LOW FOAMING SURFACTANTS

The present invention relates to the general field of formulations containing surfactants, more particularly that of formulations containing nonionic surfactants and in particular that of formulations containing alkoxylated nonionic surfactants.

[0002] It is now known that alkoxylated compounds represent a family of compounds offering a wide range of properties, with multiple applications, such as solvents, hydrotropic agents or surfactants, to name but a few. between them. Thus, alkoxylated compounds constitute a class of compounds with surface-active properties presenting a real industrial interest in very many fields of application.

[0003] The uses of alkoxylated compounds as surfactants constitute an entirely privileged application, as the volumes of surfactants are today high for such numerous and varied uses, and for example in the form of formulations for detergent or cleaning or washing to name a few examples.

[0004] Within formulations for detergents, surfactants make it possible, because of their intrinsic properties, to make soiling which is most often organic and lipophilic, compatible with a hydrophilic medium, generally an aqueous medium, and so on. being able to remove said lipophilic dirt with the hydrophilic medium.

[0005] A disadvantage, however, often encountered with such surfactants is their tendency to form a greater or lesser quantity of foam, this quantity being able to vary according to the physical, chemical, or even physico-chemical conditions of the medium in which they are present. found, and in particular as a function of the agitation (mechanical or not) of the medium, of the temperature of the medium, of the viscosity of the medium, of the pH of the medium, and others.

[0006] If, in certain applications, foaming may be desired or desired, or even necessary, there are applications for which detergent formulations are sought having the lowest possible foaming, or even a total absence of foaming during use. This is for example the case for alkaline formulations used in detergents and for example for detergent formulations intended for dishwashing machines. Indeed, in the case of formulations for dishwashers, the generation of too much foam can prove to be detrimental both for the correct operation of the appliances and for the quality of the washing of the dishes.

[0007] Still other uses require formulations based on surfactants with low foaming power, among which mention may be made, by way of illustration but not of limitation, of multi-purpose cleaners ("multi-purpose cleaner" in French). English), the cleaning of hard surfaces (“Hard Surface Cleaning” in English), the cleaning of clothes, the cleaning of toilets, the washing of cars in general, the Cleaning In Place (NEP) or “cleaning in place” ( CIP), in English, and others.

A class of surfactants particularly suitable for the manufacture of formulations for these applications is represented by alkoxylated nonionic surfactants, that is to say having at least one, and preferably, at least two units. alkoxylated.

[0009] Such surfactants are for example described in international application WO2009000852, said surfactants being alcohol alkoxylates of the Neodol type (poly branched alcohols obtained by the Fischer-Tropsch process) and of the primary type.

[0010] Still other polyalkoxylates are described in the international application WO2012005897 which discloses the alkoxylation of alcohols for use as surfactants in various applications.

[0011] Alkoxylated nonionic surfactants, such as for example those described in the documents cited above, often have foaming powers which can be moderate to high, so that today there remains a need for detergent formulations based on non-ionic surfactants with even lower foaming powers.

Another object of the present invention is to provide detergent formulations based on surfactants with low foaming power, not only when hot, but also at lower temperatures, even when cold, for example between +5 °C and + 50°C.

[0013] Yet another objective consists in proposing formulations for detergents based on surfactants with low foaming power, including at low temperatures, and which are derived from bio-sourced products, and more particularly from bio-sourced products which do not compete with the human or animal food industry.

[0014] It has now been discovered that these objectives can be achieved in whole or at least in part, thanks to the invention which is described in the description which follows. Still other advantages will become apparent from said description of this invention.

[0015] The Applicant has now surprisingly discovered that certain alkoxylates exhibit foaming powers lower than those observed with

alkoxylates known in the prior art and that these alkoxylates can advantageously enter into the composition of detergent formulations as a surfactant.

Thus, and according to a first aspect, the present invention relates to a detergent formulation comprising at least one secondary alcohol alkoxylate, in which said secondary alcohol comprises from 3 to 22 carbon atoms, preferably from 5 to 22 carbon atoms. of carbon, more preferably from 5 to 20 carbon atoms, very particularly preferably from 5 to 18 carbon atoms, limits included, and said secondary alcohol is alkoxylated by oxyalkylene units, chosen from oxyethylene (OE), oxypropylene ( OP) and oxybutylene (OB), the total number of oxyalkylene units being between 2 and 100, preferably between 3 and 100, more preferably between 3 and 50, better still between 3 and 40, and very particularly between 3 and 30 , terminals included.

