COPOLYMERS WITH GRADIENT STRUCTURE

Description

Technical area

[0001] The invention relates to a copolymer, in particular for use as a dispersant for solid particles, especially for use as a dispersant for mineral binder compositions, having a polymer backbone and bonded side chains comprising at least one ionizable monomer unit and at least one side-chain-bearing monomer unit. Furthermore, the invention relates to a process for producing a copolymer, the use of copolymers, a mineral binder composition, and molded articles containing copolymers formed therefrom. State of the art

[0002] Dispersants or superplasticizers are used in the construction industry as plasticizers or water-reducing agents for mineral binder compositions, such as concrete, mortar, cement, gypsum, and lime. Dispersants are generally organic polymers that are added to the mixing water or incorporated as solids into the binder compositions. This can advantageously modify both the consistency of the binder composition during processing and its cured properties. WO 2011015780 discloses the use of controlled-polymerization polymers as superplasticizers in hydraulically setting compositions.

[0003] Polycarboxylate-based comb polymers, for example, are known to be particularly effective dispersants. Such comb polymers have a polymer backbone and attached side chains. Such polymers are described, for example, in EP 1 138 697 A1 (Sika AG).

[0004] Also known as concrete admixtures are copolymer mixtures, such as those mentioned in EP 1 110 981 A2 (Kao). These copolymer mixtures are produced by reacting ethylenically unsaturated monomers in a free radical polymerization reaction, with the molar ratio of the two monomers being changed at least once during the polymerization process.

[0005] Although such comb polymers are very effective, they sometimes require relatively high dosages depending on the application, which is disadvantageous from an economic perspective. Depending on the binder composition, the comb polymers also lose their effectiveness after a short period of time.

[0006] These disadvantages of comb polymers can be at least partially compensated for by combining them with other additives. However, such solutions are usually complicated to use and expensive.

[0007] There is therefore still a need for improved dispersants that do not have the disadvantages mentioned. Description of the invention

[0008] The object of the invention is therefore to overcome the aforementioned disadvantages. In particular, an improved dispersant, especially for solid particles and especially for mineral binder compositions, is to be provided. The dispersant should, in particular, enable effective liquefaction and good processing of mineral binder compositions. In particular, the effect of the dispersant should be maintained for as long as possible. Furthermore, it is desirable that the dispersant can be produced as flexibly and controlled as possible.

[0009] Surprisingly, it has been found that this object can be achieved by the features of independent claim 1.

[0010] The core of the invention is therefore a copolymer, in particular for use as a dispersant for solid particles, in particular for use as a dispersant for mineral binder compositions, with a polymer backbone and side chains bound thereto, comprising at least one ionizable monomer unit M1 and at least one side-chain-bearing monomer unit M2, wherein the copolymer in at least one section in a direction along the polymer backbone with respect to the ionizable monomer unit M1 and / or with respect to the side chain-bearing monomer unit M2 has a gradient structure.

[0011] As has been shown, such copolymers, compared to known dispersants, provide very good plasticizing effects in mineral binder compositions, which are also maintained for a comparatively longer time. Compared to comparable polymers with a purely statistical (= random) distribution of the monomer units or with a purely block-wise arrangement of the monomer units, significantly better plasticizing performance can be observed in some cases. Furthermore, the copolymers according to the invention can be reliably produced in a wide variety of modifications using an efficient process. The copolymers according to the invention can therefore be produced very flexibly and in a controlled manner.

[0012] Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims. Ways to implement the invention

[0013] A first aspect of the present invention relates to a copolymer, in particular for use as a dispersant for solid particles, in particular for use as a dispersant for mineral binder compositions, having a polymer backbone and side chains attached thereto, comprising at least one ionizable monomer unit M1 and at least one side-chain-bearing monomer unit M2, wherein the copolymer in at least one section A in a direction along the polymer backbone with respect to the ionizable monomer unit M1 and / or with respect to the side chain-bearing monomer unit M2 has a gradient structure.

[0014] In other words, in the copolymer according to the invention, at least one section A in a direction along the polymer backbone with respect to the ionizable monomer unit M1and / or with respect to the side chain-bearing monomer unit M2 a concentration gradient exists.

[0015] The term "gradient structure" or "concentration gradient" refers in particular to a continuous change in the local concentration of a monomer unit in at least one section in one direction along the backbone of the copolymer. Another term for "concentration gradient" is "concentration gradient."

[0016] The concentration gradient can, for example, be essentially constant. This corresponds to a linear decrease or increase in the local concentration of the respective monomer unit in at least one section Aalong the direction of the backbone of the copolymer. However, it is possible that the concentration gradient changes along the direction of the backbone of the copolymer. In this case, there is a nonlinear decrease or increase in the local concentration of the respective monomer unit. The concentration gradient extends in particular over at least 10, in particular at least 14, preferably at least 20 or at least 40, monomer units of the copolymer.

[0017] In contrast, abrupt or sudden changes in the concentration of monomers, such as those that occur in block copolymers, are not referred to as concentration gradients.

[0018] In this context, the term "local concentration" refers to the concentration of a specific monomer at a given location on the polymer backbone. In practice, the local concentration or the average of the local concentration can be determined, for example, by determining the monomer conversion during copolymer production. This allows the monomers converted within a specific period of time to be determined. The average local concentration corresponds, in particular, to the ratio of the molar fraction of a specific monomer converted during the period under consideration to the total molar amount of monomers converted during the period under consideration.

[0019] The conversions of the monomers can be determined in a manner known per se, for example, using liquid chromatography, in particular high performance liquid chromatography (HPLC), and taking into account the amounts of monomers used.

[0020] In particular, it is also possible to analyze and determine the structure of the copolymers using nuclear magnetic resonance spectroscopy (NMR spectroscopy). In particular, 13< C NMR and 1< H NMR spectroscopy can be used to determine the sequence of monomer units in the copolymer in a conventional manner based on neighboring group effects and statistical analyses.

[0021] The copolymer may also have more than one section A with a gradient structure, in particular two, three, four or more sections A, which are arranged one after the other. If available, the different sections can A different gradient structures or concentration gradients are present.

[0022] The terms "ionizable monomers" and "ionizable monomer units" refer in particular to monomers or polymerized monomers that are present in anionic form or negatively charged at a pH value > 10, especially at a pH value > 12. These are, in particular, H-donor groups or acid groups. Particularly preferred ionizable groups are acid groups, such as carboxylic acid, sulfonic acid, phosphoric acid, and / or phosphonic acid groups. Carboxylic acid groups are preferred. The acid groups can also be present as anions in deprotonated form or as a salt with a counterion or cation.

