KR20200037145A - Aqueous polymer composition and copolymer - Google Patents

Abstract

(I)
본발명은 추가로 상기 공중합체 자체, 이를 제조하기 위한 방법, 및 고성능 감수제로서의 그의 용도에 관한 것이다.The present invention relates to an aqueous composition comprising a polymerizable olefinically unsaturated and anionic monomer having a carboxylic acid functional group, and a copolymer obtained by a special polymerization reaction involving a monomer of formula (I):

(I)
The present invention further relates to the copolymer itself, a method for preparing it, and its use as a high performance water reducing agent.

Description

Aqueous polymer composition and copolymer

The present invention relates to an aqueous composition comprising an anionic monomer comprising polymerizable olefinically unsaturated and carboxylic acid groups and a copolymer obtained by a specific polymerization reaction involving monomers of formula (I):

(I)

The present invention also relates to the copolymer itself and to a method for preparing it and its use as a high performance water reducing agent.

The composition according to the invention is advantageously used in the technical field of mortar, concrete, plaster or other compounds based on hydraulic compounds or binders, in particular cement and plaster. Such compositions can advantageously be used in the field of construction and public works, or in the use of hydrocarbons.

Dispersant compounds of hydraulic binders are typically used for their ability to change the rheology of the medium in which they are present, especially for their ability to control the workability of this medium.

Workability is usually defined as the properties of a composition comprising a hydraulic binder that remains as long as possible workable, especially slag or cement or mortar slurries, or concrete, such as ready-to-use concrete or concrete molded into blocks. Advantageously, operability control makes it possible to transport or move the aqueous composition comprising a hydraulic binder, for example during transport or movement from one tank to another. Workability also makes it possible to control the conditions under which such aqueous compositions are stored. It also makes it possible to pump this composition, or to pump it easily. Controlling the operability of such a composition thus makes it possible to improve the conditions of use, especially to increase its use time under satisfactory or effective conditions. In general, the workability of an aqueous composition comprising a hydraulic binder can be evaluated by measuring the slump time of the hydraulic binder. In particular, the hydraulic binder or high performance water reducing agent makes it possible to obtain a composition having a stable, controlled viscosity and, preferably, a stable viscosity over a long period of time.

Preferably, improving the workability of the aqueous hydraulic composition comprising the hydraulic binder should be possible even for compositions containing a small amount of water.

Accordingly, an important aspect of the present invention is the provision of an aqueous composition comprising a hydraulic binder with improved workability time. Workability control should not cause changes in other properties, especially mechanical properties, especially when the composition is newly developed.

The workability of the aqueous composition comprising the hydraulic binder can be evaluated, for example, by measuring the slump according to standard EN 12350-2. In fact, slump and workability are proportional.

Slump retention is another property that is controlled in aqueous compositions comprising hydraulic binders.

These properties are particularly sought for certain applications, for example when filling the formwork of an aqueous composition comprising a hydraulic binder.

Another aspect of the invention relates to obtaining an aqueous composition comprising a hydraulic binder that allows to limit or reduce shrinkage during drying.

The improvement of the properties of the aqueous composition comprising the hydraulic binder should be achieved without changing the composition setting, especially without delaying the setting.

Aqueous compositions comprising a hydraulic binder should have the lowest possible weight ratio of water / hydraulic binder, generally water / cement or W / C, without altering its properties as well.

One effect that is also sought in aqueous compositions comprising a hydraulic binder is to enable control of the amount of air trapped in the material resulting from the composition settings, thus avoiding or reducing the use of antifoam agents in the hydraulic composition. .

In general, an aqueous composition comprising a hydraulic binder should be able to improve the mechanical properties of the material obtained, in particular its mechanical properties in new developments; These properties can be evaluated by measuring the change in compressive strength over time.

In addition, the mixtures used in the preparation of aqueous compositions comprising hydraulic binders should be used in smaller amounts.

The mixtures used in the preparation of aqueous compositions comprising hydraulic binders are aqueous, including hydraulic binders, in particular by being miscible in all proportions with these other components to avoid or limit the risk of separation of the components of the aqueous composition comprising hydraulic binders. It must also be highly or completely compatible with the other components of the composition.

An increase in residence time of the properties of aqueous compositions comprising hydraulic binders must also be sought.

Patent application US 2011 0186773 describes polymer preparation with disodium dipropionate trithiocarbonate without mention of improving workability of concrete compositions or reducing the amount of water in such compositions. Patent application US 2014 0343240 describes polymer additives to hydraulic compositions; This polymer additive is prepared using a chain transfer reagent, thiol. Patent application US 2014 0088250 relates to a method for preparing a polymer using disodium dipropionate trithiocarbonate. Patent application US 2016 0289120 describes workability-retaining agents for concrete compositions.

There are known dispersant compounds or high performance water reducing agents that can be used in aqueous compositions comprising hydraulic binders. However, these compounds do not make it possible to provide a solution to the problem at hand. In particular, these compounds do not make it possible to maintain a good initial slump level of the aqueous composition comprising the hydraulic binders they contain, without changing their mechanical properties or initiating separation phenomena while maintaining their workability.

Accordingly, there is a need for dispersant compounds or high performance water reducing agents for aqueous compositions comprising hydraulic binders that make it possible to provide solutions to some or all of the compounds in the prior art.

The present invention makes it possible to provide solutions to some or all of the problems facing polymer compositions in the prior art. In particular, the present invention makes it possible to obtain copolymers using, for example, production methods that are particularly effective for controlling the polymerization reaction temperature. In particular, it is essential to be able to use a production method which makes it possible to avoid the need to maintain the low temperature of the reaction medium used during the polymerization reaction known in the prior art.

In addition, a method of making it possible to polymerize unsaturated monomers with different molecular mass M _W , for example in the range of 800 to 5,000 g / mol molecular mass M _W measured by SEC, in the presence of comonomers comprising vinyl groups What is available is also essential.

Similarly, when using the methods in the prior art, it is essential to be able to carry out a polymerization reaction that makes it possible to copolymerize monomers with reactivity which limit or hinder their polymerization.

It is also essential to control these polymerization reactions, in particular to be able to control the proportion of polymerized comonomers relative to the proportion of said comonomer introduced during the reaction. The copolymer preparation can thus include comonomer residues in a proportion equal or similar to the proportion of monomers used.

Thus, the present invention is in water and at temperatures ranging from 10 to 90 ° C.

In the presence of:

(i) 0.05 to 5% by weight of at least one compound of formula (II) relative to the amount of monomer:

(II)

here:

- x independently represents H, Na or K,

- R independently represents a C1-C5 alkyl group; And

(ii) hydrogen peroxide, ammonium persulfate, alkali metal persulfate, mixtures thereof or combinations thereof with alkali metal bisulfites or combinations thereof with ions selected from Fe ^II , Fe ^III , Cu ^I , Cu ^II At least one radical-generating compound

Provided is an aqueous composition comprising at least one copolymer having a polymerization molecular weight index P _I less than 3, obtained by at least one radical polymerization reaction of the following components:

(a)  At least one anionic monomer comprising at least one polymerizable olefinically unsaturated and at least one carboxylic acid group or salt thereof, and

(b) At least one monomer of formula (I):

(I)

here:

-R ¹ and R ² are the same or different and independently represent H or CH ₃ ,

-L independently represents a group selected from (CH ₂ -CH ₂ O) _x , (CH ₂ CH (CH ₃ ) O) _y , (CH (CH ₃ ) CH ₂ O) _z and combinations thereof, and

- x, y and z are the same or different and independently represent an integer or decimal number included in the range 0 to 150, and the sum of x + y + z is included in the range 10 to 150.