[0017] The oxyalkylene units of the secondary alcohol alkoxylate can be identical or different and, if they are different, they can be arranged in any way whatsoever and for example randomly, in blocks, in an alternating manner or sequenced or whatever. It is in particular preferred to use, for the purposes of the present invention, a secondary alcohol alkoxylate as defined above and having oxyalkylene units arranged in blocks.

As indicated above, the alcohol used as starting substrate for the alkoxylation reaction(s) comprises from 3 to 22, preferably from 5 to 22 carbon atoms, more preferably from 5 to 20 , most preferably from 5 to 18 carbon atoms. Carbon atoms can be straight chain, branched or partially or fully cyclic.

According to another preferred aspect of the present invention, the alcohol used as starting substrate for the alkoxylation reaction(s) has a degree of branching equal to 0, 1 or 2, more preferably 1 or 2.

The expression "degree of branching" denotes, within the meaning of the present invention, the total number of terminal methyl (-CH 3 ), methylene (=CH ) and methyne (ºCH) groups (known as the "terminal groups") ) present on the alcohol used as starting substrate for the alkoxylation reaction(s), total number from which the value 1 is subtracted. In other words, the degree of branching, noted D is an integer equal to the difference between the sum of the end groups present on the alcohol used as the starting substrate for the alkoxylation reaction(s) and 1. This equation can be expressed as:

D = å(terminal groups) - 1

[0021] Thus, if the starting alcohol comprises 2 terminal methyl groups, the degree of branching is then equal to 1 (D=å(terminal groups)-1=2-1=1). For example, the degree of branching of cardanol (1 terminal methylene group) is 0, that of 2-octanol is 1, and that of 4-methyl-2-pentanol is 2.

According to a preferred embodiment, in the formulation according to the present invention, the secondary alcohol has a weight-average molar mass ranging from 45 g mol 1 to 300 g mol -1 , preferably from 70 g mol 1 to 250 g mol 1 , more preferably from 80 g mol 1 to 200 g mol 1 , limits included.

[0023] The secondary alcohol used as starting substrate and intended to be alkoxylated can be of any type and of any origin, and in particular of petroleum origin, or of bio-sourced origin, for example of plant or animal origin. . However, a secondary alcohol of bio-sourced origin is preferred, for obvious reasons of environmental protection.

[0024] A secondary alcohol comprising from 3 to 14 carbon atoms, more preferably still from 6 to 12 carbon atoms, is also preferred, and according to a very particularly preferred embodiment, the secondary alcohol is chosen from 2-octanol and 4-methyl-2-pentanol, very particularly advantageously, the secondary alcohol is 2-octanol.

[0025] 2-octanol is in fact of very particular interest in several respects, in particular because it comes from a bio-sourced product and which does not compete with human or animal food. Furthermore, 2-octanol, which has a high boiling point, is biodegradable and has a good ecotoxicological profile.

As indicated above, the alkoxylated repeating units are chosen from ethylene oxide, propylene oxide and butylene oxide units and mixtures thereof. “Ethylene oxide unit” means a unit resulting from ethylene oxide after opening of the oxirane ring, “propylene oxide unit” means a unit resulting from propylene oxide after opening of the oxirane ring, and “butylene oxide unit” means a unit derived from butylene oxide after opening of the oxirane ring.

The alkylene oxides mentioned above can be of various origins, and in particular "mass balance" alkylene oxides, in particular "mass balance" ethylene oxide, alkylene oxides of bio-sourced origin. Advantageously, the ethylene oxide is of bio-sourced origin, for example the ethylene oxide can be obtained by oxidation of bio-sourced ethylene coming from the dehydration of bio-ethanol, itself coming from starch corn, lignocellulosic materials, agricultural residues such as for example sugar cane bagasse, and others.

The secondary alcohol alkoxylate as it has just been defined and useful for the preparation of formulations for detergents with low foaming power according to the present invention can be prepared by any means known to those skilled in the art, and in particular according to any known method of alcohol alkoxylation.

Conventionally, the alkoxylation of alcohol is advantageously carried out in the presence of a catalyst, and advantageously the alkoxylation is carried out by basic or alkaline catalysis, using for example sodium hydroxide (NaOH) or potassium hydroxide, called soda or potash catalysis, respectively.

[0030] Other types of catalysts can be used, and in particular those now known to those skilled in the art specializing in alkoxylation, to lead to alkoxylates having a narrow, or even very narrow, distribution in number of alkoxylate units. Such catalysts are known under the name of "narrow range" catalysts (narrow distribution), and are for example chosen from catalysts based on calcium, based on boron derivatives (such as acid catalysts of the type derived from BF 3 ), catalysts of the hydrotalcite type, and catalysts of the dimetallic cyanide type (“DiMetallic Cyanide” in English, or DMC).

