EP2121889A1

EP2121889A1 - Use of betaines as foaming agents and foam drainage reducing agents

Info

Publication number: EP2121889A1
Application number: EP08717318A
Authority: EP
Inventors: Evelyne Prat; Sylvie Touzet; Florence Deschaseaux
Original assignee: Rhodia Operations SAS
Current assignee: Rhodia Operations SAS
Priority date: 2007-03-08
Filing date: 2008-03-03
Publication date: 2009-11-25
Also published as: WO2008110474A1; FR2913350B1; FR2913350A1; US20100069269A1; JP2010520344A

Abstract

The invention relates to the use of a betaine as a foaming agent and a foam drainage reducing agent. The invention also relates to the use of betaine in processes involving foam.

Description

Use of betaines as foaming agent and suds drainage reducing agent

The present invention relates to the use of betaine as a foaming agent and a foam drainage reducing agent. The present invention also relates to the implementation of betaine in processes involving the presence of foam.

Some industrial processes or those operated in the private domain use foams. In some detergent compositions, foam is a consumer valued signal of good cleaning ability. In these compositions, the foam also makes it possible to suspend the cleaned dirt and thus to separate them from the cleaned object or the cleaned surface. Foams are also used in fire suppression products. Foams are also used to generate light and / or porous materials: the material cures from the bubble wall forming composition, resulting in a structure comprising pores corresponding to the bubbles. Foams are also used to suspend and transport cuttings in construction operations, in the field of building and public works, particularly in excavation operations and / or tunnel drilling. Foam is also used as a visual marker on terrain. Foams are also used in the treatment of water as a depollution agent to remove particles or soiling.

There are many agents that can generate foam. Among these the most used are anionic surfactants including alkyl ether sulfates, which have a useful detergency and generate a preferred foam. A zwitterionic surfactant, cocoamidopropyldimethylbetaine, is also known and widely used.

In order to increase the volume of foam, numerous "foam-toning" compounds have been described, in particular polymers. Such polymers are especially used in dishwashing compositions by hand.

The processes described above may require a relatively long lifetime of the foam, otherwise the operations and phenomena can not be completed or their effectiveness diminished. For example in the generation of a light material, the foam must remain present during the hardening time. The sooner the foam drains, the less pores will induce lightness and / or the desired porosity. In excavation operations, the earlier the foam disappears, the less material will be evacuated.

There is a need to generate decreased drainage foams, i.e., foams whose water content is maintained high longer and / or retaining a certain volume of foam for a longer time. Maintaining the high water content results in, for example, a high durability of the properties, especially mechanical and / or the preservation of the shape of bubbles and / or homogeneity. There is a need for agents to this effect.

The invention responds to this need by proposing the use in a foaming aqueous composition, as foaming agent and agent for reducing the drainage of the foam, of a betaine surfactant chosen from the following:

the alkylbetaines of formula (I) below:

R ¹ -N ⁺ R ² R ³ -CH ₂ -COO ^" (I) - the alkylamidoalkylbetaines of formula (II) below:

R ^'1 -CO-NH-R ₄ -N ⁺ R ² R ³ -CH ₂ -COO ^"(II), and

- their mixtures and associations, where:

R ¹ represents a linear or branched, saturated or unsaturated alkyl group comprising from 16 to 24 carbon atoms,

- R ' ¹ represents a linear or branched, saturated or unsaturated alkyl group comprising from 15 to 23 carbon atoms,

- R ⁴ represents a divalent C 1 -C ⁴ alkyl group, optionally substituted with a hydroxyl group, - R ² and R ³ , which may be identical or different, represent a C ₁ -C ₂ alkyl group, optionally substituted with a hydroxyl group.

The surfactant described above is hereinafter referred to as "agent of the invention" or "betaine surfactant".

The invention also relates to a process for the preparation of foam in which the aqueous composition comprising the agent of the invention is foamed, for example by stirring and / or propelling with the aid of a gas.

The invention also relates to processes comprising a step of preparing foam and another step, simultaneous or subsequent. These may be industrial processes or operated in the private domain. The interest is particularly marked in the context of industrial processes. The invention makes it possible in particular:

- keep the foam longer, - to preserve the foam as much time, but with lesser amounts of agent, which is economical and / or beneficial for the environment, or at least perceived as such,

- Keep longer the homogeneity of the foam, and / or - to have a presence of a quantity of foam, cumulated over time, more important.

The agent of the invention provides in particular an excellent compromise between the amount of foam generated and its duration over time.