[0023] Preferably, in the at least one section A a local concentration of the at least one ionizable monomer unit M1 along the polymer backbone continuously increases, while a local concentration of the at least one side chain-bearing monomer unit M2continuously decreases along the polymer backbone, or vice versa.

[0024] A local concentration of the ionizable monomer unit M1 at the first end of at least one section A is particularly lower than at the second end of the section A, while a local concentration of the side chain-bearing monomer unit M2 at the first end of the section A is larger than at the second end of the section A, or vice versa.

[0025] In particular, if at least one section is divided A into 10 equally long subsections, the average local concentration of the at least one ionizable monomer unit M1in the respective subsections along the polymer backbone in at least 3, in particular in at least 5 or 8, consecutive subsections, while the average local concentration of the at least one side-chain-bearing monomer unit M2 in the respective subsections along the polymer backbone in at least 3, in particular in at least 5 or 8, consecutive subsections, or vice versa.

[0026] In particular, an increase or decrease in the average local concentration of the at least one ionizable monomer unit M1 in the successive subsections is substantially constant, while advantageously a decrease or increase in the average local concentration of the at least one side-chain-bearing monomer unit M2is also essentially constant in the successive subsections. A weight-average molecular weight MW of the entire copolymer is in particular in the range of 10,000–150,000 g / mol, advantageously 12,000–80,000 g / mol, especially 12,000–50,000 g / mol. In the present context, molecular weights, such as the weight-average molecular weight MW or the number-average molecular weight Mn, are determined by gel permeation chromatography (GPC) using polyethylene glycol (PEG) as a standard. This technique is known per se to the person skilled in the art.

[0027] According to a preferred embodiment, the polydispersity (= weight-average molecular weight MW / number-average molecular weight M n ) of the copolymer is < 1.5. In particular, the polydispersity is in the range of 1.0 - 1.4, especially 1.1 - 1.3.

[0028] The

[0029] At least one section A,based on a total number of monomer units in the polymer backbone, has a proportion of

[0030] at least 30%, in particular at least 50%, preferably at least 75% or 90%, of monomer units.

[0031] In particular, at least one section A, based on the weight-average molecular weight of the total copolymer, over a weight fraction of at least 30%, in particular at least 50%, preferably at least 75% or 90%.

[0032] This brings us to the section A with the concentration gradient or the gradient structure in particular.

[0033] At least one section A with the concentration gradient advantageously comprises at least 5, in particular at least 7, preferably at least 10 monomer units M1 and / or at least 5, in particular at least 7, preferably at least 10, monomer units M2.

[0034] At least one section A with the concentration gradient advantageously comprises at least 5, in particular at least 7, preferably at least 10 monomer units M1 and at least 5, in particular at least 7, preferably at least 10, monomer units M2. At least one section A with the concentration gradient advantageously comprises 5 - 70, in particular 7 - 40, preferably 10 - 25 monomer units M1 and 5 - 70, in particular 7 - 40, preferably 10 - 25, monomer units M2.

[0035] In particular, the copolymer consists of at least 50 mol%, in particular at least 75 mol%, especially at least 90 mol% or 95 mol%, of ionizable monomer units M1 and side chain-bearing monomer units M2.

[0036] It is advantageous if at least 30 mol%, in particular at least 50 mol%, preferably at least 75 mol%, in particular at least 90 mol% or at least 95 mol%, of the ionizable monomer units M1 in at least one section A, which has a gradient structure.

[0037] Likewise advantageously, at least 30 mol%, in particular at least 50 mol%, preferably at least 75 mol%, in particular at least 90 mol% or at least 95 mol%, of the side-chain-bearing monomer units M2 in at least one section which has a gradient structure.

[0038] It is especially preferable for the last two conditions mentioned above to apply simultaneously.

[0039] In another advantageous embodiment, the copolymer has, in addition to the at least one section A, which has a gradient structure, over a further section B,where over the entire section B there is essentially a constant local concentration of the monomers and / or a statistical or random distribution of the monomers. Section B can consist of monomers of a single type or of several different monomers that are statistically distributed. In the section B However, in particular, there is no gradient structure or concentration gradient along the polymer backbone.

[0040] The copolymer may also have more than one further section B e.g. two, three, four or more sections B, which may differ chemically and / or structurally.

[0041] Preferably, the at least one section A directly to the next section B to.

[0042] Surprisingly, it has been found that such copolymers may be even more advantageous with regard to the liquefaction effect and the maintenance of this effect over time.

[0043] In particular, the further section B ionizable monomer units M1 and / or side chain-bearing monomer units M2.

[0044] In relation to all monomer units contained therein, the further section B in one embodiment of the invention, for example, advantageously at least 30 mol%, in particular at least 50 mol%, preferably at least 75 mol%, in particular at least 90 mol% or at least 95 mol%, ionizable monomer units M1. Any portion of side chain-bearing monomer units M2 in the further section Bis in particular less than 25 mol%, especially less than 10 mol% or less than 5 mol%, based on all monomer units M1 in the following section. In particular, the following section B no side chain-bearing monomer units M2 before.

[0045] According to a further and particularly advantageous implementation of the invention, the further section comprises B, based on all monomer units contained therein, at least 30 mol%, in particular at least 50 mol%, preferably at least 75 mol%, in particular at least 90 mol% or at least 95 mol%, of side-chain-bearing monomer units M2. In this case, any portion of ionizable monomer units M1 in the further section B in particular less than 25 mol%, in particular less than 10 mol% or less than 5 mol%, based on all monomer units M2in the further section B. In particular, there are no ionizable monomer units in the further section B M1 before.

[0046] It has proved useful that the further section B a total of 5 - 70, in particular 7 - 40, preferably 10 - 25 monomer units. These are in particular monomer units M1 and / or M2, Side chain-bearing monomer units M2.

[0047] A ratio of the number of monomer units in at least one section A with gradient structure to the number of monomer units in at least one further section B with the essentially constant local concentration is advantageously in the range of 99:1 - 1:99, in particular 10:90 - 90:10, preferably 80:20 - 20:80, especially 70:30 - 30:70.

[0048] The side chain-bearing monomer unit M2contains in particular polyalkyne oxide side chains, in particular polyethylene oxide and / or polypropylene oxide side chains.

