US3499841A - Low foaming washing and cleansing agents - Google Patents

Description

United States Patent M US. Cl. 252170 10 Claims ABSTRACT OF THE DISCLOSURE This invention relates to low foaming washing and cleansing compositions comprising a content of:

(A) polymers of (3-hydroxymethyl-3-ethyl)-oxacyclobutane containing p'olyoxyalkylene radicals selected from the group consisting of (1) compounds of the formula wherein x is an integer of from 5 to 12, m is an integer of from 2 to 16, n is an integer of from 1 to 8 and the ratio of m to n is between about 1.5 to 1 and 10 to 1; and

(B) surface-active polyoxyalkylene polymers containing oxyalkylene units selected from the group consisting of oxyethylene units and oxypropylene units, said polymers containing from 2 to 90 oxypropylene units, the amount of oxypropylene units in said polymer being more than 50 mol percent of the total number of said oxyalkylene units.

CLAIM OF PRIORITY Priority based on the corresponding German patent application H 58,255, filed Jan. 15, 1966, is hereby claimed under the provisions of 35 U.S.C. 119.

THE PRIOR ART In an increasing measure, mechanical washing methods are being employed to wash china, glass, porcelain, ceramic, metal and synthetic articles. Detergents containing specific surface-active compounds are generally utilized. These detergents should be low foaming, so that they do not affect the function of the washing apparatus. A foam formation of too large a volume, caused and increased by the vigorous motion of the bath in the machine, leads to considerable trouble, a the foam mass decreases the mechanical effect of the liquid sprayed onto the articles tobe cleaned and furthermore may cause the bath in the machine to run over.

Recently, developments in washing apparatus have been directed toward further increasing the intensity of the liquor motion as well as the water volume cycled per minute, and in this way to further improve the mechanical cleansing effect. As a result of such developments, it was found that conventional washing agents, such as alkylene oxide adducts, were no longer satisfactory under these turbulent washing conditions. Instead, due to volu- 3,499,841 Patented Mar. 10, 1970 minous foam formation, the conventional washing agents gave rise to the disadvantages mentioned previously.

It is an object of this invention to provide novel compositions of washing and cleansing agents having either low foaming properties or no foaming properties at all, which compositions are particularly suited for the me chanical washing of china.

Another object of the invention is to obtain low foaming washing and cleansing compositions comprising a content of:

(A) Polymers of (3-hydroxymethy1-3-ethy1)-oxacyclobutane containing polyoxyalkylene radicals selected from the group consisting of (1) compounds of the formula wherein at is an integer of from 5 to 12, m: is an integer of from 2 to 16, n is an integer of from 1 to 8 and the ratio of m to n is between about 1.5 to 1 and 10 to 1; and

(B) Surface-active polyoxyalkylene polymers containing oxyalkylene units selected from the group consisting of oxyethylene units and oxypropylene units, said polymers containing from 2 to oxypropylene units, the amount of oxypropylene 'units in said polymer being more than 50 mol percent of the total number of said oxyalkylene units.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF INVENTION These objects have been attained by employing a combination of non-ionic agents comprising a content of:

(A) Polymers of (3-hydroxymethyl-3-ethyl)-oxacyclobutane containing polyoxyalkylene radicals of the general formula wherein x represents any number from 5' to 12, m represents any number from 2 to 16, n represents any number from 1 to 8, and the ratio of m to n is between about 1.5 to 1 and 10to 1; and

(B) Surface-active compounds with a content of oxypropylene radicals or polyoxypropylene radicals containing 2 to 90 oxypropylene units, and preferably with a further content of oxyethylene radicals or polyoxyethylene radicals, the amount of oxypropylene units in the total number of the oxyalkylene units being more than 50 mol percent.

These combinations of non-ionic agents possess a remarkable cleansing, degreasing and draining effectiveness and due to their low forming properties, they are particularly suitable for mechanical washing and cleaning methods.