By drainage is meant the flow of the water contained in the foam, which can lead to the degradation of the walls of the bubbles and finally to the gradual return to the state of aqueous composition free of bubbles.

Composition and agent invention

The composition is an aqueous composition comprising the agent of the invention. The agent of the invention has the ability to generate foam. The foam can be generated by any conventional method, including agitation, relaxation, implementation of a propellant, implementation of an aerosol device etc. The generated foam is low drainage. It is therefore an agent both foaming and reducing drainage. The composition may comprise a foaming agent other than betaine surfactant. If this is the case, the weight ratio between the betaine surfactant and the other foaming agent is preferably greater than 4, preferably greater than 5, preferably greater than 10.

Preferably the composition is free of other foaming agent. For example, it is meant that the composition comprises less than 0.1% by weight, preferably less than 0.05%, preferably not at all other foaming agent. The generation of foam and the low drainage may therefore be, under the invention, the consequence of the agent of the invention substantially alone.

Foaming agents are known to those skilled in the art. Alkyl ether sulfates, alkylsulfates and alkylbenzenesulfonates, which are widely used, are mentioned in particular.

The foaming composition may in particular comprise from 0.05 to 5%, preferably from 0.1 to 2%, preferably from 0.15 to 1.5%, for example from 0.2 to 1%, or from

0.3 to 0.7%, by weight, betaine surfactant.

Preferably, in the agent of the invention:

R ² and R ³ are methyl groups, and

- R ⁴ is the group -CH ₂ -CH ₂ -CH ₂ -. advantageously:

- R ¹ represents an alkyl group, linear or branched, saturated or unsaturated, comprising from 18 to 22 carbon atoms, or - R ' ¹ represents an alkyl group, linear or branched, saturated or unsaturated, comprising from 17 to 21 atoms of carbon.

It is mentioned that the groups R ¹ and R ' ¹ can correspond to residues of fatty acids, generally of natural origin, most often vegetable. The fatty acid to which R ' ¹ corresponds is the fatty acid of formula R' ¹ -COOH. The fatty acid to which R ¹ corresponds is the fatty acid having the same number of carbon atoms. Thus, the group R ' ¹ may correspond to a linear or branched, saturated or unsaturated fatty acid comprising from 15 to 23, preferably from 17 to 21, carbon atoms. The group R ¹ may correspond to a linear or branched, saturated or unsaturated fatty acid comprising from 16 to 24, preferably from 18 to 22, carbon atoms. It is customary to assimilate the groups R ¹ and R ' ¹ to the fatty acid to which they correspond.

These fatty acids and groups are known. These are generally derived from vegetable oils. They can be present in mixtures. In the case of mixtures, all the groups (or corresponding fatty acids), irrespective of the number of carbon atoms, are included in the definition if the group (or corresponding acid) predominates in weight (relative majority, preferably absolute, preferably at least 75%) corresponds to the definition. It is common to reduce the name to the group (or corresponding acid) group (or acid) majority.

The groups R ¹ and R ^'1 may correspond to fatty acids -C ₈ or C ₂₂ as stearic, oleic or erucic acid. They preferably correspond to an oleyl or erucyl group.

The composition may include all kinds of additional ingredients, depending on its purpose and use. The water of the composition preferably has a moderate hardness, preferably of hardness ranging from 5 to 100 ⁰ TH, for example from 20 to 60. Such conditions can improve the reduction of drainage.

The pH of the composition can be varied. It can be controlled using known agents. The pH may in particular be greater than or equal to 4 or 5, preferably greater than or equal to 7, for example 8-9 to 1 1-12. High pH can improve drainage reduction. The composition, and the processes in which it is implemented, can be of varied temperature. It is for example between 20 ⁰ C and 80 ⁰ C, preferably between 20 ⁰ C and 40 ⁰ C or between 40 and 80 ⁰ C. Moderate temperatures can improve the deduction of drainage. The invention makes it possible in particular to maintain a low drainage at relatively high temperatures, for example between 40 ⁰ C and 80 ⁰ C, which makes it particularly useful and advantageous in certain processes operated at relatively high temperatures.

The composition may be prepared by simple mixing of water, the agent of the invention, and possibly other ingredients.

Uses and processes

The foaming composition may especially be:

a composition comprising a hydraulic binder, a composition for the manufacture of ceramics, which may in particular comprise a slip,

a drilling fluid,

a composition comprising compounds capable of generating a crosslinked polymeric material, a field marking composition,

a fire extinguishing composition,

a water depollution composition,

a foaming bath composition, or

a detergent composition. Such compositions are known to those skilled in the art. They most often comprise additional compounds, in addition to the agent of the invention. These are known to those skilled in the art. Foam processes with such compositions are known to those skilled in the art.