[0049] The ionizable monomer unit M1 preferably comprises acid groups, in particular carboxylic acid, sulfonic acid, phosphoric acid and / or phosphonic acid groups.

[0050] The ionizable monomer unit M1 has a structure of the formula I,

[0051] The side chain-bearing monomer unit M2 contains a structure of the formula II where R 1< , each independently of one another, represents -COOM, -SO 2 -OM, -O-PO(OM) 2 and / or -PO(OM) 2 , R 2< , R 3< , R 5< and R 6< , each independently of one another, represent H or an alkyl group having 1 to 5 carbon atoms, R 4< and R 7< , each independently of one another, represent H, -COOM or an alkyl group having 1 to 5 carbon atoms, or wherein R 1< forms a ring with R 4< to form -CO-O-CO-, M, independently of one another, represents H +< , an alkali metal ion, an alkaline earth metal ion, a divalent or trivalent metal ion, an ammonium ion or an organic ammonium group; m = 0, 1 or 2, p = 0 or 1, X, each independently of one another, represents -O- or -NH-, R 8< represents a group of the formula -[AO] n -R a<, where A = C 2 - to C 4 -alkylene, R a< represents H, a C 1 - to C 20 -alkyl group, -cycloalkyl group or -alkylaryl group, and n = 2 - 250, in particular 10 - 200.

[0052] It is advantageous to have a molar ratio of the ionizable monomer units M1 to the side chain-bearing monomer units M2 in the copolymer in the range of 0.5 - 6, in particular 0.7 - 4, preferably 0.9 - 3.8, more preferably 1.0 - 3.7 or 2 - 3.5. This achieves an optimal dispersing effect in mineral binder compositions.

[0053] In particular, R 1< = COOM, R 2< = H or CH 3 , and R 3< = R 4< = H. This allows the copolymer to be produced based on acrylic or methacrylic acid monomers, which is economically advantageous. Furthermore, such copolymers exhibit particularly good dispersing properties in this context.

[0054] Copolymers with R 1< = COOM, R 2< = H, R 3< = H, and R 4< = COOM may also be advantageous. Such copolymers can be prepared based on maleic acid monomers.

[0055] The group X in the ionizable monomer unitM2 is advantageously at least 75 mol%, in particular at least 90 mol%, especially at least 95 mol% or at least 99 mol% of all monomer units M2 for -O- (= oxygen atom).

[0056] Advantageously, R 5< = H or CH 3 , R 6< = R 1< = H and X = -O-. Such copolymers can be prepared, for example, starting from (meth)acrylic acid esters, vinyl, (meth)allyl, or isoprenol ethers.

[0057] In a particularly advantageous embodiment, R 2< and R 5< each represent mixtures of 40 - 60 mol% H and 40 - 60 mol% -CH 3 .

[0058] According to a further advantageous embodiment, R 1< = COOM, R 2< = H, R 5< = -CH 3 and R 3< = R 4< = R 6< = R 7< = H.

[0059] In another advantageous embodiment, R 1< = COOM, R 2< = R 5< = H or -CH 3 and R 3< = R 4< = R 6< = R 7< = H.

[0060] Particularly advantageous are copolymers in which: R 1< = COOM; R 2< and R 5< each independently represent H, -CH 3 or mixtures thereof; R 3< and R 6< each independently represent H or -CH 3, preferably H; R 4< and R 7< each independently represent H or -COOM, preferably H.

[0061] The residue R 8< in the side chain-bearing monomer unit M2 consists, based on all R 8< radicals in the copolymer, in particular at least 50 mol%, in particular at least 75 mol%, preferably at least 95 mol% or at least 99 mol%, of a polyethylene oxide. The proportion of ethylene oxide units based on all alkylene oxide units in the copolymer is in particular more than 75 mol%, in particular more than 90 mol%, preferably more than 95 mol%, and especially 100 mol%.

[0062] In particular, R 8< has essentially no hydrophobic groups, in particular no alkylene oxides having three or more carbon atoms. This means, in particular, that the proportion of alkylene oxides having three or more carbon atoms, based on all alkylene oxides, is less than 5 mol%, in particular less than 2 mol%, preferably less than 1 mol% or less than 0.1 mol%. In particular, no alkylene oxides having three or more carbon atoms are present, or their proportion is 0 mol%.

[0063] R a< advantageously represents H and / or a methyl group. Particularly advantageous is A = C 2 -alkylene and R a< represents H or a methyl group.

[0064] In particular, the parameter n = 10 - 150, in particular n = 15 - 100, preferably n = 17 - 70, especially n = 19 - 45 or n = 20 - 25. In particular in the preferred ranges mentioned, excellent dispersing effects are achieved.

[0065] Furthermore, it may be advantageous if the copolymer contains at least one further monomer unit MS which differs in particular from the monomer units M1 and M2 chemically different. In particular, several different additional monomer units MS This allows the properties of the copolymer to be further modified and, for example, adapted for specific applications.

[0066] Particularly advantageous is the at least one further monomer unit MS a monomer unit of formula III: where R 5'< , R 6'< , 7'< , m' and p' are defined as R 5< , R 6< , R 7< , m and p; Y, each independently of one another, stands for a chemical bond or -O-; Z, each independently of one another, stands for a chemical bond, -O- or -NH-; R 9< , each independently of one another, stands for an alkyl group, cycloalkyl group, alkylaryl group, aryl group, hydroxyalkyl group or an acetoxyalkyl group, each having 1 - 20 C atoms.

[0067] For example, additional monomer units are advantageous MS where m' = 0, p' = 0, Z and Y represent a chemical bond and R 9< stands for an alkylaryl group with 6 - 10 C atoms.

[0068] Also suitable are particularly further monomer units MS where m' = 0, p' = 1, Y stands for -O-, Z represents a chemical bond and R 9< stands for an alkyl group with 1 - 4 C atoms.

[0069] Further monomer units are MSsuitable where m' = 0, p' = 1, Y stands for a chemical bond, Z stands for -O- and R 9< represents an alkyl group and / or a hydroxyalkyl group with 1 - 6 C atoms.

[0070] Particularly advantageously, the at least one further monomer unit MS from polymerized vinyl acetate, styrene and / or hydroxyalkyl (meth)acrylate, in particular hydroxyethyl acrylate.