The present invention also provides an aqueous composition comprising at least one copolymer selected from:

· In water and at temperatures ranging from 10 to 90 ° C

In the presence of:

(i) 0.05 to 5% by weight of at least one compound of formula (II) relative to the amount of monomer:

(II)

here:

- x independently represents H, Na or K,

- R independently represents a C1-C5 alkyl group; And

(ii) at least one selected from hydrogen peroxide, an alkali metal persulfate, a mixture thereof, or a combination thereof with an alkali metal bisulfite or a combination thereof with an ion selected from Fe ^II , Fe ^III , Cu ^I and Cu ^II . Radical-generating compounds,

A copolymer having a polymerization molecular weight index P _I of less than 3, obtained by at least one radical polymerization reaction of the following components,

(a)  At least one anionic monomer comprising at least one polymerizable olefinically unsaturated and at least one carboxylic acid group or salt thereof, and

(b) At least one monomer of formula (I):

(I)

here:

-R ¹ and R ² are the same or different and independently represent H or CH ₃ ,

-L independently represents a group selected from (CH ₂ -CH ₂ O) _x , (CH ₂ CH (CH ₃ ) O) _y , (CH (CH ₃ ) CH ₂ O) _z and combinations thereof, and

- x, y and z are the same or different, independently represent an integer or decimal number included in the range 0 to 150, and the sum of x + y + z is included in the range 10 to 150,

And

· In water and at temperatures ranging from 10 to 90 ° C.,

In the presence of:

(i) 0.05 to 5% by weight of at least one compound of formula (II) relative to the amount of monomer:

(II)

here:

- x independently represents H, Na or K,

- R independently represents a C1-C5 alkyl group; And

(ii) hydrogen peroxide, ammonium persulfate, alkali metal persulfate, mixtures thereof or combinations thereof with alkali metal bisulfites or combinations thereof with ions selected from Fe ^II , Fe ^III , Cu ^I , Cu ^II At least one radical-generating compound,

A copolymer having a polymerization molecular weight index P _I of less than 3, obtained by at least one radical polymerization reaction of the following components,

(a)  At least one anionic monomer comprising at least one polymerizable olefinically unsaturated and at least one carboxylic acid group or salt thereof, and

(b) At least one monomer of formula (I):

(I)

here:

-R ¹ and R ² are the same or different and independently represent H or CH ₃ ,

- L is _{(CH (CH 3) CH 2} O) z in combination with _{(CH 2 -CH 2 O) x} , and _{(CH (CH 3) CH 2} O) z in combination with (CH ₂ CH (CH ₃₎ O) independently represents a group selected from _y and combinations thereof, and

- x, y and z are the same or different and independently represent an integer or decimal number included in the range 0 to 150, and the sum of x + y + z is included in the range 10 to 150.

The conditions for preparing the composition according to the invention are particularly advantageous. In fact, these conditions for preparing the composition according to the invention make it possible to reduce or avoid the formation of the homopolymer of monomer (a). Thus, preferably, the composition according to the invention does not contain any homopolymer of monomer (a) relative to the dry weight basis of the copolymer. Also preferably, the composition according to the invention comprises a small or very small amount of the homopolymer of the monomer (a), which is reduced relative to the dry weight basis of the copolymer. Similarly, the present invention makes it possible to avoid or greatly limit the formation of different copolymers of monomer (a).

 According to the present invention, the absence or presence of a reduced, small or very small amount of the monomer (a) homopolymer in the composition according to the present invention is when the composition according to the present invention is used for its plasticizing properties in concrete formulations. It is possible to avoid or limit the risk of inhibiting the crystallization of the concrete. In general, the homopolymer of the monomer (a) has the property of dispersing mineral material particles and thus can disturb or inhibit crystallization in the concrete formulation. Therefore, the properties of the concrete formulation or the final material prepared using the formulation may be changed or changed.

Particularly advantageously and particularly effectively, the present invention makes it possible to prepare copolymers from monomers (a) and (b) while controlling the polymerization reactions of (a) and (b). The present invention thus makes it possible to obtain an aqueous composition comprising a very small amount of residual monomer (a) relative to the dry weight basis of the copolymer. Preferably, the aqueous composition according to the invention comprises less than 2,000 ppm by weight or less than 1,500 ppm by weight of residual monomer (a) relative to the amount of dry weight of the copolymer. More preferably, the aqueous composition according to the invention comprises less than 1,000 ppm by weight or less than 500 ppm by weight residual monomer (a) relative to the amount of dry weight of the copolymer. In particular, the aqueous composition according to the invention may comprise less than 200 ppm by weight or less than 100 ppm by weight residual monomer (a) relative to the dry weight of the copolymer.

The aqueous composition according to the present invention comprises at least one copolymer having a molecular weight index P _I of less than 3. Preferably according to the present invention, the polymeric molecular index P _I is in the range of 1.5 to 3, more preferably 1.8 to 2.8 or 1.8 to 2.5, even more preferably 2 to 2.8 or 2 to 2.5.

The copolymer of the composition according to the invention is at least one in water and at a temperature in the range of 10 to 90 ° C, preferably in the range of 30 to 85 ° C, more preferably in the range of 40 to 75 ° C or 50 to 70 ° C It is obtained by a radical polymerization reaction. More preferably, only one radical polymerization reaction is involved.

The preparation of the aqueous composition according to the invention involves a radical polymerization reaction carried out in water in the presence of at least one compound of formula (II) of 0.05% to 5% by weight relative to the amount of monomer.

Preferably according to the present invention, this compound (i) is a compound of formula (II) in which R represents a C ₁ -C ₃ -alkyl group, preferably a methyl group. A preferred compound of formula (II) according to the present invention is disodium dipropionate trithiocarbonate (DPTTC-CAS No. 86470-33-2).

Also preferably according to the present invention, the polymerization reaction is 0.05 to 4% by weight, 0.05 to 3% by weight, 0.05 to 2% by weight, 0.5 to 4% by weight, 0.5 to 3% by weight, 0.5 to 2 relative to the amount of the monomer Compounds of formula (II) in amounts of 1% by weight, 1% by weight, 1% by weight, 1% by weight and 2% by weight are used.

The preparation of the aqueous composition according to the invention also uses certain at least one radical-generating compound (ii). The radical-generating compound (ii) is preferably hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, mixtures thereof or a combination thereof with sodium bisulfite or potassium bisulfite or Fe ^II , Fe ^III , Cu ^I and Cu ^II are selected from combinations thereof. The radical-generating compound (ii) is more preferably hydrogen peroxide, sodium persulfate, potassium persulfate, mixtures thereof or a combination thereof with sodium bisulfite or potassium bisulfite or Fe ^II , Fe ^III , Cu ^I , Cu ^II is selected from a combination thereof with an ion selected from ^II . According to the present invention, Fe ^II , Fe ^III , Cu ^I or Cu ^II ions are iron sulfate, hydrated iron sulfate, iron sulfate hemihydrate, iron sulfate hexahydrate, iron carbonate, hydrated iron carbonate, iron carbonate hemihydrate, iron And at least one compound selected from chloride, copper carbonate, hydrated copper carbonate, copper carbonate hemihydrate, copper acetate, copper sulfate, copper sulfate pentahydrate, copper hydroxide, and copper halide.

 According to the present invention, the particular radical-generating compound is more preferably hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, sodium bisulphite and potassium bisulphite, more particularly sodium persulfate or sodium bisulfate Choose among fights. According to the present invention, the specific radical-generating compound is even more preferably selected from hydrogen peroxide, sodium persulfate, and potassium persulfate.

According to the invention, the polymerization reaction is in the absence of a compound comprising phosphorus in the I oxidation state, in particular in the absence of a hypophosphorous acid (H ₃ PO ₂ ) or a derivative of hypophosphorous acid (H ₃ PO ₂ ), for example at least one phosphate ions (H ₂ PO ₂ ^-) compound, in particular, sodium hypophosphite (H ₂ PO ₂ Na), potassium hypophosphite (H ₂ PO ₂ K), calcium hypophosphite _{([H 2 PO 2] 2} Ca) containing It is carried out in the absence of a compound selected from.

In preparing the copolymers according to the present invention, the amounts of monomers (a) and (b) used can vary widely. Preferably, the polymerization reaction uses:

-  1 to 25% by weight of monomer (a) and

- 75 to 99% by weight of monomer (b).