For compositions comprising a hydraulic binder, it may especially be cementitious compositions or plaster compositions for obtaining a porous material and / or lightweight and / or refractory and / or insulating, for example a material for thermal and / or acoustic insulation. The agent of the invention can in particular be used in a process (generally of industrial type) where the hydraulic binder composition is foamed and then the composition is allowed to harden in the form of a foam to obtain the material. Another process may be to prepare a dispersion of the binder in water to incorporate a foam obtained using the system of the invention, and then leave the composition harden. Such processes may in particular be implemented to obtain pre-manufactured materials, such as pre-fabricated building elements.

It is the same for the compositions capable of generating an optionally crosslinked polymeric material, the hydraulic binder being replaced by a polymer, which may optionally crosslink in contact with the ambient air, or by a multi-compound chemical system comprising at least a polymer or oligomer, said system possibly being crosslinkable when the several compounds are brought into contact, where appropriate under the action of a contact of the ambient air. The compositions capable of generating a polymeric material may for example be latex-based compositions for addition to fibrous products, for example carpet backing and / or non-woven surfaces. . Compositions capable of generating a polymeric material may also be used in the paper industry. The invention can confer on the hydraulically bound or polymeric based materials a good uniformity.

For compositions for the production of porous ceramics (for example based on oxides), they may especially be compositions comprising a slip. The agent of the invention may in particular be used in a process where the foam is introduced into the slip (water-based composition and ceramic precursor) so as to obtain a porous piece that can be handled manipulably which is then subjected to a temperature profile in an oven so as to obtain a porous piece by sintering the oxides at high temperature.

For drilling fluids, it can be excavated excavation fluids implemented in tunneling operations, or in well digging operations, before well cementing. The agent of the invention can in particular be used in a process (generally industrial type) where the composition is foamed, injected at the level of a drilling or digging tool, such as a tunnel boring machine, and evacuated. the foam carrying (usually) cuttings out of the contact area of the tool and the rock drilled or dug. The foam makes it possible in particular to prevent collapses of the rock, to evacuate the cuttings, to fluidify the pierced or dug rock, to homogenize it, and / or to waterproof it locally and if necessary temporarily. For fire extinguishing compositions, it may especially be extinguisher compositions or compositions used in building safety systems. The invention provides foams having good heat resistance, which makes them particularly suitable for use in extinguishing fires. This could include extinguishing fires in buildings and / or in forests or farms, and / or fires related to the burning of hydrocarbons for example during unintentional or criminal fires of installation of extraction, storage or transport of oil and / or gas.

For detergent compositions, it may be hand dishwashing compositions, shampoos or shower gels for the body and hair, liquid soaps for handwashing, laundry washing compositions for hand-held or semi-automatic machine, detergent formulations for washing vehicles such as cars and trucks, compositions for household cleaning or industrial surfaces, where it can be interesting that the foam has a life time sufficient to allow cleaning action (eg for cleaning toilets). In these compositions the invention can provide by the presence of foam a visual signal of complete coverage of the object or part of the object to be cleaned. The agent of the invention can in particular be used in a process (operated in the private domain generally) where the composition is diluted and foamed (by agitation, often generated by the movement of the hands or by a jet of water dilution), and the dirty dishes are brought into contact with the diluted composition and having foam.

A process involving terrain marking includes a foam generation step, and a step where the foam is left on the ground to mark it. The longer the foam lasts, the longer the marking is persistent. You can leave the foam on the ground by projecting it from an aircraft, an airplane for example. This can be used in the military field to identify areas of operations, or in the agricultural field, to identify treatment areas.

Other details or advantages of the invention may appear in light of the examples which follow without limitation.

EXAMPLES

Products used - Mirataine BET C30, Rhodia ("BET C30"): cocoamidopropyldimethyl betaine

- EMPICOL ESB3M, Huntsman ("SLES"): sodium lauryl ether sulfate - active substance 27%

- Mirataine BET O-30, Rhodia ("BET O30"): oleamidopropyldimethyl betaine - Mackam OB-30, Mclntyre ("OB30"): oleyldimethyl betaine

Mirataine BET E-40, Rhodia ("BET E40"): A mixture comprising erucylamidopropyldimethyl betaine (40% by weight of active material) and 20% by weight of isopropanol.

Mixture 1: Mixture of Mirataine BET E-40 and 10% by weight of benzyltrimethylammonium chloride.