[0071] The at least one further monomer unit MS may be part of at least one section A and / or the further section B It is also possible that the at least one further monomer unit MS is part of an additional section of the copolymer. In particular, different additional monomer units can be present in the different sections MS present.

[0072] If at least one section Apresent, the at least one further monomer unit MS in at least one section A advantageously a proportion of 0.001 - 80 mol%, preferably 20 - 75 mol%, especially 30 - 70 mol%, based on all monomer units in the first section A, on.

[0073] If in the following section B present, the at least one further monomer unit MS in the further section B in particular a proportion of 0.001 - 80 mol%, preferably 20 - 75 mol%, especially 30 - 70 mol% or 50 - 70 mol%, based on all monomer units in the further section B, on.

[0074] According to an advantageous embodiment, in at least one section A and / or in the further section B which has at least one further monomer unit MSwith a proportion of 20 - 75 mol-%, especially 30 - 70 mol-%, based on all monomer units in the respective section.

[0075] According to an advantageous embodiment, the copolymer consists of at least one section A. In another advantageous embodiment, the copolymer consists of at least one section A and the further section B. Especially in the latter case, very good and long-lasting liquefaction effects result.

[0076] However, it is also possible, for example, that the copolymer has at least two different sections A and / or at least two different further sections B contains.

[0077] A particularly advantageous copolymer has at least one or more of the following features: (i) The copolymer consists of at least 75 mol%, especially at least 90 mol% or 95 mol%, of ionizable monomer units M1 and side chain-bearing monomer units M2; (ii) The copolymer comprises or consists of at least one section A and another section B; (iii) The further section B comprises side chain-bearing monomer units M2, in particular at least 50 mol%, preferably at least 75 mol%, in particular at least 90 mol% or at least 95 mol%, based on all in section B contained monomer units. Any portion of ionizable monomer units M1 in the further section B is less than 25 mol%, in particular less than 10 mol% or less than 5 mol%, based on all monomer units M2 in the further section B. (iv) A molar ratio of the monomer units M1 to the monomer unitsM2 in the copolymer is in the range of 0.5 - 6, preferably 0.8 - 3.5; (v) R 1< stands for COOM; (vi) R 2< and R 5< stand for H or CH 3 , preferably CH 3 ; (vii) R 3< = R 4< = R 6< = R 7< = H; (viii) m = 0 and p = 1; (ix) X = -O- (x) A = C 2 -alkylene and n = 10 - 150, preferably 15 - 50; (xi) Ra< = H or -CH 3 , preferably CH 3 ;

[0078] Especially preferred is a copolymer consisting of the sections A and B, which has at least all features (i) - (iv). Further preferred is a copolymer which has all features (i) - (xi). Even more preferred is a copolymer which realizes all features (i) - (xi) in the respectively preferred embodiments.

[0079] A copolymer is, in particular, a polymer with an essentially linear structure. This means, in particular, that all monomer units of the copolymer are arranged in a single and / or unbranched polymer chain. Specifically, the copolymer does not have a star-shaped structure and / or the copolymer is not part of a branched polymer. In particular, the copolymer is not part of a polymer in which several, in particular three or more, polymer chains extending in different directions are attached to a central molecule.

[0080] The copolymer can be in liquid or solid form. The copolymer is particularly preferably present as a component of a solution or dispersion, with the copolymer content being in particular 10-90 wt.%, preferably 25-65 wt.%. This makes the copolymer very suitable for addition to binder compositions, for example.

[0081] According to another advantageous embodiment, the copolymer is in the solid state, particularly in the form of a powder, pellets, and / or plates. This particularly simplifies the transport of the copolymers. Solutions or dispersions of the copolymers can be converted into the solid state, for example, by spray drying.

[0082] A further aspect of the present invention relates to a process for producing a copolymer, in particular a copolymer as described above, wherein ionizable monomers m1 and side-chain-bearing monomers m2 polymerized together to form a concentration gradient and / or a gradient structure.

[0083] The ionizable monomers m1 After polymerization, they correspond to the above-mentioned ionizable monomer units M1of the copolymer. Likewise, the side chain-bearing monomers m2 after polymerization, the side chain-bearing monomer units described above M2.

[0084] In particular, during polymerization a molar ratio of free ionizable monomers m1 to free side-chain-bearing monomers m2 at least temporarily. Specifically, the change in the molar ratio involves a continuous change. This allows a concentration gradient or gradient structure to be formed in a well-controllable manner.

[0085] Optionally, a stepwise change of the molar ratio of the free ionizable monomers is carried out m1 to the free side chain-bearing monomers m2. This is especially important before the continuous change is carried out. This allows, for example, a copolymer with a further section Bavailable.

[0086] According to a preferred embodiment, in a first step a) a portion of the ionizable monomers m1 essentially in the absence of side chain-bearing monomers m2 reacted or polymerized and after reaching a predetermined conversion in a second step b) the not yet reacted ionizable monomers m1 together with the side chain-bearing monomers m2 polymerized. This allows a copolymer with a further section B, which consists essentially of polymerized ionizable monomers m1 exists, can be produced.

[0087] Also advantageously, in a first step a) a part of the side chain-bearing monomers m2 essentially in the absence of ionizable monomers m1reacted or polymerized and after reaching a predetermined conversion in a second step b) the unreacted side chain-bearing monomers m2 together with the ionizable monomers m1 This variant is particularly preferred. It allows a copolymer with a further section to be produced in a simple and cost-effective manner. B, which consists essentially of polymerized side chain-bearing monomers m2 exists, available.

[0088] It is advantageous to carry out steps a) and b) immediately one after the other. This allows the polymerization reaction in steps a) and b) to be maintained as best as possible.

[0089] The polymerization in step a) is carried out in particular until 0.1 - 85 mol%, in particular 1 - 74 mol%, preferably 10 - 70 mol%, in particular 25 - 70 mol%, especially 28 - 50 mol% or 30 - 50 mol% of the ionizable monomers m1 or the side chain-bearing monomers m2 reacted or polymerized. A conversion of 40 - 45 mol% is particularly advantageous.

[0090] The conversion of the monomers m1 and m2 or the progress of the polymerization can be monitored in a manner known per se, for example by means of liquid chromatography, in particular high performance liquid chromatography (HPLC).

[0091] In particular, the ionizable monomers m1 a structure according to formula IV: and the side chain-bearing monomers m2 have a structure according to formula V: where R 1< , R 2< , R 3< , R 4< , R 5< , R 6< , R 7< , R 8< , m, p and X are as defined above.

