MXPA99006491A - Defoaming compositions - Google Patents

Abstract

Defoamers are the products of the reaction of epichlorohydrin and compounds having the formula (II) R3(EO)n(PO)mOH, wherein R3 is an alkyl, alkenyl or arenyl group having from 4 to 22 carbon atoms;a substituted alkyl or alkenyl group having from 4 to 22 carbon atoms wherein;n is a number from 0 to 50 and m is a number from 0 to 10;wherein the mole ratio of epichlorohydrin to (II) is from about 0.60/1 to about 2/1 are extremely efficient defoamers for aqueous surfactant systems. The defoamers are added to a surfactant in an amount sufficient to reduce or eliminate foam and have the advantage of being totally dispersible in water, are readily biodegradable, contain no organic solvents and do not affect the detergency of surfactants with which they are used because they are nonionic surfactants in themselves.

Description

DEPRECIATING COMPOSITIONS 1. FIELD OF THE INVENTION The invention relates to the reaction products of alkoxylated alcohols and epichlorohydrin and the use of alkoxylated alcohols to control foam formation in surfactant compositions. 2. BACKGROUND OF THE INVENTION Aqueous cleaning compositions show a tendency with regard to foam formation because they contain active surface oils such as soaps, and synthetic detergents. In many instances, such cleaning compositions produce excessive foam and the consumer must use known substances such as adding antifoam or defoaming oils. Some defoamers such as silicones tend to interfere with the function of the cleaning compositions in that they leave unwanted residues after the cleaners have been ** while others are environmentally unacceptable because they are not biodegradable. Alkyl polyglucosides are a class of nonionic surfactants that exhibit significantly higher foam forming profiles than other nonionic surfactants, such as ethoxylated alcohols. In fact, it can be said that the foaming tendencies of polyglycoside alkyls more closely resemble those of anionic surfactants, such as alcohol sulfates, of the foaming tendencies of non-ionic surfactants. This increased foaming tendency makes the use of undesirable alkyl polyglucosides for many applications, for example cleaning at plant sites for food processing, high pressure spray cleaning, bottle washing, floor cleaning and automatic dishwashing, in where high levels of foam interfere with the operation of cleaning and rinsing and reduces the efficiency of the operation. Block copolymers such as EO / PO, low foaming nonionics, can be used to reduce the foaming properties of alkyl polyglucoside surfactants, but these materials have undesirable properties, for example, low biodegradability, relatively high aquatic toxicity and poor caustic compatibility. *** f is necessary for the development of defoamers that do not interfere with the cleaning ability of aqueous cleaning compositions that are biodegradable, showing low aquatic toxicity and good caustic compatibility.

COMPENDIUM OF THE INVENTION The surprising discovery has been made that the products of the reaction of epichlorohydrin and compounds having the formula II R3 (EO) n (PO) m-OH (II) where R3 is an alkyl, alkenyl or arenyl group having from 4 to 22 carbon atoms; a substituted alkyl or alkenyl group having from 4 to 22 carbon atoms wherein; n is a number from 0 to 50 and m is a number from 0 to 10; wherein the molar ratio of epichlorohydrin to (II) is from about 0.60 / 1 to about 2/1 an extremely efficient defoamer for aqueous surfactant systems. These reaction products are added to a surfactant in an amount sufficient to reduce or eliminate the foam. The reaction products have the advantage of being totally water dispersible, are rapidly biodegradable, contain non-organic solvents and do not affect the detergency of the surfactants with which they are used because they are non-ionic surfactants by themselves.

BRIEF DESCRIPTION OF THE DRAWING Figure 1 shows the relative defoaming effect of 0. 1% by weight of a defoamer of Examples 1-3 in GLUCOPON® 220 surfactant in soapy water at 35 ° C under the test protocol of Example 4.

DESCRIPTION OF THE PREFERRED MODALITIES The defoamers according to the invention are reaction byproducts as described hereinbelow and are added to a water surfactant system comprising 1 to more surfactants in an effective amount to eliminate or decrease the foam -generated by the surfactant as a result of some kind of mechanical action such as mixing, **** and / or shaken. The amount required to remove and / or decrease foam is defined as an effective defoaming amount and may vary from one instance to another depending primarily on the nature of the surfactant or mixture of surfactants and the desired defoaming effect. A defoaming effective amount should be readily ascertainable by one of ordinary skill in the art. When the surfactant is one or more alkyl polyglucoside, the defoaming effective amount will usually vary from a weight ratio of alkyl polyglucoside / defoamer 4.0 / 1.0 to about 1.0 / 1.0. The defoaming compositions according to the invention are the products of the reaction of epichlorohydrin and compounds having the formula II.

