FR2680781A1 - Adjuvant composition containing a foaming agent, usable in the building and public works industry for the manufacture of lightweight materials based on hydraulic binder - Google Patents

Abstract

Adjuvant composition, usable in the building and public works industry. This adjuvant composition includes a foaming agent and is characterised in that the foaming agent contains a protein derivative belonging to the class of salts of fatty acid condensate and of protein(s) and of protein hydrolysates. The adjuvant composition according to the invention makes it possible to obtain a foam with increased stability, in which the bubble walls are stronger.

Description

 The present invention essentially relates to an adjuvant composition containing a foaming agent, in particular usable in the building industry and public works for the manufacture and prefabrication of light and lightweight materials, based on hydraulic binder.

 This adjuvant composition according to the invention makes it possible to improve the quality of the foams obtained from the point of view of their stability and of their particular ability to be incorporated into hydraulic binders, in particular concretes, mortars, thereby enabling cati light and light materials, as well as mortars and insulating plasters, with excellent mechanical performance.

 It is well known, according to the current technology for manufacturing cellular mortars, that the stability of the mechanical and other performances of these materials depends essentially on the quality of the foam produced, in particular in a specific foam generator and its more or less great attitude to be incorporated in the binder + sabLe + water elances.

 According to the prior art, in general, foaming agents based on synthetic surfactants, such as sodium lauryl ether sulfates, are used in combination with foam stabilizers in solution in an alcohol, generally glycol ethers.

 Existing foaming products additionally require the use of fluidifying or superplasticizing additives which are incorporated in primary mortars.

 This additional use of fluidizers or superplasticizers requires perfect control of the metering of water, which, in ready-mixed concrete plants, is difficult to achieve, despite the care taken, given the inevitable variations in the quality of the sands and their water content.

 We know that an excess of water causes segregation of mortars. Conversely, an insufficient dosage of water will result in the production of too firm mortars in which the foam "breaks" and cannot be incorporated properly.

 The problems encountered, according to the prior art, result in significant drops in mechanical strengths, mortars that are too "soft", and in heterogeneities of the mixtures, which lead to instability of the foam, with as a consequence the difficulty of controlling the volumes. of the material used.

 Various attempts have been made to overcome some of these problems, and the use of compositions containing trietholinolamine salts has been proposed in particular.

Thus, patent SU-1,114,644 has proposed, in an attempt to improve the phase ratio and the stability of the foam in the aeration of gypsum mixtures, to use foaming agents containing water. and C7-C15 chain alkyl sulfate triethanolamine salts.

 Furthermore, European patent EP-AO 296 94, has proposed a foaming agent composed of two compounds A and B, compound A containing in particular approximately 42% of a seL of trietanolamine of fatty-chain alkyl sulphate of the form CH3 (CH2) 10CH20 SO3 NH (C2H4OH) 3 and B containing in particular a C14 fatty alcohol or a mixture of C10-C16 fatty alcohols. The mixing of these two components requires stirring for several hours, which constitutes an industrial disadvantage.

 The applicant has now found new adjuvant compositions containing new foaming agents, making it possible for the first time to solve all of the problems not resolved by the products of the prior art and in particular to produce finer foams, of greater stability, and whose walls of air bubbles are more resistant, stiffened and can therefore be incorporated better into concrete without being destroyed during mixing.

 The present invention also aims to solve a new technical problem consisting in the supply of a new adjuvant composition improving the mechanical strengths of light or lightened materials manufactured, in particular based on hydraulic binder, such as cements, lime, plaster and anhydrites.

 Another object of the present invention is to provide a new adjuvant composition making it possible to prepare light or light materials which are not very sensitive to water absorption and whose thermal insulation is thus improved.

The present invention also aims to provide an adjuvant composition whose compatibility and synergy between the constituents allow the optimization of their activity at the same time as the particularly simple production of a homo-genie mixture,
The present invention also aims to provide a new adjuvant composition allowing the manufacture of light and light materials, such as mortars or cellular concretes, in cold weather, that is to say at temperatures below 50C, more easily, due to better fluidity in aqueous solution and in the absence of deposit formation.

 These technical problems are solved for the first time by the present invention simultaneously, in an easy manner, usable on an industrial scale.

 Thus, according to a first aspect, the present invention provides an adjuvant composition containing at least one foaming agent, in particular usable in the building industry and public works for the manufacture and prefabrication of light and light materials, based on hydraulic binder. , in particular cement, lime, plaster, anhydrite, as well as insulating mortars and plasters, characterized in that at least one of said foaming agents is a protein derivative belonging to the family of fatty acid and protein condensate salts (s) and protein hydrolysates.