[0092] According to a further advantageous embodiment, during the polymerization or during step a) and / or during step b) at least one further polymerizable monomer ms which is in particular a monomer of formula VI: where R 5'< , R 6'< , R 7'< , R 9< , m', p', Y and Z are as defined above.

[0093] The further monomer ms After polymerization, corresponds to the further monomer unit described above MS.

[0094] It is particularly advantageous that at least one further monomer ms selected from vinyl acetate, styrene, N-vinylpyrrolidone and / or hydroxyalkyl (meth)acrylate, in particular hydroxyethyl acrylate.

[0095] The process can be carried out, for example, by reacting monomers in step a)m2 in a solvent, e.g. water, and then to another section B polymerized. As soon as the desired conversion of monomer m2 is reached (e.g. 30 - 45 mol-%; see above), monomers are added without delay in step b) m1 added and the polymerization continues. The monomers m1 and the unreacted monomers m2 attached to the already formed section B, creating a section A with a gradient structure. The polymerization is advantageously continued until the desired conversion of monomer m1 (e.g. 75 - 95 mol-%, especially 80 - 92 mol-%; see above) is reached. This results, for example, in a copolymer comprising a section A and a related further section B receive.

[0096] According to a further advantageous embodiment, in step a) and / or in step b) at least one further polymerizable monomer as described above ms The at least one further polymerizable monomer ms In this case, it is used in particular together with the monomer m1 and / or the monomer m2 polymerized.

[0097] However, it is also possible, in addition to step a) and step b), to carry out a further step c) of polymerising the at least one further polymerisable monomer ms This allows a copolymer to be provided with an additional section C In particular, step c) can be carried out between steps a) and b). This way, the additional section C spatially between the sections A and B arranged.

[0098] However, it is also possible to perform step c) before or after steps a) and b). This allows the additional section C according to section A or before section B be arranged.

[0099] The polymerization is advantageously carried out by controlled free radical polymerization and / or by living free radical polymerization. Reversible addition-fragmentation chain transfer polymerization (RAFT) is particularly preferred. Radical polymerization can basically be divided into three steps: initiation, growth, and termination.

[0100] "Living free radical polymerization" is also referred to as "controlled free radical polymerization" and is known per se to those skilled in the art in other contexts. The term refers to chain growth processes in which essentially no chain termination reactions (transfer and termination) occur. Living free radical polymerization thus essentially occurs in the absence of irreversible transfer or termination reactions. These criteria can be met, for example, if the polymerization initiator is consumed very early during polymerization and an exchange between the various reactive species occurs that occurs at least as rapidly as the chain propagation itself. In particular, the number of active chain ends remains essentially constant during polymerization.This allows for essentially simultaneous and sustained chain growth throughout the entire polymerization process. This results in a narrow molecular weight distribution, or polydispersity.

[0101] In other words, controlled radical polymerization, or living radical polymerization, is characterized by reversible or even nonexistent termination or transfer reactions. After initiation, the active centers remain intact throughout the reaction. All polymer chains are formed (initiated) simultaneously and grow continuously throughout the reaction. Ideally, the radical functionality of the active center is retained even after complete conversion of the monomers to be polymerized. This special property of controlled polymerizations makes it possible to produce well-defined structures such as gradient or block copolymers by sequentially adding different monomers.

[0102] In contrast, in conventional free radical polymerization, as described, for example, in EP 1 110 981 A2 (Kao), all three steps (initiation, growth, and termination) occur in parallel. The lifetime of the active, growing chains is very short, and the monomer concentration remains essentially constant during chain growth. The polymer chains formed in this way do not have any active centers suitable for the addition of further monomers. This mechanism therefore does not allow any control over the structure of the polymers. The preparation of gradient or block structures by means of conventional free radical polymerization is therefore usually not possible (see, for example,"Polymers: Synthesis, Synthesis and Properties"; Authors: Koltzenburg, Maskos, Nuyken; Publisher: Springer Spektrum; ISBN: 97-3-642-34772-6 and "Fundamentals of Controlled / Living Radical Polymerization"; Publisher: Royal Society of Chemistry; Editors: Tsarevsky, Sumerlin; ISBN: 978-1-84973-425-7).

[0103] Thus, "living free radical polymerization" is clearly different from conventional "free radical polymerization" or non-living or non-controlled free polymerization.

[0104] In reversible addition-fragmentation chain transfer polymerization (RAFT), polymerization control is achieved through a reversible chain transfer reaction. Specifically, a growing radical chain adds a so-called RAFT agent, leading to the formation of an intermediate radical. The RAFT agent then fragments, forming a new RAFT agent and a radical available for propagation. In this way, the propagation probability is evenly distributed across all chains. The average chain length of the formed polymer is proportional to the RAFT agent concentration and the reaction conversion. Organic sulfur compounds are particularly used as RAFT agents. Dithioesters, dithiocarbamates, trithiocarbonates, and / or xanthates are particularly suitable. Polymerization can be initiated conventionally using initiators or by thermal self-initiation.

[0105] Preferably, the polymerization or steps a) and / or b) take place in an aqueous solution. In particular, the polymerizations in both steps a) and b) take place in aqueous solutions. This also applies to step c), if it is carried out. This has been shown to have a positive effect on the dispersing effect of the copolymer.

[0106] However, it is also possible to use other solvents, such as ethanol.

[0107] A radical initiator, preferably an azo compound and / or a peroxide, is used as the initiator for the polymerization. Suitable peroxides are selected, for example, from the group consisting of dibenzoyl peroxide (DBPO), di-tert-butyl peroxide, and diacetyl peroxide.

[0108] An azo compound such as azobisisobutyronitrile (AIBN) is particularly advantageous as an initiator. α,α'Azodiisobutyramidine dihydrochloride (AAPH) or azobisisobutyramidine (AIBA). Other radical initiators, such as sodium persulfate or di-tert-butylhyponitrite, may also be used under certain circumstances.

[0109] If the polymerization takes place in an aqueous solution or in water, it is advantageous α,α' -Azodiisobutyramidine dihydrochloride (AAPH) is used as initiator.

[0110] Preferably, one or more representatives from the group consisting of dithioesters, dithiocarbamates, trithiocarbonates, and xanthates are present during the polymerization or in steps a) and / or b). These are so-called "RAFT agents," which make it possible to control the polymerization process. This also applies accordingly to step c), if it is carried out.