R3 (EO) n (PO) mOH (II) wherein R3 is a saturated or unsaturated, aliphatic, substituted or unsubstituted moiety having from 4 to 22 carbon atoms; a substituted alkyl or alkenyl group has from 4 to 22 carbon atoms wherein; n is a number from 0 hata 50 and m is a number from 0 to 10; and epichlorohydrin wherein the molar ratio of epichlorohydrin to (II) is from about 0.60 / 1 to about 2/1 and preferably from about 0.80 / 1 to about 2/1. In relation to the alkoxylates of the formula II, R3 can be any saturated or unsaturated, substituted or unsubstituted aliphatic fraction having from 4 to 22 carbon atoms. In this manner R3 may be a linear or branched alkyl group, a straight or branched alkenyl or alkenyl group, a saturated carbocyclic fraction, an unsaturated carbocyclic fraction having one or more multiple bonds, a saturated heterocyclic fraction, an unsaturated heterocyclic fraction having one or more multiple bonds, a linear or branched substituted alkyl group, a linear or branched substituted alkynyl or alkenyl group, a substituted saturated carbocyclic fraction, a substituted unsaturated carbocyclic moiety having one or more multiple bonds, a substituted heterocyclic saturated moiety , a substituted unsaturated heterocyclic fraction having one or more multiple bonds. Examples of the foregoing include but are not limited to an alkyl group having from 4 to 22 carbon atoms, an alkynyl group having from 4 to 22 carbon atoms. R3 can be an arenyl group. Arenyl groups are alkyl substituted aromatic radicals having a free valence at an alkyl carbon atom such as a benzylic group. The preferred value of R3 is an alkyl group having from 4 to 22 carbon atoms and more preferably an alkyl group having from 8 to 10 carbon atoms. The degree of ethoxylation is preferably from 2 to about 50 with the most preferred being from about 4 to about 50 while the degree of oxidation may vary from 0 to 10. The degree of propoxylation will be determined by the desired degree of water solubility or miscibility . The solubility or solubility in water will finally be determined by such factors as the number of carbon atoms in R3, the relative amounts of EO for PO and the effect of PO on the biodegradability of the final defoamer. The miscibility or water solubility of a defoamer according to the invention and the correlations between the number of carbon atoms of R 3, the relative amounts of EO and PO and the biodegradability of the final product will be readily determinable by a person skilled in the art. . The reaction products of the alkoxylates of the formula II and epichlorohydrin are described in U.S. Patent No. 5,728,895 dated March 17, 1998 and can be made by the process stated in the examples below. While the method according to the invention can be used to control *** generated by any type of surfactant or mixture of surfactants it is especially used to control the foam in compositions containing one or more polyglycoside alkyl surfactants. The alkyl polyglucosides which can be used in the invention have the formula I R!? (R20) b (Z) to I wherein Ri is a monovalent organic radical having from about 6 to about 30 carbon atoms; R2 is a divalent alkylene radical having from 2 to 4 carbon atoms; Z is saccharide residue having 5 or 6 carbon atoms; b is a number that has a value of 0 up to about 12; a is a number having a value from 1 to about 6. Preferred polyglycosides that can be used in the compositions according to the invention have the formula I wherein Z is a glucose residue and b is zero. Such alkyl polyglucosides are especially available, for example, by APG®, GLUCOPON® or PLATNAREN® surfactants from Henkel Corporation, Ambler, PA 19002. Examples of such surfactants include but are not limited to: 1. APG® 225 surfactant - an alkyl polyglucoside in which the Alkyl group contains 8 to 10 carbon atoms and has an average degree of polymerization of 1.7. 2. APG® 425 surfactant - an alkyl polyglucoside in which the alkyl group contains 8 to 16 carbon atoms and has an average degree of polymerization of 1.5. 3. APG® 625 surfactant - an alkyl polyglucoside in which the alkyl group contains 12 to 16 carbon atoms and has an average degree of polymerization of 1.6. 4. APG® 325 surfactant - an alkyl polyglucoside in which the alkyl group contains 9 to 11 carbon atoms and has an average degree of polymerization of 1.5. 5. GLUCOPON® 600 surfactant - an alkyl polyglucoside in which the alkyl group contains 12 to 16 carbon atoms and has an average degree of polymerization of 1.4. 6. PLANTAREN® 2000 surfactant - an alkyl polyglycoside of Cg-iß in which the alkyl group contains from 8 to 16 carbon atoms and has a degree of polymerization of 1.5. 7. PLANTAREN® 1300 surfactant - a C1-16 alkyl polyglucoside in which the alkyl group contains from 12 to 16 carbon atoms and has an average degree of polymerization of 1.6. 8. GLUCOPON® 220 surfactant an alkyl polyglucoside in which the alkyl group contains from 8 to 10 carbon atoms and has an average degree of polymerization of 1.5. Other examples include alkyl polyglucoside surfactant compositions which are composed of mixtures of compounds of the formula I wherein Z represents a fraction derived from a reducing saccharide containing 5 or 6 carbon atoms; a is a number that has a value from 0 to approximately 6; b is zero; and Ri is an alkyl radical having from 8 to 20 carbon atoms. The compositions were characterized in that they have increased surfactant properties and an HLB in the range from about 10 to about 16 and a non-Flory glycoside distribution which is composed of a mixture of alkyl monoglycoside and a mixture of alkyl polyglucosides having various degrees of polymerization of 2 higher amounts of progressive reduction, in which the amount by weight of polyglucoside having a degree of polymerization of 2, or mixtures thereof with the polyglucoside have a degree of polymerization of 3, predominantly in relation to the amount of monoglycoside, this composition has an average degree of polymerization of about 1.8 up to about 3. Such compositions are also known as alkyl polyglucoside ***, they can be prepared by separating the msnoglucoside from the monoglycoside reaction mixture of Alkyl and alkyl polyglucosides after removing the alcohol l. This separation can be carried out by molecular distillation and usually results in the removal of about 70-95% by weight of alkyl monoglycosides. After removing the alkyl monoglycosides, the relative distribution of the various components, mono and poly-glucosides, in the resulting product changes and the concentration in the product of the polyglucosides derived from monoglycosides is implemented both in the concentration of the individual polyglucosides in the total, that is, fractions DP2 and DP3 in relation to the sum of all DP fractions. Such compositions are described in U.S. Patent No. 5,266,690, the entire content of such is incorporated herein by reference.