 According to an advantageous embodiment of the invention, the fatty acid condensate salt and protein (s) is an alkaline salt, for example a potassium salt or preferably a triethanolamine salt.

 According to one embodiment of the invention, the fatty acid of said condensate is a C12-C18 fatty acid. As proteins in said condensate, any type of protein can be used.

However, exceptional, unexpected results are obtained by using collagen as protein, and more preferably collagen hydrolysates. Particularly preferred collagen hydrolysates are those for which the peptides obtained by the hydrolysis of collagen have a low average molecular weight, advantageously less than approximately 1000, for example between 100 and 1000. A particularly preferred example is the use collagen peptides having an average molecular weight of about 300.

 According to a preferred embodiment of the invention, a potassium salt is used as the alkaline salt of fatty acid condensate and protein (s).

 Preferably, a triethanoeamine salt of fatty acid condensate and protein (s) is used.

ou M désigne un métal alcalin, et de préférence le potassium (M=K) et

pour le sel de triéthanolamine dans lesquelles
R représente les chaînes latérales des acides aminés des
protéines, en particulier des peptides du collagène, n représente un nombre entier, déterminé par la nature et le poids
moléculaire de la protéine, avantageusement compris entre 3 et 5, m est un nombre entier compris entre 6 et 16, en particulier 10.These salts correspond to the following formulas

or M denotes an alkali metal, and preferably potassium (M = K) and

for the triethanolamine salt in which
R represents the side chains of the amino acids of
proteins, in particular collagen peptides, n represents an integer, determined by the nature and the weight
molecular of the protein, advantageously between 3 and 5, m is an integer between 6 and 16, in particular 10.

encore plus avantageusement, le sel de triéthanolamine du même condensat

ou R désigne une channe Latérale des acides aminés du collagène.Advantageously, the product corresponding to your formula will be used as the fatty acid condensate salt and protein (s).

even more advantageously, the triethanolamine salt of the same condensate

or R denotes a lateral chain of the amino acids of the collagen.

 When the protein foaming agent is a protein hydrolyzer, it is advantageously a partial hydrolyzate of collagen proteins.

dans laquelle p est un entier compris entre 8 et Il et
R représente les chaînes latérales d'acides aminés du collagène
On utilisera également avantageusement un se de cet acide, par exemple un sel alcalin, par exemple le sel de sodium

ou p et R ont les significations données ci-dessus. Preferably, this partial hydrolyzate corresponds to the following formula

in which p is an integer between 8 and Il and
R represents the side chains of amino acids of collagen
One will also advantageously use a se of this acid, for example an alkaline salt, for example the sodium salt

where p and R have the meanings given above.

 Advantageously, these protein hydrolysates are chosen from products having a molar mass of between 500 and 2,000.

 According to an advantageous embodiment of the invention, the foaming agent also contains an anionic surfactant, in particular an alkyl ether sulphate and / or an alkyl sulphate and / or an alkylarylsulphonate in which the alkyl chains are fatty chains derived in particular from fatty alcohol C12-C18.

 These alkyl ether sulfates, alkyl sulfates or alkylarylsulfo notes are advantageously alkali salts, in particular sodium salts or preferably alkanolamine salts in particular triethanolamine salts.

 According to an advantageous characteristic, the triethanolamine alkyl ether sulphates comprise an alkyl ether part resulting from the condensation of two ethylene oxide groups on a fatty alcohol, preferably a C 12 or C 14 alcohol or a mixture of these alcohols.

 According to another advantageous characteristic, the triarylamineamine alkylarylsulfonates have a fatty alkyl chain, for example a dodecyl chain.

 Advantageously, the composition of the invention contains plasticizing agents and stabilizing agents.

 As plasticizing agent, it is possible, for example, to use derivatives of naphthalene sulfonate.

 In a preferred variant, a mixture of ethoxylated fatty alcohols is used as plasticizing agent. Advantageously, the mixture of ethoxylated fatty alcohols will consist of a mixture of C8 to C18 ethoxylated fatty alcohols mainly containing C12 to C16 alcohols. Preferably, the mixture of fatty alcohols will comprise 20 to 50% of C12 chains and 20 to 50% of C16 chains. This plasticizing mixture will be incorporated into the composition in doses such that this plasticizing agent simultaneously plays the role of stabilizing agent.