Also preferably, the polymerization reaction uses:

- 2 to 25% by weight of monomer (a) and

- 75 to 98% by weight of monomer (b).

Also preferably, the polymerization reaction uses:

- 3 to 15% by weight of monomer (a) and

- 85 to 97% by weight of monomer (b).

Also preferably, the polymerization reaction uses:

- 3 to 10% by weight of monomer (a) and

- 90 to 97% by weight of monomer (b).

Also preferably, the polymerization reaction uses:

- 5 to 10% by weight of monomer (a) and

- 90 to 95% by weight of monomer (b).

The present invention includes the use of a radical polymerization reaction in water of at least one anionic monomer (a) comprising at least one polymerizable olefinically unsaturated and at least one carboxylic acid group or one of its salts. Preferably, the composition according to the invention comprises a copolymer prepared by a polymerization reaction involving an anionic monomer (a) comprising one of polymerizable olefinically unsaturated and carboxylic acid groups or salts thereof. More preferably, the monomer (a) used is selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylic acid salt, methacrylic acid salt, itaconic acid salt, maleic acid salt and mixtures thereof. Even more preferably, the monomer (a) used is selected from acrylic acid, methacrylic acid, acrylic acid salt, methacrylic acid salt and mixtures thereof, more particularly acrylic acid or acrylic acid salt, especially sodium salt of acrylic acid.

During the radical polymerization reaction in water, the present invention also includes the use of at least one monomer (b) of formula (I).

Preferably, compound (b) of formula (I) is a compound that is:

- x represents an integer or decimal number included in the range of 15 to 140,

- y + z represents an integer or decimal number included in the range of 10 to 135,

- x is strictly greater than y + z and the sum of x + y + z falls within the range of 10 to 150.

Also preferably, compound (b) of formula (I) is a compound that is:

- x represents an integer or decimal number included in the range of 15 to 140,

- y + z represents an integer or decimal number included in the range of 1 to 135, and

- x is strictly greater than y + z and the sum of x + y + z falls within the range of 10 to 150.

Even more preferably, compound (b) x represents an integer or decimal number included in the range of 10 to 150 or 30 to 120, y + z represents an integer or decimal number included in the range of 10 to 135, and x is strictly A compound of formula (I) that is greater than y + z and the sum of x + y + z falls within the range of 10-150.

Also more preferably, compound (b) is a compound of formula (I), wherein x represents an integer or decimal number included between 15 and 80, and y + z represents an integer or decimal number included within the range of 10 to 65, preferably Is a compound of formula (I), wherein x represents an integer or decimal number falling within the range of 30 to 65 and y + z represents an integer or decimal number falling within the range of 15 to 40 or 10 to 25, especially x is within the range of 40 to 60 A compound of formula (I) representing an integer or decimal number included and y + z representing an integer or decimal number included in the range of 20 to 30 or 10 to 20.

Also more preferably, the monomer (b) is a compound of formula (I) wherein x is strictly greater than y + z.

 According to the present invention, preferred compound (b) is compound (b1) of formula (I), wherein:

-R ¹ and R ² represent H,

-L represents a (CH ₂ -CH ₂ O) _x group, and

- x represents an integer or decimal number included in the range of 10 to 150.

 According to the present invention, preferred compound (b) is compound (b2) of formula (I), wherein:

-R ¹ and R ² represent H,

-L independently represents a group selected from (CH ₂ CH (CH ₃ ) O) _y and (CH (CH ₃ ) CH ₂ O) _z , and

- y and z are the same or different, and independently represent an integer or decimal number included in the range 1 to 150, and the sum of y + z is included in the range 10 to 150.

 According to the present invention, preferred compound (b) is compound (b3) of formula (I), wherein:

-R ¹ and R ² represent H,

-L independently represents a group selected from (CH ₂ -CH ₂ O) _x , (CH ₂ CH (CH ₃ ) O) _y , (CH (CH ₃ ) CH ₂ O) _z , and

- x, y and z are the same or different and independently represent an integer or decimal number included in the range 1 to 150, and the sum of x + y + z is included in the range 10 to 150.

 According to the present invention, preferred compound (b) is compound (b4) of formula (I), wherein:

-R ¹ and R ² represent CH ₃ ,

-L represents a (CH ₂ -CH ₂ O) _x group, and

- x represents an integer or decimal number included between 10 and 150.

 According to the present invention, preferred compound (b) is compound (b5) of formula (I), wherein:

-R ¹ and R ² represent CH ₃ ,

-L independently represents a group selected from (CH ₂ CH (CH ₃ ) O) _y and (CH (CH ₃ ) CH ₂ O) _z , and

- y and z are the same or different, independently represent an integer or a decimal number included in the range 1 to 150, and the sum of y + z is included in the range 10 to 150.

 According to the present invention, preferred compound (b) is compound (b6) of formula (I), wherein:

-R ¹ and R ² represent CH ₃ ,

-L independently represents a group selected from (CH ₂ -CH ₂ O) _x , (CH ₂ CH (CH ₃ ) O) _y , (CH (CH ₃ ) CH ₂ O) _z , and

- x, y and z are the same or different and independently represent an integer or decimal number included in the range 1 to 150, and the sum of x + y + z is included in the range 10 to 150.

 According to the present invention, preferred compound (b) is compound (b7) of formula (I), wherein:

-R ¹ represents H,

-R ² represents CH ₃ ,

-L represents a (CH ₂ -CH ₂ O) _x group, and

- x represents an integer or decimal number included in the range of 10 to 150.

 According to the present invention, preferred compound (b) is compound (b8) of formula (I), wherein:

-R ¹ represents H,

-R ² represents CH ₃ ,

-L independently represents a group selected from (CH ₂ CH (CH ₃ ) O) _y and (CH (CH ₃ ) CH ₂ O) _z , and

- y and z are the same or different, independently represent an integer or a decimal number included in the range 1 to 150, and the sum of y + z is included in the range 10 to 150.

 According to the present invention, preferred compound (b) is compound (b9) of formula (I), wherein:

-R ¹ represents H,

-R ² represents CH ₃ ,

-L independently represents a group selected from (CH ₂ -CH ₂ O) _x , (CH ₂ CH (CH ₃ ) O) _y , (CH (CH ₃ ) CH ₂ O) _z , and

- x, y and z are the same or different and independently represent an integer or decimal number included in the range 1 to 150, and the sum of x + y + z is included in the range 10 to 150.

 According to the present invention, preferred compound (b) is compound (b10) of formula (I), wherein:

-R ¹ represents CH ₃ ,

-R ² represents H,

-L represents a (CH ₂ -CH ₂ O) _x group, and

- x represents an integer or decimal number included in the range of 10 to 150.

 According to the present invention, preferred compound (b) is compound (b11) of formula (I), wherein:

-R ¹ represents CH ₃ ,

-R ² represents H,

-L independently represents a group selected from (CH ₂ CH (CH ₃ ) O) _y and (CH (CH ₃ ) CH ₂ O) _z , and

- y and z are the same or different, independently represent an integer or a decimal number included in the range 1 to 150, and the sum of y + z is included in the range 10 to 150.

 According to the present invention, preferred compound (b) is compound (b12) of formula (I), wherein:

-R ¹ represents CH ₃ ,

-R ² represents H,

-L independently represents a group selected from (CH ₂ -CH ₂ O) _x , (CH ₂ CH (CH ₃ ) O) _y , (CH (CH ₃ ) CH ₂ O) _z , and

- x, y and z are the same or different and independently represent an integer or decimal number included in the range 1 to 150, and the sum of x + y + z is included in the range 10 to 150.