EXAMPLE 1 Approximately 150 grams of ethoxylated decyl alcohol with an average of 4 moles of ethylene oxide (0.45 equivalents of OH) were mixed with 685 grams of toluene and 54 grams of aq NaOH. 50% (0.675 equivalents). The water was separated by azeotropic distillation and a humidity level of less than 0.8% was reached, approximately 46 grams (0.51 equivalents) of epichlorohydrin were added slowly. This mixture was allowed to react at 100-110 ° C for 24 hours. An aliquot of this mixture was removed and filtered to remove the NaCl and stripped by vacuum to remove the ice to give a liquid product easily flowable, and amber that was dispersible in water. Approximately 1 gram of this liquid was stirred with one gram of ethoxylated decyl alcohol with an average of 4 moles of ethylene oxide in 50 grams of DI water, very little foam was observed. When one gram of ethoxylated decyl alcohol with an average of 4 moles of ethylene oxide was stirred in 50 grams of DI water, a very large amount of foam was observed.

EXAMPLE 2 Approximately 51 grams of ethoxylated butanol with an average of 2 moles of ethylene oxide (0.32 equivalents of OH) were mixed with 120 grams of toluene and 25 grams of 50% aq NaOH (0.32 equivalents). The water was removed by azeotropic distillation when a moisture level of less than 0.8% was reached, approximately 46 grams (0.24 equivalents) of epichlorohydrin were added slowly. This mixture was allowed to react at 100-110 ° C for 24 hours. An aliquot of this mixture was separated and filtered to remove the NaCl and stripped by vacuum to remove the toluene to give a liquid product easily flowable, amber which was insoluble in water. When about 1 gram of this liquid was stirred with one gram of ethoxylated decyl alcohol with an average of 4 moles of ethylene oxide in 50 grams of DI water, very little foam was observed.

EXAMPLE 3 Approximately 200.0 g (0.654 equivs hydroxyl) of ethoxylated octyl alcohol with an average of 4 moles of ethylene oxide was mixed with 400 gm of toluene and 78.4 gm (0.98 equivs) of 50% NaOH. The water was removed by azeotropic distillation until the level was less than 0.8%. the mixture was cooled to 80 ° C and 67.2 gm (0.72 mol) of epichlorohydrin were added for 45 mins. The mixture was stirred for 24 hours at 110 ° C until the epoxy titration showed no epoxide * * *. The material was cooled, filtered and the toluene was removed by vacuum distillation leaving a dark brown low viscosity liquid.