For the purposes of the present invention, formulations are preferred in which said at least one secondary alcohol alkoxylate is chosen from narrow distribution secondary alcohol alkoxylates and in particular those obtained by alkoxylation of a secondary alcohol via "narrow range" catalysis, and more preferably via DMC catalysis.

According to one embodiment, the secondary alcohol alkoxylate used as a surfactant with low foaming power in the detergent formulation according to the present invention is a capped (or capped) secondary alcohol alkoxylate, that is to say whose terminal -OH part is substituted, as described for example in document EP2205711, or in international application WO2004037960.

According to a preferred aspect, the substituent of the terminal part, also called cap of the terminal part, or more simply terminal cap is a group chosen from linear or branched alkyls comprising from 1 to 6 carbon atoms, the phenyl group , the benzyl group, the hydrocarbon groups bearing a carboxy -COO- function, and the groups bearing a sugar unit.

Preferably, the end cap of the secondary alcohol alkoxylate is chosen from methyl, ethyl, propyl, butyl, benzyl and alkylcarboxyl groups and their salts. Among the possible salts of the carboxyl function, mention may be made of the salts well known to those skilled in the art and in particular the salts of metals, alkali metals,

alkaline earth metals, ammonium, to name only the main ones. Very particularly preferred salts are the sodium, potassium, calcium and ammonium salts.

According to another embodiment, the end cap of the secondary alcohol alkoxylate is chosen from alkylene carboxyls and their salts, optionally functionalized. A typical and non-limiting example is represented by the sulfosuccinate group, and in particular sodium sulfosuccinate, potassium sulfosuccinate, calcium sulfosuccinate and ammonium sulfosuccinate.

According to yet another embodiment, the end cap of the secondary alcohol alkoxylate is chosen from groups bearing a sugar unit, such as for example glucose (case of monoglucosides), or two or more sugar units (case of alkypolyglucosides, also called “APG”).

According to yet another embodiment of the present invention, formulations for detergents in which said at least one secondary alcohol alkoxylate comprises at least ethylene oxide (EO) units are preferred. According to another preferred embodiment of the present invention, the detergent formulation comprises at least one secondary alcohol alkoxylate having at least ethylene oxide (EO) units and at least propylene oxide (OP) units, said patterns that can be distributed randomly, alternately or in blocks, and preferably in blocks.

According to yet another preferred embodiment, the total number of repeating units carried by the secondary alcohol alkoxylate included in the detergent formulation according to the present invention is between, limits included, 1 and 30, preferably between 2 and 20, more preferably between 3 and 20, advantageously between 3 and 15.

In a very particularly preferred embodiment, the detergent formulation according to the present invention comprises at least one 2-octanol alkoxylate. Very particularly advantageously, said alkoxylate is chosen from 2-octanol with ethoxylated units, 2-octanol with ethoxylated and propoxylated units, 2-octanol with ethoxylated and butoxylated units, 2-octanol with propoxylated units, 2- octanol with propoxylated and butoxylated units, and 2-octanol with butoxylated units. However, formulations for detergents comprising at least one 2-octanol with ethoxylated units or at least one 2-octanol with ethoxylated and propoxylated units are preferred.

Examples of secondary alcohol alkoxylates which are particularly suitable for the formulations according to the present invention are those chosen from 2-octanol 2-15 EO, 2-octanol 2-15 OE 1 OP, 2 -octanol 2-15 OE 1-15 OB, 2-octanol 2-15 OE 1 -15 OP, and 2-octanol 1 -6 OE 1 -15 OP.

The content of secondary alcohol alkoxylate(s) in the detergent formulation according to the present invention can vary within large proportions depending on the nature of the alkoxylate(s) and the nature and intended use of the formulation. As a general rule, the content of secondary alcohol alkoxylate(s) is between 1% and 99%, more generally between 1% and 50%, advantageously between 1% and 25%, by weight of alkoxylate(s) per relative to the total weight of the formulation.

The formulation according to the present invention may comprise any type of additives, fillers known to those skilled in the art specializing in formulations and in particular formulations for detergents.

Thus, and by way of non-limiting examples, the detergent formulation according to the present invention may comprise one or more of the additives and fillers chosen from detergent agents, in particular basic, such as for example sodium hydroxide, surfactants, perfumes, dyes, inert fillers, impregnating agents, aqueous, organic, hydro-organic solvents, chosen from water, alcohols, glycols, polyols, mineral oils, vegetable oils, waxes, and the like, singly or in mixtures of two or more of them, in all proportions.