The aqueous compounds according to the present invention include at least one copolymer obtained by at least one radical polymerization reaction in at least one monomer (a) of formula (I) and at least one monomer (b) in water. The polymerization reaction may also involve one or several other monomers. The radical polymerization reaction then also uses at least one other monomer selected from:

· Another anionic monomer, preferably selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, salts thereof, and mixtures thereof;

Of non-ionic monomers comprising at least one polymerizable olefinically unsaturated, preferably at least one polymerizable ethylenically unsaturated and especially polymerizable vinyl group, more preferably of acids comprising at least one monocarboxylic acid group Esters, especially esters of acids selected from acrylic acid, methacrylic acid, and mixtures thereof, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, styrene, Vinyl caprolactam, alkyl acrylates, especially C ₁ -C ₁₀ -alkyl acrylates, preferably C ₁ -C ₄ -alkyl acrylates, more preferably methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n- butyl acrylate, alkyl methacrylates, in particular C ₁ -C ₁₀ - alkyl methacrylate Sites, preferably C ₁ -C ₄ - alkyl methacrylates, more preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, n- butyl methacrylate, aryl acrylate Rate, preferably phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, aryl methacrylate, preferably phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, compound of formula (III) :

Q ^1- (L ¹ ) _m- (L ² ) _n -Q ²

(III)

here:

-Q ¹ represents a polymerizable acrylate group or a polymerizable methacrylate group,

-Q ² represents an H group or a CH ₃ group,

-L ¹ and L ² are the same or different and independently represent an ethylene-oxy group or a propylene-oxy group, and

- m and n are the same or different, at least one of which is not 0, represents a number of 150 or less, and the sum m + n is less than 150, a non-ionic monomer selected from;

· Another monomer of formula (I) different from compound (b), wherein:

-R ¹ and R ² are the same or different and independently represent H or CH ₃ ,

-L represents a group selected from (CH ₂ -CH ₂ O) _x ,

- x represents 1;

· Another monomer of formula (I) different from compound (b), wherein:

-R ¹ and R ² are the same or different and independently represent H or CH ₃ ,

-L independently represents a group selected from (CH ₂ CH (CH ₃ ) O) _y , (CH (CH ₃ ) CH ₂ O) _z and combinations thereof,

- y + z represents 1 or 2; And

· 2-acrylamido-2-methylpropanesulfonic acid, salt of 2-acrylamido-2-methylpropanesulfonic acid, salt of 2- (methacryloyloxy) ethanesulfonic acid,

· 2- (methacryloyloxy) ethanesulfonic acid, sodium methallyl sulfonate, styrene sulfonate and mixtures thereof.

The polymerization reaction may also involve the monomer of formula (IV):

(IV)

here:

-T ¹ and T ² are the same or different and independently represent H or CH ₃ ,

-V ¹ independently represents a group selected from CH ₂ , CH ₂ -CH ₂ , O-CH ₂ -CH ₂ -CH ₂ -CH ₂ ,

-V ² independently represents a group selected from (CH ₂ -CH ₂ O) _p , (CH ₂ CH (CH ₃ ) O) _q , (CH (CH ₃ ) CH ₂ O) _r and combinations thereof, and

- p, q and r are the same or different and independently represent an integer or decimal number included in the range of 0 to 150; Preferably, p is strictly greater than q + r and the sum of p + q + r is included within the range of 10-150.

Preferably according to the present invention, this additional monomer is a compound of formula (IV) wherein:

-T ¹ and T ² represent H or CH ₃ H or

-V ¹ represents a group selected from CH ₂ or

-V ² represents a group combining (CH ₂ -CH ₂ O) _p and (CH ₂ CH (CH ₃ ) O) _q or (CH (CH ₃ ) CH ₂ O) _r or

- p represents an integer or decimal number included in the range of 10 to 140, or

- q + R represents an integer or decimal number included in the range of 10 to 140, or

- p is strictly greater than q + r and the sum of p + q + r falls within the range of 10 to 150.

According to the present invention, more preferred compounds of formula (IV), T ¹ and T ² represent H, V ¹ represents CH ₂ , V ² represents (CH ₂ -CH ₂ O) _p and (CH ₂ CH ( CH ₃ ) O) _q or (CH (CH ₃ ) CH ₂ O) represents a group that combines _r , p represents an integer or decimal number included in the range 10 to 140, and q + R is included in the range 10 to 140 Represents an integer or decimal number, p is strictly greater than q + r, and the sum of p + q + r is in the range 10 to 150 and is a phosphorus compound.

According to the present invention, further preferred compounds of formula (IV), T ¹ represents CH ₃ , T ² represents H, V ¹ represents CH ₂ , and V ² represents (CH ₂ -CH ₂ O) _p And (CH ₂ CH (CH ₃ ) O) _q or a group combining (CH (CH ₃ ) CH ₂ O) _r , p denotes an integer or a decimal number included in the range of 10 to 140, and q + R denotes Represents an integer or decimal number included between 10 and 140, p is strictly greater than q + r and the sum of p + q + r is within the range of 10 to 150 and is a phosphorus compound.

According to the present invention, further preferred compounds of formula (IV), T ¹ represents CH ₃ , T ² represents H, V ¹ represents CH ₂ , and V ² represents (CH ₂ -CH ₂ O) _p And p is a compound representing an integer or decimal number included in the range of 10 to 140.

According to the present invention, further preferred compounds of formula (IV), T ¹ and T ² represent H, V ¹ represents O-CH ₂ -CH ₂ -CH ₂ -CH ₂ ,

V ² represents (CH ₂ -CH ₂ O) _p , and p is a compound representing an integer or decimal number included between 10 and 140.

According to the present invention, further preferred compounds of formula (IV), T ¹ represents CH ₃ , T ² represents H, V ¹ represents CH ₂ -CH ₂ ,

V ² represents (CH ₂ -CH ₂ O) _p , and p is a compound representing an integer or decimal number included in the range of 10 to 140.

Certain copolymers according to the present invention are non-crosslinked copolymers.

The present invention provides water of at least one anionic monomer (a) and at least one monomer (b) of formula (I) comprising at least one polymerizable olefinically unsaturated and at least one carboxylic acid group or one of its salts. Provided is an aqueous composition comprising at least one copolymer obtained by at least one radical polymerization reaction. The invention also relates to such copolymers themselves, in particular those copolymers obtained from the aqueous composition according to the invention and subsequently obtained from the separation of the copolymer according to the invention, in particular the separation of water from the aqueous composition according to the invention.

The present invention is thus _in water and at temperatures ranging from 10 to 90 ° C.

In the presence of:

(i)  At least one compound of formula (II) in an amount of 0.05 to 5% by weight relative to the amount of monomer:

(II)

here:

- x independently represents H, Na or K,

- R independently represents a C1-C5 alkyl group; And

(ii) hydrogen peroxide, ammonium persulfate, alkali metal persulfate, mixtures thereof or combinations thereof with alkali metal bisulfites or combinations thereof with ions selected from Fe ^II , Fe ^III , Cu ^I , Cu ^II At least one radical-generating compound,

Provides a copolymer having a polymerization molecular weight index P _I less than 3, obtained by at least one radical polymerization reaction of the following components,

(a)  At least one anionic monomer comprising at least one polymerizable olefinically unsaturated and at least one carboxylic acid group or salt thereof, and

(b) At least one monomer of formula (I):

(I)

here:

-R ¹ and R ² are the same or different and independently represent H or CH ₃ ,

-L independently represents a group selected from (CH ₂ -CH ₂ O) _x , (CH ₂ CH (CH ₃ ) O) _y , (CH (CH ₃ ) CH ₂ O) _z and combinations thereof, and

- x, y and z are the same or different and independently represent an integer or decimal number included in the range 0 to 150, and the sum of x + y + z is included in the range 10 to 150.