[0111] In particular, the polymerization or step a), step b) and / or step c) takes place at a temperature in the range of 50 - 95°C, in particular 70 - 90°C.

[0112] It is advantageous to work under an inert gas atmosphere, e.g. under a nitrogen atmosphere.

[0113] A further aspect of the present invention includes a copolymer obtainable by the process described above.

[0114] Furthermore, the present invention relates to the use of a copolymer as described above as a dispersant for solid particles.

[0115] The term "solid particles" refers to particles made of inorganic and / or organic materials. In particular, these are inorganic and / or mineral particles.

[0116] The copolymer is particularly advantageously used as a dispersant for mineral binder compositions. The copolymer can be used in particular for liquefaction, water reduction, and / or to improve the processability of a mineral binder composition.

[0117] In particular, the copolymer can be used to extend the processability of a mineral binder composition.

[0118] Furthermore, the present invention also relates to a mineral binder composition containing at least one copolymer as described above.

[0119] The mineral binder composition contains at least one mineral binder. The term "mineral binder" refers, in particular, to a binder that reacts in the presence of water in a hydration reaction to form solid hydrates or hydrate phases. This can be, for example, a hydraulic binder (e.g., cement or hydraulic lime), a latently hydraulic binder (e.g., slag), a pozzolanic binder (e.g., fly ash), or a non-hydraulic binder (gypsum or white lime).

[0120] In particular, the mineral binder or binder composition contains a hydraulic binder, preferably cement. Particular preference is given to a cement with a cement clinker content of ≥ 35 wt.%. In particular, the cement is of the CEM I, CEM II, CEM III, CEM IV, or CEM V type (according to standard EN 197-1). The proportion of the hydraulic binder in the total mineral binder is advantageously at least 5 wt.%, in particular at least 20 wt.%, preferably at least 35 wt.%, especially at least 65 wt.%. According to a further advantageous embodiment, the mineral binder consists of ≥ 95 wt.% hydraulic binder, in particular cement or cement clinker.

[0121] However, it can also be advantageous if the mineral binder or the mineral binder composition contains or consists of other binders. These are, in particular, latent hydraulic binders and / or pozzolanic binders. Suitable latent hydraulic and / or pozzolanic binders are, for example, slag, fly ash and / or silica fume. The binder composition can also contain inert substances such as limestone, quartz flour and / or pigments. In an advantageous embodiment, the mineral binder contains 5-95 wt.%, in particular 5-65 wt.%, particularly preferably 15-35 wt.%, of latent hydraulic and / or pozzolanic binders. Advantageous latent hydraulic and / or pozzolanic binders are slag and / or fly ash.

[0122] In a particularly preferred embodiment, the mineral binder contains a hydraulic binder, in particular cement or cement clinker, and a latent hydraulic and / or pozzolanic binder, preferably slag and / or fly ash. The proportion of the latent hydraulic and / or pozzolanic binder is particularly preferably 5-65 wt.%, particularly preferably 15-35 wt.%, while at least 35 wt.%, especially at least 65 wt.%, of the hydraulic binder is present.

[0123] The mineral binder composition is preferably a mortar or concrete composition.

[0124] The mineral binder composition is in particular a processable and / or water-mixed mineral binder composition.

[0125] A weight ratio of water to binder in the mineral binder composition is preferably in the range of 0.25 - 0.7, in particular 0.26 - 0.65, preferably 0.27 - 0.60, especially 0.28 - 0.55.

[0126] The copolymer is advantageously used in a proportion of 0.01–10 wt.%, particularly 0.1–7 wt.% or 0.2–5 wt.%, based on the binder content. The proportion of the copolymer refers to the copolymer itself. For a copolymer in solution form, the solids content is decisive.

[0127] An additional aspect of the present invention relates to a shaped body, in particular a component of a structure, obtainable by curing a mineral binder composition as described above containing a copolymer after the addition of water. A structure can be, for example, a bridge, a building, a tunnel, a roadway, or a runway.

[0128] Further advantageous embodiments of the invention emerge from the following exemplary embodiments. Short description of the drawing

[0129] The figures used to explain the embodiments show: Fig.1: The time course of the monomer conversions in the preparation of a copolymer according to the invention ( P1 ); Fig. 2: A schematic representation of a possible structure of a copolymer, which results from the conversions according to Fig. 1 can be derived. Examples of implementation 1. Production examples for polymers 1.1 Reference polymer R1 (Comparison example, block copolymer)

[0130] To prepare a block copolymer using RAFT polymerization, 57.4 g of 50% methoxypolyethylene glycol 1000 methacrylate (0.03 mol) and 22 g of deionized water are placed in a round-bottom flask equipped with a reflux condenser, stirrer, thermometer, and a gas inlet tube. The reaction mixture is heated to 80°C with vigorous stirring. A gentle stream of N2 inert gas is passed through the solution during the warm-up and the entire remaining reaction time. 378 mg of 4-cyano-4-(thiobenzoyl)pentanoic acid (1.35 mmol) are then added to the mixture. Once the substance has completely dissolved, 67 mg of AIBN (0.41 mmol) are added. From then on, the conversion is regularly determined by HPLC.

[0131] Once the conversion, based on methoxypolyethylene glycol methacrylate, reaches 90 mol%, 4.66 g of methacrylic acid (0.05 mol) are added. The mixture is allowed to react for another 4 hours and then allowed to cool. A clear, reddish, aqueous solution with a solids content of approximately 40% remains.

[0132] The copolymer thus obtained is used as a reference polymer R1 and, due to the almost complete conversion of the methoxy-polyethylene glycol methacrylate (90 mol%), has a block structure in which the side chain-bearing monomer units (methoxy-polyethylene glycol methacrylate) are present in a first block and the ionizable monomer units (methacrylic acid) are essentially spatially separated in a second block. 1.2 Reference polymer R2 (Comparative example, statistical polymer)

[0133] 1.4 g of sodium hypophosphite and 36 g of deionized water are placed in a reaction vessel. The reaction solution is heated to 80°C. A mixture of 108.3 g of 50% methoxypolyethylene glycol 1000 methacrylate, 8.6 g of methacrylic acid, and 20 g of water is added dropwise to this solution over 120 minutes. Simultaneously, a solution of 0.89 g of sodium persulfate and 20 g of water is added dropwise over 130 minutes. After the reaction, the solution is cooled. A slightly yellowish, slightly viscous polymer remains.