[0044] In particular, the formulation according to the invention may comprise one or more additives and fillers well known to those skilled in the art, such as, for example, and without limitation, anionic, cationic, amphoteric surfactants, not -ionics, rheology modifiers, de-emulsifiers, anti-settling agents, foaming agents, anti-foaming agents, hydrotropic agents, dispersants, pH control agents, colorants, anti-oxidants, preservatives, corrosion inhibitors, biocides, and other additives such as for example sulfur, boron, nitrogen, phosphorus products, and others. The natures and quantities of the additives and fillers can vary in large proportions depending on the nature of the application envisaged and can easily be adapted by those skilled in the art.

As indicated above, the formulation for detergent according to the present invention comprises a secondary alcohol alkoxylate as it has just been defined with low foaming power, thus giving the formulation which contains it quite interesting properties, particularly in terms of low foaming power, but also in terms of detergent power. It has in fact been observed that the formulations of the present invention and in particular those comprising a 2-octanol alkoxylate have an improved detergent power, in particular because of the low foaming power of the secondary alcohol alkoxylate.

The present invention finally relates to the use of at least one secondary alcohol alkoxylate, as surfactant, in a detergent formulation to lower the

foaming power. It has in fact been observed that the secondary alcohol alkoxylates as they have just been defined, and in particular the alkoxylates obtained by "narrow range" catalysis, have very low foaming properties ("low-foaming surfactant" in English) and in particular lower than with other alkoxylates having the same number of alkoxylated units but a different substrate, for example a primary alcohol.

The secondary alcohol alkoxylates as they have just been defined, and in particular those obtained by so-called "narrow range" catalysis, have very interesting application properties in terms of performance, and biodegradability profiles that are quite of interest, in particular for low levels of alkoxylation, <8 units, preferably <8 units, more preferably <6 units, and even more preferably <4 units.

The secondary alcohol alkoxylates as they have just been defined, and in particular those obtained by "narrow range" catalysis, thus find entirely suitable applications because of their very good degreasing, solubilizing and emulsifying properties. , and in particular of low foaming power, which makes them surfactants of choice when used in detergent formulations for dishwashers. In fact, a low foaming power leads to better results in terms of “spotting”, that is to say traces left on the dishes and in particular the glass.

Thus the secondary alcohol alkoxylates as they have just been defined find quite interesting applications in detergent formulations, and in particular in detergent formulations for dishwashers, for multi-purpose cleaning ( "multi-purpose cleaner" in English), for cleaning hard surfaces ("Hard Surface Cleaning" in English), for cleaning clothes ("laundry" in English), for cosmetic products, for cleaning sanitary facilities, for car washing in general, for Cleaning In Place (NEP) or "cleaning in place" (CIP), in English, and others.

The secondary alcohol alkoxylates as defined above can also be used in various formulations in which such surfactants are necessary or desired as emulsifiers, wetting agents, solvents, coalescing agents or adjuvants, in particular processing aids, and in particular in formulations for detergents, for cosmetic products, for the flotation of ores, as a lubricant, in particular for metal processing fluids (“ Metal Working Fluids"), for bituminous applications, for de-inking, as a gas hydrate anti-caking agent, for enhanced oil and gas recovery applications, for corrosion protection, for hydraulic fracturing,for soil depollution, in agrochemicals (for example coatings of granular products, in particular fertilizers and phytosanitary products), but also as a hydrotropic agent, antistatic agent, paint adjuvant, textile adjuvant, for polyols, for the production of electrodes and electrolytes for batteries, to name only the main fields of application.

The invention is now illustrated by the following examples which are in no way limiting.

EXAMPLES

Secondary alcohol alkoxylates with varying numbers of alkoxylated units are tested for their low foaming power and compared to primary alcohol alkoxylates with varying numbers of alkoxylated units. The alkoxylates are prepared according to techniques known to those skilled in the art. Unless otherwise indicated, the alkoxylates are prepared by DMC catalysis, for example according to the procedure described in WO2019092366 A1.

The tests are carried out according to the NFT 73-404 standard and has the principle of measuring the volume of foam (in mL) obtained after the fall, from a height of 450 mm, of 150 mL of a solution containing the surfactant to be tested on the liquid surface of 50 mL of the same solution, prepared with deionized water. The evolution of the volume of foam (in mL) is measured as a function of time. The operating conditions (concentrations, composition of the solution and temperature) and the results are presented in Table 1 below:

- Table 1 ~

Solution A: 0.05% by weight alkoxylate solution in water.

Solution B: aqueous solution of alkoxylate at 2 g L _1 in NaOH solution at 2 g L 1 .

* 2-octanol Oleris ® “Refined” grade (purity > 99%), marketed by Arkema France.