The present invention also provides copolymers selected from:

· In water and at temperatures ranging from 10 to 90 ° C

In the presence of:

(i)  At least one compound of formula (II) in an amount of 0.05 to 5% by weight relative to the amount of monomer:

(II)

here:

- x independently represents H, Na or K,

- R independently represents a C1-C5 alkyl group; And

(ii) at least one selected from hydrogen peroxide, an alkali metal persulfate, a mixture thereof, or a combination thereof with an alkali metal bisulfite or a combination thereof with an ion selected from Fe ^II , Fe ^III , Cu ^I and Cu ^II . Radical-generating compounds,

A copolymer having a polymerization molecular weight index P _I of less than 3, obtained by at least one radical polymerization reaction of the following components,

(a)  At least one anionic monomer comprising at least one polymerizable olefinically unsaturated and at least one carboxylic acid group or salt thereof, and

(b) At least one monomer of formula (I):

(I)

here:

-R ¹ and R ² are the same or different and independently represent H or CH ₃ ,

-L independently represents a group selected from (CH ₂ -CH ₂ O) _x , (CH ₂ CH (CH ₃ ) O) _y , (CH (CH ₃ ) CH ₂ O) _z and combinations thereof, and

- x, y and z are the same or different and independently represent an integer or decimal number included in the range 0 to 150, and the sum of x + y + z is included in the range 10 to 150.

And

· In water and at temperatures ranging from 10 to 90 ° C

In the presence of:

(i)  At least one compound of formula (II) in an amount of 0.05 to 5% by weight relative to the amount of monomer:

(II)

here:

- x independently represents H, Na or K,

- R independently represents a C1-C5 alkyl group; And

(ii) hydrogen peroxide, ammonium persulfate, alkali metal persulfate, mixtures thereof or combinations thereof with alkali metal bisulfites or combinations thereof with ions selected from Fe ^II , Fe ^III , Cu ^I , Cu ^II At least one radical-generating compound,

A copolymer having a polymerization molecular weight index P _I of less than 3, obtained by at least one radical polymerization reaction of the following components,

(a)  At least one anionic monomer comprising at least one polymerizable olefinically unsaturated and at least one carboxylic acid group or salt thereof, and

(b) At least one monomer of formula (I):

(I)

here:

-R ¹ and R ² are the same or different and independently represent H or CH ₃ ,

-L is (CH ₂ -CH ₂ O) _x , (CH (CH ₃ ) CH ₂ O) combined with _z and (CH ₂ CH (CH ₃ ) O) _y combined with (CH (CH ₃ ) CH ₂ O) independently represent a group selected from _z and combinations thereof, and

- x, y and z are the same or different and independently represent an integer or decimal number included in the range 0 to 150, and the sum of x + y + z is included in the range 10 to 150.

Preferably, copolymers according to the present invention include:

-  1 to 25% by weight of monomer (a) and

- 75 to 99% by weight of monomer (b).

Also preferably, the copolymers according to the present invention include:

- 2 to 25% by weight of monomer (a) and

- 75 to 98% by weight of monomer (b).

Also preferably, the copolymers according to the present invention include:

- 3 to 15% by weight of monomer (a) and

- 85 to 97% by weight of monomer (b).

Also preferably, the copolymers according to the present invention include:

- 3 to 10% by weight of monomer (a) and

- 90 to 97% by weight of monomer (b).

Also preferably, the copolymers according to the present invention include:

- 5 to 10% by weight of monomer (a) and

- 90 to 95% by weight of monomer (b).

Copolymers according to the invention can also be characterized by their weight average molecular mass (M _W ). Preferably, the copolymer according to the invention has a weight average molecular mass in the range of 8,000 g / mol to 600,000 g / mol or 10,000 g / mol to 500,000 g / mol or 12,000 g / mol to 200,000 g / mol. More preferably, the copolymer according to the invention is 15,000 g / mol to 150,000 g / mol or 15,000 g / mol to 90,000 g / mol or 15,000 g / mol to 90,000 g / mol or 25,000 g / mol to 75,000 g / It has a weight average molecular mass in the range of mol.

According to the present invention, the molecular weight and polymerization molecular weight index of the copolymer are determined by stereoscopic exclusion chromatography (SEC). This technique involves a Waters liquid chromatography device with a detector. This detector is a Waters refractive index detector. This liquid chromatography apparatus is equipped with a steric exclusion column to separate the various molecular weights of the copolymers studied. The liquid elution phase is an aqueous phase adjusted to pH 9.00 with 1N sodium hydroxide containing 0.05 M NaHCO ₃ , 0.1 M NaNO ₃ , 0.02 M triethanolamine and 0.03% NaN ₃ .

According to the first step, the copolymer solution is diluted to 0.9 dry weight percent in the solubilizing solvent of SEC corresponding to the liquid elution of SEC with 0.04% dimethyl formamide added serving as a flow rate marker or internal standard. The copolymer solution is then filtered using a 0.2 μm filter. Then 100 μL is injected into the chromatography (eluent: pH 9.00 using 1N sodium hydroxide containing 0.05 M NaHCO ₃ , 0.1 M NaNO ₃ , 0.02 M triethanolamine and 0.03% NaN ₃ ) Adjusted aqueous phase).

The liquid chromatography apparatus has an isocratic pump (Waters 515) with a flow rate set to 0.8 mL / min. The chromatography apparatus itself also includes an oven comprising the following series of columns: Waters Ultrahydrogel Guard precolumns 6 cm long and 40 mm inner diameter, and Waters Ultrahydrogel linear columns 30 cm long and 7.8 mm inner diameter. The detection system consists of a Waters 410 RI refractive index detector. The oven is heated to 60 ° C and the refractive index meter is heated to 45 ° C.

Molecular mass is assessed by detection of dynamic light scattering using a Viscotek 270 dual detector to determine molecular mass based on the hydrodynamic volume of the copolymer.

The specific, advantageous or preferred properties of the aqueous composition according to the invention also define copolymers according to the specific, advantageous or preferred invention.

The aqueous compositions and copolymers according to the present invention have particularly advantageous properties in many technical fields. Therefore, depending on the technical field in which these properties are performed, the aqueous composition or copolymer according to the present invention may have different forms. Aqueous compositions or copolymers according to the invention can be used in particular in various formulations.

The present invention thus provides a formulation (F1) comprising:

- An aqueous composition according to at least one invention;

- At least one hydraulic binder; Randomly

- water; Randomly

- At least one aggregate; Randomly

- At least one compound.

The present invention also provides a formulation (F2) comprising:

- At least one copolymer according to the present invention;

- At least one hydraulic binder; Randomly

- water; Randomly

- At least one aggregate; Randomly

- At least one compound.

Preferably, formulations (F1) and (F2) according to the present invention include:

- 0.01 to 5% by dry weight, each of at least one aqueous composition according to the invention or at least one copolymer according to the invention, a copolymer in its own form;

- 95 to 99.9% by weight of at least one hydraulic binder.

More preferably, formulations (F1) and (F2) according to the present invention include:

- 0.01-4 dry weight percent or 0.01-3 dry weight percent, each of at least one aqueous composition according to the invention or at least one copolymer according to the invention, a copolymer in its own form;

- 96 to 99.9% by dry weight or 97 to 99.9% by dry weight of at least one hydraulic binder.

Also more preferably, the formulations (F1) and (F2) according to the invention include:

- 0.03 to 5 dry weight percent or 0.03 to 4 dry weight percent or 0.03 to 3 dry weight percent, respectively, at least one aqueous composition according to the invention or at least one copolymer according to the invention, a copolymer in its own form;

- 95 to 99.7% dry weight or 96 to 99.7% dry weight or 97 to 99.7% dry weight at least one hydraulic binder.

Also more preferably, the formulations (F1) and (F2) according to the invention include:

- 0.05 to 5 dry weight percent or 0.05 to 4 dry weight percent or 0.05 to 3 dry weight percent or 0.05 to 2 dry weight percent or 0.05 to 1.5 dry weight percent, respectively, at least one aqueous composition or invention according to the invention At least one copolymer according to, a copolymer in its own form;

- 95 to 99.5% dry weight or 96 to 99.5% dry weight or 97 to 99.5% dry weight or 98 to 99.5% dry weight or 98.5 to 99.5% dry weight at least one hydraulic binder.

Also preferably, the formulations (F1) and (F2) according to the invention are less than 0.7, less than 0.65 or less than 0.6, preferably less than 0.5 or less than 0.4, or 0.3 by weight, based on the weight of the hydraulic binder. Less or less than 0.2. The weight-based amount of water relative to the weight-based amount of the hydraulic binder in formulations (F1) and (F2) is preferably in the range of 0.2 to 0.65 or 0.2 to 0.6 or 0.2 to 0.5 or 0.3 to 0.65 or 0.3 to 0.6 or 0.3 to 0.5.