[0134] The copolymer thus obtained is used as a reference polymer R2 and has a statistical or random distribution of the monomer units (methoxy-polyethylene glycol methacrylate units and methacrylic acid units). 1.3 Copolymer P1

[0135] To prepare the gradient polymer using RAFT polymerization, 57.4 g of 50% methoxypolyethylene glycol 1000 methacrylate (0.03 mol) and 22 g of deionized water are placed in a round-bottom flask equipped with a reflux condenser, stirrer, thermometer, and a gas inlet tube. The reaction mixture is heated to 80°C with vigorous stirring. A gentle stream of inert N2 gas is passed through the solution during the warm-up and the entire remaining reaction time. 378 mg of 4-cyano-4-(thiobenzoyl)pentanoic acid (1.35 mmol) are then added to the mixture. Once the substance has completely dissolved, 67 mg of AIBN (0.41 mmol) are added. From then on, the conversion is regularly determined by HPLC.

[0136] As soon as the reaction, based on methoxy-polyethylene glycol methacrylate, reaches 65 mol%, 4.66 g of methacrylic acid (0.05 mol) dissolved in 20 g of H 2 O are added dropwise within 20 min. After completion, the mixture is allowed to react for a further 4 h and then allowed to cool. A clear, slightly reddish, aqueous solution with a solids content of approximately 35% remains. The resulting copolymer with a gradient structure is referred to as a copolymer. P1 designated.

[0137] In Fig. 1 is the time course of the monomer conversions during the production of the copolymer P1 The monomer conversions were determined at the Fig. 1The indicated times during the preparation of the copolymer were determined by high performance liquid chromatography (HPLC) in a conventional manner. The upper dotted curve, which begins at the origin at time t = 0 minutes, represents the percentage conversion of the methoxy-polyethylene glycol methacrylate monomers (= side chain-bearing monomers m2 ) (scale on the right). The lower dotted curve, which starts at time t = 25 minutes, represents the percentage conversion of the methacrylic acid monomers (= ionizable monomers m1 ) (scale on the right). The solid line with the diamond-shaped dots indicates the number of side-chain-bearing monomers m2 which have been polymerized since the previous measurement point (= n( M2 ); left scale). Accordingly, the solid line with the triangular dots represents the number of ionizable monomers m1 which have been polymerized since the previous measurement point (= n(M1 ); left scale).

[0138] Calculating from the information in Fig. 1 for the period from 0 to 55 minutes at the respective time the ratio n( M2 ) / [n( M1 ) + n( M2 )] and n( M1 ) / [n( M1 ) + n( M2 )], the following values ​​result: Table 1: Monomer ratios during copolymer preparation P1 . time n( M2 ) / [n( M1 ) + n( M2 )] n( M1 ) / [n( M1 ) + n( M2 )] 15 100% 0% 25 100% 0% 30 33% 67% 35 29% 71% 40 25% 75% 45 17% 83% 55 10% 90%

[0139] From Table 1 it can be seen that in the preparation of the copolymer P1 during the first 25 minutes a section consisting of 100% side chain-bearing monomer units M2 is formed and then a section in which the proportion of side chain-bearing monomer units M2 continuously decreases, while the proportion of ionizable monomer units M1 continuously increases.

[0140] In Fig. 2 is also a possible structure of the copolymer P1 This can be seen directly from the Fig. 1 mentioned conversions. The side chain-bearing monomer units M2 (= polymerized methoxy-polyethylene glycol methacrylate monomers) are represented as a circle with a twisted extension. The ionizable monomer units M1 are represented as dumbbell-shaped symbols.

[0141] Out of Fig. 2 it is evident that copolymer P1 a first section A with gradient structure and another section B, consisting essentially of side chain-bearing monomer units. 1.4 Copolymer P2

[0142] To prepare the gradient polymer using RAFT polymerization, 57.4 g of 50% methoxypolyethylene glycol 1000 methacrylate (0.03 mol) and 22 g of deionized water are placed in a round-bottom flask equipped with a reflux condenser, stirrer, thermometer, and a gas inlet tube. The reaction mixture is heated to 80°C with vigorous stirring. A gentle stream of inert N2 gas is passed through the solution during the warm-up and the entire remaining reaction time. 378 mg of 4-cyano-4-(thiobenzoyl)pentanoic acid (1.35 mmol) are then added to the mixture. Once the substance has completely dissolved, 67 mg of AIBN (0.41 mmol) are added. From then on, the conversion is regularly determined by HPLC.

[0143] As soon as the reaction, based on methoxy-polyethylene glycol methacrylate, reaches 45 mol%, 4.66 g of methacrylic acid (0.05 mol) dissolved in 20 g of H 2 O are added dropwise within 20 min. After completion, the mixture is allowed to react for a further 4 h and then allowed to cool. A clear, slightly reddish, aqueous solution with a solids content of approximately 35% remains. The resulting copolymer with a gradient structure is referred to as a copolymer. P2 designated. 1.5 Copolymer P3

[0144] To prepare the gradient polymer using RAFT polymerization, 57.4 g of 50% methoxypolyethylene glycol 1000 methacrylate (0.03 mol) and 22 g of deionized water are placed in a round-bottom flask equipped with a reflux condenser, stirrer, thermometer, and a gas inlet tube. The reaction mixture is heated to 80°C with vigorous stirring. A gentle stream of inert N2 gas is passed through the solution during the warm-up and the entire remaining reaction time. 378 mg of 4-cyano-4-(thiobenzoyl)pentanoic acid (1.35 mmol) are then added to the mixture. Once the substance has completely dissolved, 67 mg of AIBN (0.41 mmol) are added. From then on, the conversion is regularly determined by HPLC.