The preparation of compound A of the new non-ionic compositions is started by polymerization of (3-hydroxymethyl-3-ethyl)-oxacylclobutane. These compounds are obtained from the monomeric oxacyclobutane derivative by polymerization in the presence of acid catalysts, according to the method described in the published German patent application (Auslegeschrift) No. 1,023,227. The average number of monomer units in the polymer is between and 12, preferably between 7 and 10.

The further reaction to obtain polymers containing the respective polyoxyalkylene radicals is effect d in a generally known manner by addition of ethylene oxide or of propylene oxide and ethylene oxide, in the presence of alkaline catalysts such as sodium hydroxide, sodium methylate and the like, preferably under pressure. Based on the monomer unit, about 2 to 16, preferably 4 to mols of ethylene oxide, possibly after the preliminary addition of 1 to 8, preferably 3 to 5 mols of propylene oxide, are added. In the polyoxyalkylenated polymer, the molar ratio of propylene oxide to ethylene oxide amounts preferably to about 0.3 to 0.7 oxypropylene units to 1 oxyethylene unit.

Examples for compounds of component A are: the adduct of 4, 6 or 8 mols of ethylene oxide, based on the monomer unit, to a poly-(3-hydroxymethyl-3-ethyl)-oxacyclobutane having a polymerization degree of 7 to 10; as well as the addition products of 3 mols of propylene oxide and 10 mols of ethylene oxide, or 4 mols of propylene oxide and 8 mols of ethylene oxide, or 6 mols of propylene oxide and mols of ethylene oxide, based on the monomer unit, to a poly-(3-hydroxymethyl-3-ethyl)-oxacyclobutane having a polymerization degree of 7 to 10.

The A components are readily water soluble, possess tenside characteristics, and tend in themselves to give a more voluminous foam formation. The turbidity points are preferably above 35 C.

As compounds of component B are primarily propylene oxide polymers as obtained by polymerization of propylene oxide or by addition of propylene oxide to compunds containing at least two reactive hydrogen atoms, in particular low molecular weight aliphatic or aromatic compounds with from 2 to 6 carbon atoms containing hydroxyl or amino groups. The reaction is effected in known manner in the presence of alkaline catalysts, preferably under pressure. These known propylene oxide polymers have a total molecular weight of 1000 to 5000, preferably 1700 to 4100. Preferably, up to mol percent of ethylene oxide, based on the total amount of alkylene oxides, may be added to these propylene oxide polymers.

Examples of propylene oxide polymers of the known kind are: the adduct of 4.5 mols of ethylene oxide to a polypropylene glycol with a molecular weight of 1740; the adduct of 7 or 16 mols of ethylene oxide to a polypropylene glycol with a molecular weight of 2750; the adduct of 8.5 mols of ethylene oxide to a polypropylene glycol consisting of 56 oxypropylene radicals; the adduct of mols of propylene oxide to glycerin; and the adduct of 48 mols of propylene oxide and 7 mols of ethylene oxide to ethylene diamine.

Another method for the preparation of suitable compounds of component B consists in the addition of 1 to mols of propylene oxide to high molecular weight aliphatic or aliphatic-aromatic compounds with 8 to 22 carbon atoms containing hydroxyl or amino groups, preferably after preliminary addition of as much as 20 mols of ethylene oxide. In the latter case, the portion of the propylene oxide to the total amount of the alkylene oxide is more than 50 mol percent, preferably 55 to 80 mol percent. The aliphatic compounds possess higher molecular weight radicals with 8 to 22, and preferably 10 to 20 carbon atoms and are preferably of the formula wherein R represents a radical having from 8 to 36 carbon atoms selected from the group consisting of alkyl, alkenyl, alkadienyl and hydroxy-alkenyl, H represents a replaceable hydrogen and Y represents a bridging link selected from the group consisting of NH, O, S, -CONH,

4 -SO NH, and CO-O. The aliphatic-aromatic compounds possess higher molecular weight radicals with 12 to 22, and preferably 14 to 18 carbon atoms and are preferably of the formula wherein Y and H have the above-assigned values and R' represents a radical having 12 to 22 carbon atoms selected from the group consisting of alkylphenyl, alkylnaphthyl, alkoxyphenyl and alkylcyclohexyl. The hydrocarbon radicals R and R may contain conventional substitutents such as hydroxyl groups, halide atoms, or alkyl side chains.