EXAMPLE 4 A test mix was prepared by mixing 51 parts (dry solid bases) of GLUCOPON® 220 surfactant and 15 parts of a defoamer of Examples 1-3. The amount of foam produced by an active test mixture 0.1% in water was compared with that of surfactant in water GLUCOPON® 220 active 0.1% according to the method below. The data of this test is represented graphically in figure 1. The foam cell consists of a 2-liter peristaltic pump with a graduated jacket with variable voltage control, and glass and silicone tubing. A test mixture is circulated at a constant flow rate and temperature, and falls from a constant height of 30 cm, also returning, creating foam. The test is run under the following series of conditions. In the first test, 0.1% of the active solution of the test surfactant in soap water (10-15 ppm) is circulated at 25 ° C and the foam volume is read every 30 seconds. In the second test, an active solution 0.1% in NaOH 1% is circulated at 25 ° C, and the foam volume is read every 30 seconds. In the third test, an active solution 0.1% in NaOH 1% is circulated. After 30 seconds, the foam volume is read and 1 ml of 1% solution of TEA-LAS is simultaneously added as a test foaming agent. After another 30 seconds, the volume of the foam is read. Approximately 30 seconds later, another ml of TEA-LAS 1% is added, and the foam volume is read 30 seconds after this. This cycle, in which the test foaming agent is added every 30 seconds and 30 seconds after the foam volume is read, is repeated until the foam volume exceeds 1,500 ml. The test is carried out at 25 ° C and 49 ° C. This method gives you an indication of the antifoam capability of the test surfactant. The relative defoaming characteristics of the compounds according to the invention as measured by this method are shown in Figure 1.

Claims (36)

1. A process for reducing or preventing the foam in an aqueous surfactant composition comprising adding to said aqueous surfactant composition a defoaming effective amount of a composition which is the product of the process comprising reacting epichlorohydrin and a compound of the formula II R3 (EO) n (PO) m-OH (II) where R3 is an alkyl, alkenyl or arenyl group having from 4 to 22 carbon atoms; a substituted alkyl or alkenyl group having from 4 to 22 carbon atoms wherein; n is a number from 0 to 50 and m is a number from 0 to 10; wherein the molar ratio of epichlorohydrin to (II) is from about 0.60 / 1 to about 2/1.

2. The process as recited in claim 1, wherein R3 is an alkyl group having from 4 to 12 carbon atoms.

3. The process of claim 1 wherein R3 is an alkyl group having from 8 to 10 carbon atoms.

4. The process of claim 1 wherein n is a number from about 2 to about 50.

5. The process of claim 1 wherein n is a number from about 4 to about 50.

The process of claim 1, wherein the molar ratio of epichlorohydrin to (II) is from about 0.80 / 1 to about 2. /1.

The process of claim 1, wherein R3 is an alkyl group having from 4 to 12 carbon atoms and n is a number from about 2 to about 50.

8. The process of claim 1, wherein R3 is an alkyl group having from 8 to 10 carbon atoms and n is a number from approximately 4 to about 50.

9. A process for reducing or preventing the foam in an aqueous surfactant composition comprising adding to said aqueous surfactant composition a defoaming effective amount is added to said aqueous surfactant composition an effective defoaming amount of a composition which is the product of the process comprising reacting epichlorohydrin and a compound of formula II R3 (EO) n (PO) m-OH (II) where R3 is an alkyl, alkenyl or arenyl group having from 4 to 22 carbon atoms; a substituted alkyl or alkenyl group having from 4 to 22 carbon atoms wherein; n is a number from 0 to 50 and m is a number from 0 to 10; wherein the molar ratio of epichlorohydrin to (II) is from about 0.60 / 1 to about 2/1 and wherein said surfactant is a compound of the formula I RiO (R20) b (Z) to I where Ri is a monovalent organic radical having from about 6 to about 30 carbon atoms; R2 is a divalent alkylene radical having from 2 to 4 carbon atoms; Z is a saccharide residue having 5 or 6 carbon atoms; b is a number that has a value from 0 to about 12; a is a number having a value from 1 to about 6.

The process of claim 9 wherein R3 is an alkyl group having from 4 to 12 carbon atoms.