 According to an advantageous alternative embodiment, the adjuvant composition is in liquid form by incorporating the foaming agents and the plasticizing and stabilizing agents into a solvent base.

 This solvent base advantageously contains an alcohol, in particular an alcohol or a lower C1-C8 diol, for example isobutyl alcohol, monopropylene glycol or a salt of one of these alcohols, for example butyl glycol acetate.

 The composition according to the invention also advantageously contains a compound intended to act as a foam enhancer and viscosifier, making it possible to obtain an optimal coating of the air bubbles. We can choose an amphoteric type product and more particularly a product of the family of diethanolamides based on coconut oil. However, the applicant has discovered that improved results are obtained by using amine oxides, generally used in cosmetology for their foaming properties, as foam-reinforcing agent. Particularly favorable results have been observed using dimethyllaurylamine oxida.

 Advantageously, the compositions according to the invention contain by mass from 6 to 30% (expressed as the active material of these products) of foaming agents consisting at least partially of protein derivatives belonging to the family of fatty acid condensate salts and protein (s) and protein hydrolysates.

Advantageously, these protein derivatives represent 3 to 20% (expressed as the active material of these products) of the foaming composition, according to the invention, the other foaming agents consisting of an alkyl sulfate or alkyl ether sulfate or dralkyl aryl sulfonate salt. , or a mixture of these products.

 The plasticizing and stabilizing agent for the foam, advantageously consisting of a mixture of ethoxylated fatty alcohols, advantageously represents, expressed as active material, 6 to 23% by weight of the adjuvant composition.

 The foam enhancer, advantageously consisting of dimethyllaurylamine oxide, advantageously represents, expressed as the active material of this product, 5 to 20% by weight of the foaming composition.

 The solvent base represents from 8 to 17% by weight of the adjuvant composition according to the invention.

 Water represents the balance of the composition.

 Finally, various additives may be contained in the composition, in particular agents having wetting and hydrotropic properties based on ethyl-2-hexyl sulfate salt, as well as amphoteric surfactants with beta structure, having excellent resistance to alkalis, in particular in mortars with a pH greater than 13. These additions advantageously represent 1.5 to 3%, expressed in weight of active material, relative to the adjuvant composition.

 The compositions according to the invention are conventionally prepared under conditions where the various ingredients are mixed while avoiding foaming during their mixing, by playing in particular on the injection flow rates and by equipping the mixing tank with propeller agitator. an external recirculating centrifugal pump. The recirculation loop must be filled with water, the assembly having been purged of the air it contains.

 By way of nonlimiting examples of composition according to the invention, a composition will be prepared containing the following proportions expressed by weight of dry matter of the various constituents.

- Foaming agent
a) Triethanolamine salt of
condensation of C12 fatty acid and
collagen peptide having a weight
average molecular of about 300 .................. 3-20%
b) Triethanolamine lauryl sulfate ................. 3-15% - Plasticizer
mixture of C8-C18 ethoxylated fatty alcohols containing
mainly C12-C16, and preferably 20 to
50% of C12 and 20 to 50% of C16 .............. 6-23% - Solvent base
a) isobutyl alcohol. 8-17%
b) water ............... 100% balance
Other advantageous examples of compositions according to the invention also include additives with a wetting and hydrotopic property and / or foam reinforcing agents, in particular those mentioned above in the proportions mentioned above.

 The adjuvant compositions of the invention are in concentrated form. Usually an amount of a liter is prepared which is then diluted in 60 liters to 80 liters of water for the production of foams in the usual way in a foam generator, as is well known to those skilled in the art. The foam thus produced itself incorporated into the material containing the hydraulic binder for the manufacture of light and light materials, as well as mortars, insulating plasters, in a usual manner well known to those skilled in the art.

Thanks to the adjuvant composition according to the invention, the determining technical advantages previously stated are obtained, namely, in particular
1. Cellular mortars in which the adjuvant is incorporated are easier to manufacture without the need to add fluidifying or superplasticizing adjuvants.

 2. The foam produced by the generator from a solution of one liter of admixture diluted in 60 liters to 80 liters of water is more fluid and lighter and quickly becomes incorporated in mortars.

 3. Air bubbles are more stable; the bubble walls are more resistant.

 4. The mechanical strengths of hardened cellular mortars are markedly increased due to a particular particle size distribution of the air bubbles and the homogeneous dispersion of the cement grains which are thus better hydrated.

 5. Hardened cell mortars are less sensitive to water absorption; the thermal conductivity of the materials produced with these cellular mortars is therefore more efficient.