As starting compounds for the preparation of the above, the following may be utilized: higher molecular weight aliphatic alcohols, carboxylic acids, mercaptans, amines, carboxylic acid amides or alkanolamides, sulfonic acid amides and the like, as well as alkylphenols.

Examples of these compounds are: the adduct of 7 mols of ethylene oxide and 10 mols of propylene oxide or of 9 mols of ethylene oxide and 16 mols of propylene oxide to a fatty alcohol admixture of the chain lengths C -C the adduct of 4 mols of ethylene oxide and 12 mols of propylene oxide to oleyl alcohol; the adduct of 7 mols of ethylene oxide and 10 mols of propylene oxide to nonylphenol; and the adduct of 10 mols of ethylene oxide and 20 mols of propylene oxide to nonylphenol.

Finally, the B component can be prepared by addition to 1 to 6 mols of ethylene oxide and 2 to 20 mols of propylene oxide to polymers of (3-hydroxymethyl-3-ethyl)-oxacyclobutane, as they were also used as starting materials for the preparation of the A components. The indicated molar amounts are based on the monomer unit of the polymer. The amount of the propylene oxide in the total amount of the alkylene oxides has to be more than 50 mol percent, preferably 55 to mol percent.

Examples for compounds of the indicated type are: the adducts of 3 mols of ethylene oxide and 6 mols of propylene oxide, or of 3 mols of ethylene oxide and 10 mols of propylene oxide, or of 4 mols of ethylene oxide and 5 mols of propylene oxide, or of 4 mols of ethylene oxide and 10 mols of propylene oxide, based on the monomer unit, to a poly-(3-hydroxymethyl-3-ethyl)-oxacyclobutane having a polymerization degree of 7 to 10.

The portions of the individual components in the washing and cleansing compositions of the invention are, in general, 70 to 98% by weight of the A components, and 2 to 30% by weight of the B components. In the practice, particularly mixtures of to by weight of the A components and of 5 to 15% by weight of the B components have proved useful. The amounts used of these mixtures in the cleansing bath are within the concentration range of about 0.05 to 0.5 g./l., preferably 0.1 to 0.4 g./l. based on the total amount of the components A and B.

The composition of the mixtures can be varied within the amount ratio indicated without losing the specific advantage of low foaming properties. Since the component A, which is inclined to a voluminous foam formation, is responsible for the cleaning and wetting effect, as well as for the draining and the clear-drying appearance of the washed china, it has to be recognized as a special advantage that the foam can already be reduced to a sufficient degree with the addition of very small amounts of the B components of the mixture.

Concentrated liquid products, such as those preferably used for dishwashers equipped with automatic metering devices, may be prepared by dissolving the mixtures of the invention in water, if so desired under concomitant usage of organic water-miscible solvents or by dissolving the mixtures in organic solvents. These concentrates contain about 20 to 85% of the mixture of A and B components. By varying the constituents, these liquid concentrates may be standardized in such a manner that they possess good temperature stability and that they are not inclined to precipitate or separate into layers. In corresponding manner, the dehydration temperature of the mixtures of the invention in aqueous solution can be varied and adjusted to the respective requirements, for example, for the rinsing temperature utilized. The utmost low foaming state of the mixtures of the invention is generally attained only when the dehydration temperature of the mixtures is below the rinsing temperature, preferably below 40 C.

The following specific embodiments of the invention are illustrative thereof. It is obvious, however, that other expedients may be employed and these specific embodiments are not to be deemed limitative in any manner.

EXAMPLES The foam behavior of various non-ionic tensides and mixtures of washing agents was examined for purpose of comparison in a special foam examination apparatus The test results, given in the following table, show the extraordinarily favorable foam behavior of the mixtures of the invention.