11. The process of claim 9 wherein R3 is an alkyl group having from 8 to 10 carbon atoms.

12. The process of claim 9 wherein n is a number from about to about 50.

The process of claim 9 wherein n is a number from about 4 to about 50.

The process of claim 9 in where the molar ratio of epichlorohydrin to (II) is from about 0.80 / 1 to about 2/1.

15. The process of claim 9 wherein R3 is an alkyl group having from 4 to 12 carbon atoms and n is a number from about 2 to about 50.

16. The process of claim 9 wherein R3 is an alkyl group having from 8 to 10 carbon atoms and n is a number from about 4 to about 50.

17. The process of claim 9 wherein Ri is an alkyl group having from about 8 to about 10 carbon atoms a is about 1.5.

18. The reaction product of epichlorohydrin and a compound of formula II R3 (EO) n (PO) m-OH (II) where R3 is an alkyl, alkenyl or arenyl group having from 4 to 22 carbon atoms; a substituted alkyl or alkenyl group having from 4 to 22 carbon atoms wherein; n is a number from 0 to 50 and m is a number from 0 to 10; wherein the molar ratio of epichlorohydrin to (II) is from about 0.60 / 1 to about 2/1

19. The reaction product of claim 18 wherein R3 is an alkyl group having from 4 to 12 carbon atoms.

20. The reaction product of claim 18 wherein R3 is an alkyl group having from 8 to 10 carbon atoms.

21. The reaction product of claim 18 wherein n is a number from about 2 to about 50.

22. The reaction product of claim 18 wherein n is a number from about 4 to about 50.

23. The reaction product of claim 18 wherein the molar ratio of epichlorohydrin to (II) is from about 0.80 / 1 to about 2/1.

24. The reaction product of claim 18 wherein R3 is an alkyl group having from 4 to 12 carbon atoms and n is a number from about 2 to about 50.

The reaction product of claim 18 wherein R3 is an alkyl group having from 8 to 10 carbon atoms and n is a number from about 4 to about 50.

26. An aqueous surfactant composition comprising A) at least one compound of the formula I RlO (R20) b (Z) a wherein Ri is a monovalent organic radical having from about 6 to about 30 carbon atoms, R 2 is a divalent alkyl radical having from 2 to 4 carbon atoms, Z is a saccharide residue having 5 or 6 carbon atoms , b is a number having a value from 0 to about 12, a is a number having a value from 1 to about 6, and B) a reducing amount of foam of at least one reaction product of epichlorohydrin and a compound of formula II R3 (EO) n (PO) m-OH (II) where R3 is an alkyl, alkenyl or arenyl group having from 4 to 22 carbon atoms; a is a substituted alkyl or alkenyl group having from 4 to 22 carbon atoms wherein; n is a number from 0 to 50 and m is a number from 0 to 10; wherein the molar ratio of epichlorohydrin to (II) is from about 0.60 / 1 to about 2/1 27.

An aqueous surfactant composition comprises a surfactant and a reducing amount of foam of the epichlorohydrin reaction product and at least one compound of the formula II R3 (EO) n (PO) m-OH (II) where R3 is an alkyl, alkenyl or arenyl group having from 4 to 22 carbon atoms; a substituted alkyl or alkenyl group having from 4 to 22 carbon atoms wherein; n is a number from 0 to 50 and m is a number from 0 to 10; wherein the molar ratio of epichlorohydrin to (II) is from about 0.60 / 1 to about 2/1.

The composition of claim 26 wherein the weight ratio of component A to component B is from about 4.0: 1.0 to about 1.0: 1.0.

29. The composition of claim 26 wherein component B) R3 is an alkyl group having from 4 to 12 carbon atoms.

30. The composition of claim 29 wherein R3 is an alkyl group having from 8 to 10 carbon atoms.

The composition of claim 29 wherein n is a number from about 2 to about 50.

The composition of claim 29 wherein n is a number from about 4 to about 50.

33. The composition of the claim 29 wherein the molar ratio of epichlorohydrin for the at least one compound of formula II is from about 0.80 / 1 to about 2/1.

34. The composition of claim 26 wherein a component B) R3 is an alkyl group having from 4 to 12 carbon atoms n is a number from about 2 to about 50.

The composition of claim 34 wherein R3 is an alkyl group having from 8 to 10 carbon atoms and n is a number from about 4 to about 50.

36. The composition of claim 26 wherein a component A) Ri is an alkyl group having from about 8 to about 10 carbon atoms and a is about 1.5