- Water: tap water ("city water") from Aubervilliers, France, December 2007.

Used equipment Raynery agitator 3 blade propeller

Plastic beaker of 2 L diameter 14,5cm Glass cone

Implementation of the drainage test The drainage is characterized by the half-life of the foam (by volume). The higher the half-life time, the lower the drainage. The procedure is as follows: 1-Preparation of 200 ml of composition by mixing the ingredients (compositions given below), optionally hot (80 ^° C.). The compositions are given below: amount of active ingredient ingredients, the remainder being water. 2- Foaming

Stirring of the composition in a 2-liter beaker with a 3 blade propeller at 2000 rpm for 5 min. The volume of foam produced is noted.

3- Follow up the drainage in a cone of 1 liter until the foam releases 100 ml of water (life time because it is half of the initial composition used to make the foam).

The drainage improvement factor F is _defined as the ratio of the life time for the test compound to the time of / 4 for a reference compound, SLES, at the same amount by weight. A factor of 1 does not bring any improvement. More Fd _r a _m age, the higher the drainage is reduced. A factor greater than 1, 5 represents an interesting improvement of the drainage, greater than 50%.

A factor for improving the amount of foam F _mOUS is _defined as the ratio between the amount of foam for the test compound and the amount of foam. for a reference compound, SLES, with the same amount by weight. A factor less than 1 corresponds to a smaller amount of foam.

An improvement factor for the presence of foam F is defined as the product of the dropping and the _foam is representative of a compromise between the foam generated and a low drainage.

In the examples, the letter C indicates a comparative example.

Examples 1 to 10

Examples 1 to 10 show that:

- Only used betaine surfactants of the invention allow to obtain a low drainage foam. A betaine surfactant whose alkyl has only 12 carbon atoms (BET C-30, comparative) does not provide this effect.

the compromise of drainage / quantity of foam is improved.

Claims

1. Use in a foaming aqueous composition, as a foaming agent and agent for reducing the drainage of the foam, of a betaine surfactant chosen from the following:

the alkylbetaines of formula (I) below:

R ¹ -N ⁺ R ² R ³ -CH ₂ -COO ^" (I)

the alkylamidoalkyl betaines of formula (II) below:

R ^'1 -CO-NH-R ₄ -N ⁺ R ² R ³ -CH ₂ -COO ^"(II), and - mixtures thereof and associations, wherein:

R ⁴ represents a divalent C 1 -C ⁴ alkyl group, optionally substituted with a hydroxyl group,

- R ² and R ³ , identical or different, represent a C ₁ -C ₂ alkyl group, optionally substituted by a hydroxyl group.

2. Use according to claim 1, characterized in that:

the composition optionally comprises a foaming agent other than betaine surfactant,

- If the composition comprises another foaming agent, then the weight ratio between the betaine surfactant and the other foaming agent is greater than 4, preferably 5.

3. Use according to claim 2, characterized in that the composition is free of other foaming agent.

4. Use according to one of the preceding claims, characterized in that:

R ² and R ³ are methyl groups, and

- R ⁴ is the group -CH ₂ -CH ₂ -CH ₂ -.

5. Use according to one of the preceding claims, characterized in that: - R ¹ represents an alkyl group, linear or branched, saturated or unsaturated, comprising from 18 to 22 carbon atoms, or - R ' ¹ represents an alkyl group, linear or branched, saturated or unsaturated, comprising from 17 to 21 carbon atoms.

6. Use according to one of the preceding claims, characterized in that: - the group R ¹ or the group R ' ¹ correspond to an oleyl or erucyl group.

7. Use according to one of the preceding claims, characterized in that

the foaming composition comprises from 0.05 to 5%, preferably from 0.1 to 2%, by weight of the betaine surfactant.

8. Use according to one of the preceding claims, characterized in that the foaming composition is:

a composition comprising a hydraulic binder,

a composition for the manufacture of ceramics, a drilling fluid,

a composition comprising compounds capable of generating an optionally crosslinked polymeric material,

a terrain marking composition,

a fire extinguishing composition, a water depollution composition, or

a foaming bath composition, or

a detergent composition.

9. Use according to claim 8, characterized in that the composition a hydraulic binder is a cementitious composition or a plaster composition for obtaining a porous material and / or light and / or refractory and / or insulating.

10. Use according to claim 8, characterized in that the drilling fluid and a cut excavation fluid implemented in tunnel piercing operations.

1. Use according to claim 8, characterized in that the detergent composition is a cleaning composition by hand dishwashing.