The foam apparatus used was constructed in similar manner as a modern dishwasher operating according to the spray system. By means of a rotating pump about 170 liters of water per minute were rotated and sprayed into the metering chamber by means of a rotating spray arm equipped with nozzles. Foam heights from to 280 mm. may be measured in reproducible manner, whereas larger foam volumes cannot be measured accurately and, therefore, they are indicated in the table as 280. The bath temperature during the tests was 50 C.; the hardness of the water used was 16 dH and the duration of the foam test lasted five minutes. The reading of the foam heights was conducted immediately after the apparatus became idle and 30 seconds thereafter. This foam apparatus is described in Fette, Seifen, Anstrichmittel, 66 (1964), 529 (Fats, Soaps, Paints).

The letters A and B indicate the components corresponding to the descriptive text.

TAB LE Foam height in mm. 30 sec.

end of run Foam height in min. at the end of run Ex. No.

1a..-. (A) Polymer tenside having a polymerization degree of 7 to 10, adducted with 4 mols of ethylene oxide. 1b...- (A) Polymer tenside having a polymerization degree of 7 to 10, adduioited with 4 mols of ethylene ox e. (B) Fatty alcohol 012-014 adducted with 9 mols of ethylene oxide and 11 mols of propylene oxide.

Cone, g./l.

Composition of Mixture 2a (A) Polymer tenside having a po- 0.12 lymerization degree of 7 to 10, adducted with 6 mols of ethylene oxide.

2b.... (A) Polymer tenside having a polymerization degree of 7 to 10, adducted with 6 mols of ethylene ox e. (B) Adduct of 6 mols of ethylene oxide to a polypropylene glycol of a molecular weight of 2,250. 2a..... (A) Polymer tenside having a polymerization degree of 7 to 10, adducted with 6 mols of ethylene oxide.

(B) Nonylphenol adducted with 9 mols of ethylene oxide and 10 mols of propylene oxide.

Foam Foam height height nmm. in mm. 30sec. at the after Ex. Cone end of end of No. Composition of Mixture g./l. run run 2f (A) Polymer tenside having a po- 0.12

lymerization degree of 7 to 10, adducted with 6 mols of ethylene ox1de. (B) Polymer tenside having a po- 0.008 20 0 lymerization degree of 7 to 10, adducted with 4 mols of ethylene oxide and 5 mols of propylene oxide.

3-- (A) Polymer tenside having a po- 0.12

lymerization degree of 7 to 10, adducted with 4 mols of propylene oxide and 8 mols of ethylene oxide. (B) Fatty alcohol 012-014 adducted 0.008 20 0 with 9 mols of ethylene oxide and 11 mols of propylene oxide.

Example 4 A concentrated liquid rinsing agent suitable for commercial dishwashers was prepared having the following composition Percent Polymer tenside having a polymerization degree of 7 to 10, adducted with 6 mols of ethylene oxide 75 Fatty alcohol C -C adducted with 9 mols of ethylene oxide and 11 mols of propylene oxide 5 Ethanol 20 The product developed practically no foam at all at application temperatures between 50" C. and C.

After a complete alkaline cleansing of the china in the main wash cycle, the water for the second rinsing was supplemented with concentrations of 0.2 to 0.3 g./l. of the above composition. Spotless dishes with a clear luster were thus obtained.

Example 5 A very low foaming washing agent for household dishwashers was prepared having the following composition:

Percent Polymer tenside having a degree of polymerization of 7 to 10, adducted with 6 mols of ethylene oxide 53 Adduct of 4.5 mols of ethylene oxide to a polypropyleneglycol having a molecular weight of 1750 l3 Ethanol 17 Water 17 At an application concentration of 0:2 to 0.4 g./l., a satisfactory clear-dry effect is obtained on the Washed articles utilizing the above composition.

The preceding specific embodiments are illustrative of the invention. It is obvious, however, that other expedients known to those skilled in the art may be employed without departing from the spirit of the invention.