[0145] As soon as the reaction, based on methoxy-polyethylene glycol methacrylate, reaches 30 mol%, 4.66 g of methacrylic acid (0.05 mol) dissolved in 20 g of H 2 O are added dropwise within 20 min. After completion, the mixture is allowed to react for a further 4 h and then allowed to cool. A clear, slightly reddish, aqueous solution with a solids content of approximately 35% remains. The resulting copolymer with a gradient structure is referred to as a copolymer. P3 designated. 2. Mortar mixtures 2.1 Production

[0146] The mortar mixture used for testing purposes has the dry composition described in Table 2: Table 2: Dry composition of mortar mix component Quantity [g] Cement (CEM I 42.5 N; Normo 4; available from Holcim Switzerland) 750 g Limestone filler 141 g Sand 0-1 mm 738 g Sand 1-4 mm 1107 g Sand 4-8 mm 1154 g

[0147] To prepare a mortar mix, the sand, limestone filler, and cement were dry-mixed for 1 minute in a Hobart mixer. The mixing water (water to cement w / c ratio = 0.49), to which the respective polymer (proportion: 0.24 wt%; based on the solids content of the polymer and based on the cement content) had previously been added, was added within 30 seconds, and mixing continued for a further 2.5 minutes. The total wet mixing time was 3 minutes in each case. 2.2 Mortar tests

[0148] To determine the dispersing effect of the polymers, the slump (SFS) of mixed mortar mixtures was measured at different times. The slump (SFS) of the mortar was determined according to EN 1015-3. 2.3 Results of the mortar tests

[0149] Table 3 provides an overview of the mortar tests conducted and the results obtained. V1is a zero test carried out for comparison purposes without the addition of a polymer.

[0150] A comparison of the experiments shows that all copolymers P1 - P3 with gradient structure show a good, long-lasting and persistent liquefaction effect. This applies particularly to copolymer P2. In comparison, the copolymers R1 and R2, which have a pure block structure or a statistical monomer distribution, perform significantly worse.

[0151] From the presented results, it can be concluded that the copolymers according to the invention are advantageous in several respects compared to known polymers. In particular, the polymers according to the invention can achieve high dispersing and liquefaction effects, which can be maintained at a level of practical interest even over a comparatively long period of time.

[0152] However, the embodiments described above are to be understood merely as illustrative examples, which can be modified as desired within the scope of the invention.

Claims

1. Copolymer, especially for use as a dispersant for solid-state particles, in particular for use as a dispersant for mineral binder compositions, having a polymer backbone and side chains bonded thereto, comprising at least one ionizable monomer unit M1 and at least one side chain-bearing monomer unit M2, characterized in that the copolymer has a gradient structure in at least one section A in a direction along the polymer backbone with regard to the ionizable monomer unit M1 and / or with regard to the side chain-bearing monomer unit M2, where the ionizable monomer unit M1 has a structure of the formula I and the side chain-bearing monomer unit M2 includes a structure of the formula II where R1, in each case independently, is -COOM, -SO2-OM, -O-PO(OM)2 and / or -PO(OM)2, R2, R3, R5 and R6, in each case independently, are H or an alkyl group having 1 to 5 carbon atoms, R4 and R7, in each case independently, are H, -COOM or an alkyl group having 1 to 5 carbon atoms, or where R1 forms a ring together with R4 to give -CO-O-CO-, M, independently of any other, is H+, an alkali metal ion, an alkaline earth metal ion, a di- or trivalent metal ion, an ammonium ion or an organic ammonium group; m is 0, 1 or 2, p is 0 or 1, X, in each case independently, is -O- or -NH-, R8 is a group of the formula -[AO]n-Ra where A is C2- to C4-alkylene, Ra is H, a C1- to C20-alkyl group, -cycloalkyl group or -alkylaryl group, and n is 2-250, especially 10-200; where the at least one section A having the gradient structure has a proportion of at least 30% of monomer units, based on a total number of monomer units in the polymer backbone.

2. Copolymer according to Claim 1, wherein the polydispersity of the copolymer is < 1.5 and is particularly in the range of 1.0-1.4, especially 1.1-1.3.

3. Copolymer according to at least one of Claims 1-2, characterized in that the at least one section A having the gradient structure has a proportion of at least 50%, preferably at least 75% or 90%, of monomer units, based on a total number of monomer units in the polymer backbone.

4. Copolymer according to at least one of Claims 1-3, characterized in that the copolymer, in addition to the at least one section A, has a further section B having an essentially constant local concentration of monomers and / or a random distribution of monomers, where the further section B comprises ionizable monomer units M1 and / or side chain-bearing monomer units M2.

5. Copolymer according to Claim 4, characterized in that the further section B having the essentially constant local concentration, based on all the monomer units present therein, comprises at least 30 mol%, especially at least 50 mol%, preferably at least 75 mol%, in particular at least 90 mol% or at least 95 mol%, of side chain-bearing monomer units M2, and wherein any proportion of ionizable monomer units M1 present in the further section is less than 25 mol%, especially not more than 10 mol% or less than 5 mol%, based on all the monomer units M2 in the further section.

6. Copolymer according to at least one of Claims 1-5, characterized in that R1 = COOM; R2 and R5, independently of one another, are H, -CH3 or mixtures thereof; R3 and R6, independently of one another, are H or -CH3, preferably H; R4 and R7, independently of one another, are H or -COOM, preferably H; and where X in at least 75 mol%, particularly in at least 90 mol%, especially in at least 99 mol%, of all monomer units M2 is -O-.

7. Process for preparing a copolymer according to at least one of Claims 1-6, wherein ionizable monomers m1 and side chain-bearing monomers m2 are polymerized together to form a concentration gradient and / or a gradient structure, wherein the ionizable monomers m1 have a structure of the formula IV: and the side chain-bearing monomers m2 have a structure of the formula V: where R1, R2, R3, R4, R5, R6, R7, R8, m, p and X are as defined in Claim 1.

8. Process according to Claim 7, characterized in that the polymerization is effected by a controlled free-radical polymerization and / or a living free-radical polymerization, especially by reversible addition-fragmentation chain transfer polymerization (RAFT).

9. Process according to at least one of Claims 7-8, wherein, in a first step a), a portion of the side chain-bearing monomers m2 is converted or polymerized essentially in the absence of ionizable monomers m1 and, on attainment of a predetermined conversion, in a second step b), the as yet unconverted side chain-bearing monomers m2 are polymerized together with the ionizable monomers m1, the polymerization in step a) being conducted until 1-74 mol%, preferably 10-70 mol%, in particular 25-70 mol%, especially 28-50 mol% or 30-45 mol%, of the side chain-bearing monomers m2 have been converted or polymerized.

10. Use of a copolymer according to at least one of Claims 1-6 as a dispersant for solid-state particles, especially as a dispersant for a mineral binder composition, especially for plasticization, for water reduction and / or for extending the workability of a mineral binder composition, preferably a mortar or concrete composition.

11. Mineral binder composition, especially a mortar or concrete composition, comprising at least one copolymer as described in any of the preceding claims.

12. Shaped body, especially a constituent of a built structure, obtainable by curing a mineral binder composition according to Claim 11 after addition of water.