 According to the present invention, the hydraulic binder or hydroless can be selected from cement, mortar, plaster, slurry or concrete.

The cement can be selected from Portland cement, white Portland cement, artificial cement, furnace cement, high strength cement, aluminate cement, quick-setting cement, magnesium phosphate cement, cement based on incineration products, fly ash cement and mixtures thereof.

Other hydraulic binders can be selected from latent hydraulic binders, pozzolanic binders, ash, slag, and clinker.

The plaster can be selected from gypsum, calcium sulfate dihydrate, calcium sulfate, calcium sulfate hemihydrate, calcium sulfate anhydride and mixtures thereof.

The aggregate can be selected from sand, coarse aggregate, gravel, crushed stone, slag, and recycled aggregate.

In general, according to their particle size, granules are classified into several known categories to those skilled in the art according to, for example, French standard XP P 18-540. Particularly according to this standard defining d and D values, the granulation group includes:

- 0 / D filler with D <2 mm and at least 70% passing at 0.063 mm.

- 0 / D fine-grained sand with D ≤ 1 mm and at least 70% passing at 0.063 mm.

- 0 / D sand with 1 <D ≤ 6.3 mm,

- 0 / D gravel-sand mixture with D ≤ 6.3 mm,

- D / D chipping with D> 1 mm and D ≤ 125 mm,

- D / D gravel with D> 25 mm and D ≤ 50 mm.

Examples of fillers are silica fume or siliceous adducts, or lime adducts such as calcium carbonate.

 According to the present invention, the mixture in formulations (F1) or (F2) is an antifoaming agent, plasticizer or high performance water reducing agent, workability-enhancing agent, slump-reducing agent, air splash-reducing agent, colorant, pigment, water-reducing agent , Surface flame retardant, hygroscopic control agent, corrosion inhibitor, shrinkage inhibitor, silicone-alkali-reaction-inhibiting agent, waterproofing agent, foaming agent.

This particular property of the aqueous composition according to the invention or the copolymer according to the invention makes it possible to use it in many technical fields, especially for its rheological control or control properties.

Accordingly, the present invention comprises the addition of at least one aqueous composition according to the present invention or at least one copolymer according to the present invention in a hydraulic preparation comprising water and a hydraulic binder, a method for altering the rheology of a hydraulic preparation. Gives

The properties of the compositions and copolymers according to the invention are particularly useful in the field of hydraulic formulations.

Accordingly, the present invention provides a method for controlling the operability of a hydraulic formulation, comprising the addition of at least one aqueous composition according to the invention or at least one copolymer according to the invention in a hydraulic formulation. Particularly advantageously, the present invention maintains the workability of the hydraulic formulation constant for at least 1 hour, preferably at least 2 hours, more preferably at least 3 hours, and even more preferably at least 3.5 hours or at least 4 hours. It provides a method for controlling workability.

The invention also provides a method for reducing the set time of a hydraulic formulation, comprising the addition of at least one aqueous composition according to the invention or at least one copolymer according to the invention in a hydraulic formulation comprising water and a hydraulic binder. to provide.

In a method for controlling the operability of the hydraulic formulation according to the present invention or reducing the setting time of the hydraulic formulation, the hydraulic formulation is preferably selected from hydraulic formulation (F1) and hydraulic formulation (F2).

The specific, advantageous or desirable properties of the hydraulic formulations (F1) and (F2) according to the invention also control the workability of the specific, advantageous or desirable, hydraulic formulations according to the invention or reduce the setting time of the hydraulic formulation. Define a method for

The following examples illustrate various aspects of the invention.

Example 1: Preparation of copolymers according to the invention and comparative copolymers

Example 1.1: Copolymer according to the invention (P1)

Water (230 g), iron sulfate hexahydrate (0.11 g) and a 20 mass% solution of DPTTC in water (3.18 g) are placed in a stirred reactor. The reactor is heated to 65 ± 2 ° C. Hydrogen peroxide is added in an aqueous solution at 35% by mass (22.4 g).

Then, for 2 hours, a mixture of water (50 g), acrylic acid (35.77 g) and monomer (b12) having a molecular mass of 3,000 g / mol (243.23 g), 20 mass of water (50 g) and DPTTC in water The mixture of% solution (12.69 g) is injected simultaneously with a mixture of sodium bisulfite in an aqueous solution in water (40 g) and 40 mass% (22.56 g).

The reactor is maintained at a temperature of 65 ± 2 ° C. for 1 hour.

The product is cooled and then partially neutralized by adding an aqueous solution of sodium hydroxide at 50% by mass (7.8 g). The aqueous polymer solution contains less than 220 ppm dry acrylic acid relative to the total amount of dry copolymer.

A copolymer (P1) comprising 12.8% by weight of acrylic acid and 87.2% by weight of monomer (b12) is obtained. It has a molecular mass MW of 71,900 g / mol and a polymerizability index P _I of 2.

Example 1.2: Copolymer according to the invention (P2)

Water (350 g) is placed in a stirred reactor and heated to 65 ± 2 ° C.

Then, for 2 hours, a mixture of water (60 g), acrylic acid (50.39 g) and monomer (b12) with a molecular mass of 3,000 g / mol (342.65 g), 20 mass of water (60 g) and DPTTC in water % Solution (15 g) was injected simultaneously with a mixture of water (55 g) and ammonium persulfate (5.64 g).

The reactor is maintained at a temperature of 65 ± 2 ° C. for 1 hour.

The product is cooled and then partially neutralized by adding an aqueous solution of sodium hydroxide at 50% by mass (1.6 g). The aqueous polymer solution contains less than 610 ppm residual acrylic acid.

A copolymer (P2) comprising 12.8% by weight of acrylic acid and 87.2% by weight of monomer (b12) is obtained. It has a molecular mass MW of 207,000 g / mol and a polymerizability index P _I of 2.2.

Example 1.3: Copolymer according to the invention (P3)

Water (400 g), iron sulfate hexahydrate (0.11 g) and a 20% by mass solution of DPTTC in water (3.18 g) are placed in a stirred reactor. The reactor is heated to 65 ± 2 ° C. Hydrogen peroxide is added in an aqueous solution at 35% by mass (22.4 g).

Thereafter, for 2 hours, a mixture of water (40 g), methacrylic acid (29.73 g) and monomer (b12) having a molecular mass of 3,000 g / mol (370.03 g), water (50 g) and DPTTC in water A mixture of 20 mass% solution (12.69 g) is injected simultaneously with a mixture of sodium bisulfite in water (40 g) and an aqueous solution at 40 mass% (22.56 g).

The reactor is maintained at a temperature of 65 ± 2 ° C. for 1 hour.

The product is cooled and then partially neutralized by adding an aqueous solution of sodium hydroxide at 50% by mass (6.7 g). The aqueous polymer solution contains less than 25 ppm residual methacrylic acid.

A copolymer (P3) comprising 7.4% by weight of methacrylic acid and 92.6% by weight of monomer (b12) is obtained. It has a molecular mass MW of 168,600 g / mol and a polymerizability index P _I of 2.

Example 1.4: Copolymer according to the invention (P4)

Water (380 g) and a 20 mass% solution of DPTTC in water (3.0 g) are placed in a stirred reactor. The reactor is heated to 65 ± 2 ° C.

Thereafter, for 2 hours, a mixture of water (40 g), methacrylic acid (29.73 g) and monomer (b12) having a molecular mass of 3,000 g / mol (370.03 g), water (60 g) and DPTTC in water A mixture of 20% by mass solution (12 g) is injected simultaneously with a mixture of water (55 g) and ammonium persulfate (5.64 g).

A solution of hydrogen peroxide at water (5 g) and 35 mass% (5 g) in water is added for 30 minutes.

The reactor is maintained at a temperature of 65 ± 2 ° C. for 30 minutes.