We claim:

1. Low foaming Washing and cleansing compositions consisting essentially of a content of:

(A) from 70% to 98% by weight of a polymer of (3 hydroxymethyl-3-ethyi)-oxacycl.obutane containing polyoxyalkylene radicals selected from the group consisting of (1) compounds of the formula and (2) compounds of the formula [-CHpO-CHz-O-h CH20(CsHe0)n(C2H40)mH wherein x is an integer of from 5 to 12, m is an integer of from 2 to 16, n is an integer of from 1 7 to 8 and the ratio of m to n is between about 1.5 to 1 and to 1; and

(B) from 2% to 30% by weight of surfaceactive polyoxyalkylene polymers containing oxyalkylene units selected from the group consisting of oxyethylene units and oxypropylene units, said polymers containing from 2 to 90 oxypropylene units, the amount of oxypropylene units in said polymer being more than 50 mol percent of the total number of said oxyalkylene units.

2. The low foaming washing and cleansing compositions of claim 1 wherein said component A is present in an amount of from 85% to 95% by weight and said component B is present in an amount of from 5% to by weight.

3. The low foaming washing and cleansing compositions of claim 1 wherein said component B is a polyoxyalkylene polymer selected from the group consisting of polyoxypropylene glycols having a molecular weight of from 1000 to 5000 and polyoxypropylene glycols having a molecular weight of from 1000 to 5000 adducted with up to 30%, based on the total amount of oxyalkylene units, of ethylene oxide.

4. The low foaming washing and cleansing compositions of claim 3 wherein said molecular weight of said polyoxypropylene glycol is from 1700 to 4100.

5. The low foaming washing and cleansing composition of claim 1 wherein said component B is a high molecular lipophilic radical having from 8 to carbon atoms and a replaceable hydrogen atom selected from the group consisting of compounds of the formula wherein R represents a member selected from the group consisting of alkyl, alkenyl, alkadienyl and hydroxyalkenyl, R represents a member selected from the group consisting of alkylphenyl, alkylnaphthyl, alkoxyphenyl and alkylcyclohexyl, Y represents a bridging link selected from the group consisting of NH, O, S, CONH, -SO NH and COO--, and H represents a replaceable hydrogen atom, adducted with 50 mol percent to 100 mol percent of oxyproplyene units and the remainder of oxyethylene units.

6. The compositions of claim 5 wherein said high molecular weight lipophilic radicals having replaceable hydrogen atoms are aliphatic and contain from 10 to 20 carbon atoms.

7. The compositions of claim 5 wherein said high molecular weight lipophilic radicals having replaceable hydrogen atoms are aliphatic-aromatic and contain from 14 to 18 carbon atoms.

8. The low foaming washing and cleansing composi tions of claim 1 wherein said component B is an alkylene oxide adduct of a polymer of (3-hydroxymethyl-3-ethyl)- oxacyclobutane having a polymerization degree of from 5 to 12, said polymer adducted with from 1 to 6 mols of ethylene oxide and from 2 to 20 mols of propylene oxides, based on the monomer units, from to 80 mol percent of the alkylene oxide units in the adduct being propylene oxide units.

9. Liquid low foaming composition consisting essentially of from 20% to by weight of the low foaming washing and cleaning compositions of claim 1 in solution in a solvent media selected from the group consisting of water, water-miscible lower alcohols and mixtures thereof.

10. The method of rinsing of solid articles which comprises rinsing said solid articles with water containing from 0.05 to 0.5 gram per liter of the low foaming, washing and cleansing composition of claim 1.

References Cited UNITED STATES PATENTS 2,677,700 5/1954 Jackson et a1. 252-89 2,828,345 3/1958 Spriggs 252-89 2,886,600 5/1959 Horsley et al. 260-615 2,944,982 7/1960 De Groote et al. 260615 2,948,757 8/1960 Pruitt et al. 260615 3,031,510 4/1962 Crecelias 35289 LEON D. ROSDOL, Primary Examiner W. SCHULZ, Assistant Examiner US. Cl. X.R.