These results show the low foaming power of the secondary alcohol alkoxylates tested alone or in a formulation with an aqueous solution of sodium hydroxide (basic formulation), compared with other alkoxylates, in particular of primary alcohols.

It is observed that the secondary alcohol alkoxylates, with an equal number of alkoxylated units, all produce a volume of foam reduced to T0. In addition, any foam produced at T0 disappears quickly (T+5min or T+1min in the basic formulation) with the secondary alcohol alkoxylate compared with all the other alkoxylates tested.

CLAIMS

1. Detergency formulation comprising at least one secondary alcohol alkoxylate, wherein said secondary alcohol comprises from 3 to 22 carbon atoms, preferably from 5 to 22 carbon atoms, more preferably from 5 to 20 carbon atoms, most preferably from 5 to 18 carbon atoms, limits included, and said secondary alcohol is alkoxylated by oxyalkylene units, chosen from oxyethylene (OE), oxypropylene (OP) and oxybutylene (OB), the total number of oxyalkylene units being between 2 and 100, preferably between 3 and 100, more preferably between 3 and 50, better still between 3 and 40, and very particularly between 3 and 30, limits included.

2. Formulation according to claim 1, in which the secondary alcohol has a weight-average molar mass ranging from 45 g mol -1 to 300 g mol -1 , preferably from 70 g mol 1 to 250 g mol 1 , preferably again from 80 g mol 1 to 200 g mol 1 , limits included.

3. Formulation according to claim 1 or claim 2, in which the secondary alcohol contains from 3 to 14 carbon atoms, more preferably from 6 to 12 carbon atoms, and very particularly preferably, the secondary alcohol is chosen from 2-octanol and 4-methyl-2-pentanol, advantageously the secondary alcohol is 2-octanol.

4. Formulation according to any one of the preceding claims, in which the said at least one secondary alcohol alkoxylate is chosen from secondary alcohol alkoxylates with a narrow distribution and in particular those obtained by alkoxylation of a secondary alcohol via “narrow” catalysis. range”, and more preferably via catalysis of the dimetallic cyanide type (“DiMetallic Cyanide” in English, or DMC).

5. Formulation according to any one of the preceding claims, in which the said at least one secondary alcohol alkoxylate comprises at least ethylene oxide (EO) units and preferably at least ethylene oxide (EO) units and at least propylene oxide (OP) units, said units possibly being distributed randomly, alternately or in blocks, and preferably in blocks.

6. Formulation according to any one of the preceding claims, in which the said at least one secondary alcohol alkoxylate is chosen from 2-octanol with ethoxylated units, 2-octanol with ethoxylated and propoxylated units, 2-octanol with ethoxylated and butoxylated, 2-octanol with propoxylated units, 2-octanol with propoxylated and butoxylated units, and 2-octanol with butoxylated units, and preferably from 2-octanol with ethoxylated units and 2-octanol with ethoxylated units and propoxylated.

7. Formulation according to any one of the preceding claims, in which the said at least one secondary alcohol alkoxylate is chosen from 2-octanol 2-15 OE, 2-octanol 2-15 OE 1 OP, 2-octanol 2-15 OE 1-15 OB, 2-octanol 2-15 OE 1-15 OP, and 2-octanol 1-6 OE 1-15 OP.

8. Formulation according to any one of the preceding claims, in which the content of secondary alcohol alkoxylate(s) is between 1% and 99%, more generally between 1% and 50%, advantageously between 1% and 25% , by weight of alkoxylate(s) relative to the total weight of the formulation.

9. Formulation according to any one of the preceding claims, further comprising one or more of the additives and fillers chosen from detergents, surfactants, perfumes, dyes, inert fillers, impregnating agents, aqueous, organic, hydro-organic solvents, chosen from water, alcohols, glycols, polyols, mineral oils, vegetable oils, waxes, and others, alone or in mixtures of two or more of them, in all proportions .

10. Use of at least one secondary alcohol alkoxylate according to any one of claims 1 to 7, as surfactant in a detergent formulation to lower the foaming power.

11. Use according to claim 10, wherein said at least one secondary alcohol alkoxylate is as described in any one of claims 1 to 7.

12. Use according to claim 10 or claim 11, wherein said at least one secondary alcohol alkoxylate is obtained by so-called “narrow range” catalysis.

13. Use according to claim 10, in a detergent formulation for dishwashers, for all-purpose cleaning, for cleaning hard surfaces, for cleaning clothes, for cosmetic products, for cleaning sanitary facilities, for washing automobiles in general, and for Cleaning In Place (NEP) or "cleaning in place" (CIP), in English.