The product is cooled and then partially neutralized by adding an aqueous solution of sodium hydroxide at 50% by mass (1.1 g). The aqueous polymer solution contains less than 190 ppm residual methacrylic acid.

A copolymer (P4) comprising 7.4 wt% methacrylic acid and 92.6 wt% monomer (b12) is obtained. It has a molecular mass of 538,000 g / mol MW and a polymerizability index P _I of 2.2.

Example 1.5: Copolymer according to the invention (P5)

Water (100 g), iron sulfate hexahydrate (0.11 g), monomer (b12) with a molecular mass of 3,000 g / mol (114.23 g), 2,400 g / mol molecule in a 60 mass% solution in water (152.31 g) A comonomer of formula (IV) having mass, wherein T ¹ represents CH ₃ , T ² represents H, V ¹ represents CH ₂ and V ² represents (CH ₂ -CH ₂ -O) _p , And a 20 mass% solution of DPTTC in water (2.54 g) is placed in a stirred reactor. The reactor is heated to 65 ± 2 ° C. Hydrogen peroxide is added in an aqueous solution at 35% by mass (5.6 g).

Thereafter, for 1 hour 15 minutes, a mixture of water (40 g) and acrylic acid (32.36 g), a mixture of water (50 g) and a 20 mass% solution of DPTTC in water (10.15 g) was added to water (55 g) and 40 Simultaneously infuse for 1 hour with a mixture of sodium bisulfite in an aqueous solution at mass% (5.64 g) and for 40 minutes for the latter mixture.

The reactor is maintained at a temperature of 65 ± 2 ° C. for 1 hour 30 minutes.

The product is cooled and then partially neutralized by adding an aqueous solution of sodium hydroxide at 50% by mass (35 g). The aqueous polymer solution contains less than 55 ppm residual acrylic acid.

A copolymer (P5) comprising 13.6 wt% acrylic acid, 38.4 wt% comonomer of formula (IV), and 48.0 wt% monomer (b12) is obtained. It has a molecular mass MW of 238,000 g / mol and a polymerizability index P _I of 2.9.

Example 1.6: Copolymer according to the invention (P6)

Water (400 g), iron sulfate hexahydrate (0.11 g) and a 20% by mass solution of DPTTC in water (3.18 g) are placed in a stirred reactor. The reactor is heated to 65 ± 2 ° C. At 35% by mass, hydrogen peroxide in aqueous solution is added all at once (22.4 g).

Then, for 2 hours, the following are simultaneously injected into the reactor:

-A mixture of water (40 g), methacrylic acid (29.73 g), and monomer (b12) having a molecular mass of 3,000 g / mol (370.03 g),

-20% by mass solution of DPTTC in water (12.69 g) with 50 g of water,

-A mixture of sodium bisulfite in an aqueous solution in water (35 g) and 40 mass% (33.84 g).

The reactor is maintained at a temperature of 65 ± 2 ° C. for 1 hour.

The product is cooled and then neutralized by adding an aqueous solution of sodium hydroxide at 50% by mass until pH 7.5 is reached.

The aqueous polymer solution contains less than 1,500 ppm residual dry methacrylic acid relative to the total amount of dry copolymer.

A copolymer (P6) comprising 7.44% by weight of methacrylic acid and 92.56% by weight of monomer (b12) is obtained. It has a molecular mass MW of 194,560 g / mol and a polymeric molecular index P _I of 1.6.

Example 1.7: Copolymer according to the invention (P7)

Water (380 g), iron sulfate heptahydrate (0.11 g) and a 20% by mass solution of DPTTC in water (3 g) are placed in a stirred reactor. The reactor is heated to 65 ± 2 ° C. Hydrogen peroxide in aqueous solution is added all at once at 35% by mass (20 g).

Then, for 2 hours, the following are simultaneously injected into the reactor:

-A mixture of water (40 g), methacrylic acid (29.73 g), and monomer (b12) having a molecular mass of 3,000 g / mol (370.03 g),

-20% by mass solution of DPTTC in water (12 g) with 50 g of water,

-Mixture of water (55 g) and sodium persulfate (8.46 g).

The reactor is maintained at a temperature of 65 ± 2 ° C. for 1 hour.

The product is cooled and then neutralized by adding an aqueous solution of sodium hydroxide at 50% by mass until pH 7.2 is reached.

The aqueous polymer solution contains less than 2 ppm residual dry methacrylic acid relative to the total amount of dry copolymer.

A copolymer (P7) comprising 7.44% by weight of methacrylic acid and 92.56% by weight of monomer (b12) is obtained. It has a molecular mass MW of 202,755 g / mol and a polymeric molecular index P _I of 1.6.

Example 1.8: Comparative copolymer

Water (400 g) is placed in a stirred reactor and heated to 65 ± 2 ° C.

Thereafter, for 3 hours, a mixture of water (40 g), acrylic acid (49.35 g) and monomer (b12) having a molecular mass of 3,000 g / mol (312.81 g), water (30 g), DMDO (1,8- A mixture of dimercapto-3,6-dioxaoctane) (1.80 g) and monomer (b12) having a molecular mass of 3,000 g / mol (50.00 g) was added with water (84.9 g) and ammonium persulfate (1.51 g). Infuse with the mixture at the same time. The reactor is maintained at a temperature of 65 ± 2 ° C. for 1 hour and 30 minutes.

The product is cooled and then partially neutralized by adding an aqueous solution of sodium hydroxide at 50% by mass (4.1 g). The aqueous polymer solution contains more than 4,930 ppm residual dry acrylic acid relative to the total amount of dry copolymer.

Example 2: Evaluation of water reduction properties in mortar

The composition of the mortar formulation shown in Table 1 was prepared according to the following procedure:

- Incorporating the mixture and the water into balls of an automatic Perrier mixer for standardized cement and mortar,

- Impregnating all fines (cement and / or hydraulic binder),

- Mixing at a slow speed of 140 rpm,

- Impregnating sand after 30 seconds,

- Mixing at a slow speed of 140 rpm for 60 seconds,

- Stopping for 30 seconds to clean the sides of the ball,

- Mixing at a slow speed of 140 rpm for 90 seconds.

Similarly, a comparative formulation (CF) of mortar containing no copolymer is prepared.

The water-reducing properties of the copolymers according to the invention are evaluated using a mortar formulation.

The workability of the mortar T0 formulated with the copolymer according to the invention was evaluated by measuring the slump flow according to the standard EN 12350-2 (Abrams mini-conical test) adapted to the mortar.

To perform the slump flow test, the cone filled with the formulated mortar is lifted vertically to the horizontal plate while rotating by 1/4 turn. The slump is measured with a ruler after 5 minutes along the two 90 ° diameters. The result of the slump test is an average of 2 values for ± 1 mm. The test is performed at 20 ° C. The dose in the mixture is determined so that a target slump of 220 mm ± 5 mm can be reached. Capacity is expressed as percent dry weight relative to the weight of the hydraulic binder or mixture of hydraulic binders. Table 1 shows the results.

The use of the copolymer according to the present invention makes it possible to reduce the amount of water in the hydraulic formulation by 25% while maintaining an initial slump level (workability) similar to that of the comparative formulation without the copolymer.

The copolymers according to the invention are thus qualified as highly water-reducing agents according to the French standard ADJUVANT NF EN 934-2. In fact, the copolymer according to the invention makes it possible to reduce the water in the mixed mortar by at least 12% compared to the comparative mortar.

The use of the copolymer according to the invention makes it possible to achieve similar results in mixed concrete by reducing the amount of water by at least 12% compared to the reference concrete not comprising the copolymer according to the invention.

