower alcohol fractions.
There appears to be a wide range of relative contents of higher and lower alcohol ethoxylates over which a liquid material is obtained. Broadly, very satisfactory are compositions containing from 30% to around 75% by weight of higher alcohol ethoxylates although, subject to liquidity at ambient temperature, somewhat higher contents of higher alcohol ethoxylate may be satisfactory. These compositions, especially, perform extremely well as detergent materials, as assessed by a number of different standard tests of detergency performance, and compare -very favourably with commercially produced alkyl phenol ethoxylates on a weight/Weight basis even though a proportion of the compositions of the invention is provided by lower alcohol ethoxylates which are not themselves considered as active detergent materials.
-. The applicants attach greatest importance to compositions which, as supplied to the trade and to consumers, are essentially non-aqueous. No advantage is seen in converting an already liquid material which has a high content of active material'into a diluted form, for distribution, by water incorporation. However, if desired, the compositions of the present invention may contain a proportion of water. Furthermore, for many outlets there will be no need or desire to incorporate into the present compositions anyof the various incidental or auxiliary ingredients which already find use as components of detergent ticular advantage is anticipated to follow from so doing for the primary purpose for which the present compositions have been developed. These formulated products may be in solid particulate or bar form or in liquid form as desired.
The ethoxylates of alcohols derived by hydroformylation of mixed olefines may be contained in or provide the whole of the ethoxylates of the lower alcohol fraction or be contained in or provide the whole of the ethoxylates of the higher alcohol fraction.
Preferred compositions according to the present inventions are those wherein the higher alcohol ethoxylate fraction is produced from alcohols derived by a process including hydroformylation of mixed olefines.
The liquid mixtures or blends contained in or constituting the detergent compositions of the present invention are biodegradable to a substantial extent. Differences in the degree of biodegradability or the ease of biodegradability are, however, shown by ethoxylation of alcohols of different molecular structures, linearity of the carbon chains favouring rapid biodegradation.
The following examples illustrate the invention and include comparisons with relevant commercially available detergent materials.
EXAMPLE 1 Component alcohol (percent by weight) (3 C Ca a 010 C11 13 15 Mixture 1 13 23 28 21 10 Mixture 2 25. 5 27. 5 11 21 5 Both mixtures were ethoxylated by standard ethoxylation procedures to an average ethylene oxide content of 7 moles per mole of alcohol. The resultant mixed ethoxylates were liquids at 10 C. and showed excellent detergent properties as assessed by surface tension measurement, wetting tests, foam development and stability, and washing trials and, additionally, were biodegradable.
The quantitative results of these tests (and the corresponding performance of a commercial nonyl phenol 8.5 mole ethoxylate and a commercial higher alcohol 9 mole ethoxylate) were as follows:
(A) Surface tension measured by the standard Du Nouy method at 0.1% by weight concentration in Water:
Surface tension (dynes/cm. Mixture l ethoxylate 27.4 Mixture 2 ethoxylate 28.6 Nonyl phenol ethoxylate 31.6 Higher alcohol ethoxylate 32.0
(B) Wetting properties as measured by the standard Draves-Clarkson method at 0.2% by weight concentration in water:
Wetting time (seconds) Mixture 1 ethoxylate 8.7 Mixture 2 ethoxylate 10.5 Nonyl phenol ethoxylate 10.3 Higher alcohol ethoxylate 19 (C) Detergency test using Lauderometer machine, a working temperature of 60 C., a solution of 0.25% by weight concentration in water of 50 ppm. hardness, and, as the sample, EMC soiled wool. The results indicate relative soil removal with the results for the commercial nonyl phenol ethoxylate arbitrarily set as 100 units.
Relative soil removal (arbitrary units) Mixture 1 ethoxylate 105 Mixture 2 ethoxylate 105 Nonyl phenol ethoxylate 100 Higher alcohol ethoxylate 90 (D) Foam height and foam stability as determined by the standard RossMiles test:
In 50 p.p.m. hardness water Mixtures were prepared by blending an ethoxylate of a C1445 alcohol (derived from hydroformylation of olefines) containing 6 molecular proportions of ethylene oxide per hydroxyl group, with ethoxylates of Ziegler C alcohols containing 6 and 9 molecular proportions, respectively, of ethylene oxide per hydroxyl group.
The percentage compositions by weight of the mixtures are given in the following table.
Cwis it-10 Ca-ro alcohol/6 mol alcohol/6 inol alcohol/9 mol ethoxylate ethoxylate ethoxylate Mixture 1 75 25 Mixture 2 75 25 Detergency tests carried out on synthetically soiled wool serge showed the above mixtures to be superior in detergent efliciency to a well established product of proved performance, viz., nonyl phenol condensed with 8 molecular proportions of ethylene oxide and additionally to be biodegradable.
1. A liquid cleaning agent whose detergent active material consists essentially of a liquid mixture or blend of V substantially linear higher and lower primary alcohol ethoxylates, said higher primary alcohol ethoxylates being ethoxylates of alcohols of carbon contents in the range C to C derived by hydroformylation of mixed olefins and containing from 5 to 10 moles of ethylene oxide per mole of alcohol and said lower primary alcohol ethoxylates being ethoxylates of mixed alcohols of carbon contents in the range C to C that include as a principal component at least one alcohol having 7 to 8 carbon atoms and containing from 5 to 10 moles of ethylene oxide per mole of alcohol, the proportion by weight of said higher primary alcohol ethoxylates in said mixture or blend of higher and lower alcohol ethoxylates in the range of about 30 to 75%.
2. A liquid cleaning agent as claimed in claim 1 wherein said higher alcohol ethoxylates include as a principal component ethoxylated C alcohol and said lower alcohol ethoxylates include as a principal component ethoxylated C alcohol.
5 6 3. A liquid cleaning agent as claimed in claim 1 where- 2,870,220 1/1959 Carter 260-615 in the average carbon content of said higher alcohols is 3,372,201 3/1968 Leary et al. 260-615 B around 12 and the average carbon content of said lower alcohols is around 8. FOREIGN PATENTS 4. A liquid cleaning agent as claimed in claim 1 where- 5 719,445 12/1954 Great Britain 260 615 B in said higher alcohol ethoxylates are ethoxylates of alcohols derived by hydroformylation of wax-cracked olefins. Soap & Chem Specialties, J l 1955 57 References Cited LEON D. ROSDOL, Primary Examiner UNITED STATES PATENTS 10 W. E. SCHULZ, Assistant Examiner 2,920,045 1/1960 Hearn et a1. 252DIG. 1 US. Cl. X.R.
1,970,578 8/1934 Schoeller et a1. 252-DIG. 1 252-DIG. 1, DIG. 6