Better still, the formulation of the present example is compatible with water-repellent products of the stearate or oleate type, which makes it possible to obtain mortars and concretes which are completely non-absorbent of water.

 6. The manufacture of cellular mortars in cold weather, at 5 degrees for example, is much easier, because the adjuvant dissolved in water remains very fluid and does not form a deposit.

 7. Optimization of the activity of the various components due to the total compatibility between the various constituents of the composition.

 8. An easy industrial preparation not requiring recourse to violent agitation since a simple stirring leads to a homogeneous mixture.

 9. An absence of influence of hard water on .'action of the formulation according to the invention.

 10. The cost of manufacturing cellular mortars is considerably reduced, because the addition of fluidifying or plasticizing additives in the primary mortar is no longer essential.

The invention also covers products, in particular light and light materials, based on hydraulic binder, in particular cement, lime, plaster, anhydrite, as well as mortars, insulating plasters, characterized in that they are obtained by
The use of an adjuvant composition according to the invention.

Claims (16)

 I. Additive composition containing at least one foaming agent, in particular usable in the building industry and public works for the manufacture and the prefabrication of light and light materials, based on hydraulic binder, in particular of cement, lime, plaster, anhydrite, as well as gatekeepers and insulating plasters, characterized in that at least one of said foaming agents is a protein derivative belonging to The daughter of the fatty acid condensate salts and protein (s) and protein rydrolysates.  2 Composition according to claim 1, characterized in that the protein derivative is a salt of fatty avid condensate and protein (s), advantageously an alkaline salt or a triethanolamine salt.  3. Composition according to claim 2, characterized in that the aforementioned fatty acid is a C12-C18 fatty acid.  4. Composition according to one of claims 2 or 3, characterized in that the aforementioned proteins comprise collagen, preferably collagen hydrolysates, have the peptides have a low average molecular weight advantageously less than approximately 1000, more preferably between 100 and 1000.  5. Composition according to one of claims 2 to 4, characterized in that The condensate salt of ras acid and proteins corresponds to the formula

 or

 where M represents an alkali metal, m is an integer between 6 and 16, in particular m = O n is an integer determined by the nature and the molecular weight of  protein, advantageously between 3 and 5 R represents the side chains of the amino acids of proteins,  especially collagen peptides.  6. Composition according to one of claims 2 to 5, characterized in that the condensate salt of fatty acid and protein (s) corresponds to one of the following formulas

 or

 7. The composition as claimed in claim 1, characterized in that the protein derivative is a protein hydrolyzate.  where p is an integer between 8 and 11 and R represents side chains of amino acids of collagen or being in the form of a salt of this acid, in particular an alkaline salt.

 8. Composition according to claim 7, charac-ersee in that the protein derivative is a partial hydrolyzate of collagen proteins corresponding to the following formula  9. Composition according to one of Claims 1 to 8, characterized in that the foaming agent also contains at least one anionic surfactant chosen from alkylsulphates, alkylethersulphates, Alkylarylsulphonates derived from C12-C18 fatty alcohol.  10. Composition according to one of claims 1 to 9, characterized in that it comprises a plasticizing agent.  11. Composition according to Claim 10, characterized in that the said plasticizing agent is a mixture of ethoxylated fatty alcohols.  12. Composition according to one of claims 1 to 11, characterized in that it further comprises a solvent base.  13. Composition according to one of claims 1 to 12, characterized in that it also contains a foam-enhancing agent.  14. Composition according to claim 13, characterized in that the foam-strengthening agent is an amine oxide, in particular the dimethyllaurylamine oxida.  15. Composition according to one of claims 1 to 13, characterized in that it contains the following proportions by weight - Foaming agent  a) Triethanolamine salt of  condensation of C12 fatty acid and  collagen peptide having a weight  average molecular of about 300 .................. 3-20%  b) Triethanolamine lauryl sulfate ................. 3-15% - Plasticizer  mixture of ethoxylated fatty alcohols in  C8-C18 containing mainly C12-C16,  and preferably 20 to 50% of C12 and 20 to 50%  of C16 ....................... 6-23% - Solvent base  a) isobutyl alcohol .............................. 8-17%  b) water ....................................... 100% balance  16. Products, in particular light and light materials, based on hydraulic binder, in particular cement, lime, plaster, anhydrite, as well as mortars, insulating plasters, characterized in that they are obtained by the use of a adjuvant composition according to any one of claims I to 15.