Claims (18)

In the presence of:
(i) 0.05 to 5% by weight of at least one compound of formula (II) relative to the amount of monomer:

(II)
here:
-x independently represents H, Na or K,
-R independently represents a C1-C5 alkyl group; And
At least one selected from hydrogen peroxide, ammonium persulfate, alkali metal persulfate, mixtures thereof, or combinations thereof with alkali metal bisulfites or combinations thereof with ions selected from Fe ^II , Fe ^III , Cu ^I , Cu ^II Radical-generating compounds of,
An aqueous composition comprising at least one copolymer having a polymerizability index P _I of less than 3, obtained by at least one radical polymerization reaction of the following components in water and at a temperature ranging from 10 to 90 ° C.,
(a) at least one anionic monomer comprising at least one polymerizable olefinically unsaturated and at least one carboxylic acid group or a salt thereof, and
(b) at least one monomer of formula (I):

(I)
here:
-R ¹ and R ² are the same or different and independently represent H or CH ₃ ,
-L independently represents a group selected from (CH ₂ -CH ₂ O) _x , (CH ₂ CH (CH ₃ ) O) _y , (CH (CH ₃ ) CH ₂ O) _z and combinations thereof, and
-x, y and z are the same or different and independently represent an integer or decimal number included in the range 0 to 150, and the sum of x + y + z is included in the range 10 to 150. The composition of claim 1, wherein the composition comprises a small or very small amount of the homopolymer of the monomer (a), which is free of the homopolymer of the monomer (a) or reduced relative to the amount on a dry weight basis of the copolymer. The composition of any one of claims 1 and 2, wherein the polymerization reaction uses:
-1 to 25% by weight of monomer (a) and
-75 to 99% by weight of monomer (b). The composition of claim 1, wherein the copolymer comprises:
-1 to 25% by weight of monomer (a) and
-75 to 99% by weight of monomer (b). 5. The method according to claim 1, wherein the amount of the copolymer is less than 2,000 ppm by weight or less than 1,500 ppm by weight, preferably less than 1,000 ppm by weight or less than 500 ppm by weight, in particular relative to the amount by dry weight of the copolymer, in particular. A composition comprising less than 200 ppm by weight or less than 100 ppm by weight residual monomer (a). The composition according to any one of claims 1 to 5, wherein the monomer used is selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylic acid salt, methacrylic acid salt, itaconic acid salt, maleic acid salt and mixtures thereof. . The composition of claim 1, wherein x is strictly greater than y + z.  The composition according to any of the preceding claims, wherein the polymerization reaction is carried out at a temperature in the range of 30 to 85 ° C, preferably 40 to 75 ° or 50 to 70 ° C. The composition according to any one of claims 1 to 8, wherein the polymerization reaction also uses at least one other monomer selected from:
Another anionic monomer, preferably selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, salts thereof, and mixtures thereof;
Of non-ionic monomers comprising at least one polymerizable olefinically unsaturated, preferably at least one polymerizable ethylenically unsaturated and especially polymerizable vinyl group, more preferably of acids comprising at least one monocarboxylic acid group Non-ionic monomers selected from esters, especially esters of acids selected from acrylic acid, methacrylic acid, and mixtures thereof, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy Hydroxypropyl methacrylate, styrene, vinylcaprolactam, alkyl acrylates, especially C ₁ -C ₁₀ -alkyl acrylates, preferably C ₁ -C ₄ -alkyl acrylates, more preferably methyl acrylate, ethyl acrylic Acrylate, propyl acrylate, isobutyl acrylate, n-butyl acrylate, alkyl methacrylate, In particular C ₁ -C ₁₀ -alkyl methacrylate, preferably C ₁ -C ₄ -alkyl methacrylate, more preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate , n-butyl methacrylate, aryl acrylate, preferably phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, aryl methacrylate, preferably phenyl methacrylate, benzyl methacrylate, phenoxyethyl Methacrylate, compound of formula (III):
Q ^1- (L ¹ ) _m- (L ² ) _n -Q ²
(III)
here:
-Q ¹ represents a polymerizable acrylate group or a polymerizable methacrylate group,
-Q ² represents an H group or a CH ₃ group,
-L ¹ and L ² are the same or different and independently represent an ethylene-oxy group or a propylene-oxy group, and
-m and n are the same or different and at least one of them is non-zero and represents a number of 150 or less and its sum m + n is less than 150;
Another monomer of formula (I) different from compound (b), wherein:
-R ¹ and R ² are the same or different and independently represent H or CH ₃ ,
-L represents a group selected from (CH ₂ -CH ₂ O) _x ,
-x represents 1;
Another monomer of formula (I) different from compound (b), wherein:
-R ¹ and R ² are the same or different and independently represent H or CH ₃ ,
-L independently represents a group selected from (CH ₂ CH (CH ₃ ) O) _y , (CH (CH ₃ ) CH ₂ O) _z and combinations thereof,
-y + z represents 1 or 2; And
2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, salt of 2- (methacryloyloxy) ethanesulfonic acid, 2- (methacryloyloxy ) Salts of ethanesulphonic acid, sodium methallyl sulfonate, styrene sulfonate and mixtures thereof. In the presence of:
(i) 0.05 to 5% by weight of at least one compound of formula (II) relative to the amount of monomer:

(II)
here:
-x independently represents H, Na or K,
-R independently represents a C1-C5 alkyl group; And
(ii) hydrogen peroxide, ammonium persulfate, alkali metal persulfate, mixtures thereof or combinations thereof with alkali metal bisulfites or combinations thereof with ions selected from Fe ^II , Fe ^III , Cu ^I , Cu ^II At least one radical-generating compound,
A copolymer having a polymerization molecular weight index P _I less than 3, obtained by at least one radical polymerization reaction of the following components in water and at a temperature ranging from 10 to 90 ° C.,
(a) at least one anionic monomer comprising at least one polymerizable olefinically unsaturated and at least one carboxylic acid group or a salt thereof, and
(b) at least one monomer of formula (I):

(I)
here:
-R ¹ and R ² are the same or different and independently represent H or CH ₃ ,
-L independently represents a group selected from (CH ₂ -CH ₂ O) _x , (CH ₂ CH (CH ₃ ) O) _y , (CH (CH ₃ ) CH ₂ O) _z and combinations thereof, and
x, y and z are the same or different and independently represent an integer or decimal number included in the range 0 to 150, and the sum of x + y + z is included in the range 10 to 150. The copolymer of claim 11 comprising:
-1 to 25% by weight of monomer (a) and
-75 to 99% by weight of monomer (b). Formulations containing:
-At least one aqueous composition according to any one of claims 1 to 9 or at least one copolymer according to any one of claims 10 and 11;
-At least one hydraulic binder; Randomly
-Water; Randomly
-At least one aggregate; Randomly
-At least one mixture. The formulation of claim 12 comprising:
-0.01 to 5% by dry weight, respectively, at least one aqueous composition according to any one of claims 1 to 9 or at least one copolymer according to any one of claims 10 and 11 itself;
-95 to 99.9% by dry weight of at least one hydraulic binder. The method according to any one of claims 12 and 13, based on weight, based on the weight of the hydraulic binder, less than 0.7, less than 0.65 or less than 0.6, preferably less than 0.5 or less than 0.4, or less than 0.3 or less than 0.2, or A formulation comprising water in an amount ranging from 0.2 to 0.65 or 0.2 to 0.6 or 0.2 to 0.5 or 0.3 to 0.65 or 0.3 to 0.6 or 0.3 to 0.5.  A method for modifying the rheology of a hydraulic formulation, comprising the addition in the hydraulic formulation of at least one aqueous composition according to any one of claims 1 to 9 or at least one copolymer according to any one of claims 10 and 11. Way.  Controlling the operability of a hydraulic formulation, comprising the addition in the hydraulic formulation of at least one aqueous composition according to any one of claims 1 to 9 or at least one copolymer according to any one of claims 10 and 11. Way for. 17. The workability of claim 16, wherein the workability of the hydraulic formulation remains constant for at least 1 hour, preferably at least 2 hours, more preferably at least 3 hours, even more preferably at least 3.5 hours or at least 4 hours. Method to control it. Reducing the setting time of a hydraulic formulation, comprising the addition of at least one aqueous composition according to any one of claims 1 to 9 or at least one copolymer according to any one of claims 10 and 11 in a hydraulic formulation. Way for.