EP3353136A1 - Additif contenant un fluidifiant et un copolymère - Google Patents

Additif contenant un fluidifiant et un copolymère

Info

Publication number
EP3353136A1
EP3353136A1 EP16775136.1A EP16775136A EP3353136A1 EP 3353136 A1 EP3353136 A1 EP 3353136A1 EP 16775136 A EP16775136 A EP 16775136A EP 3353136 A1 EP3353136 A1 EP 3353136A1
Authority
EP
European Patent Office
Prior art keywords
copolymer
mol
group
monomer units
independently
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP16775136.1A
Other languages
German (de)
English (en)
Inventor
Jürg WEIDMANN
Lukas Frunz
Jörg ZIMMERMANN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sika Technology AG
Original Assignee
Sika Technology AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Publication of EP3353136A1 publication Critical patent/EP3353136A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C04B40/0042—Powdery mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0061—Block (co-)polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0063—Polymers chosen for their physico-chemical characteristics obtained by an unusual polymerisation process, e.g. by changing the molar ratio of the different monomers during the polymerisation process
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/308—Slump-loss preventing agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/32—Superplasticisers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants
    • C04B2103/408—Dispersants

Definitions

  • the invention relates to an additive, in particular a dispersant for solid particles, in particular a dispersant for mineral binder compositions, comprising a flow agent and a copolymer. Furthermore, the invention relates to the use of an additive as a dispersant for solid particles, a mineral binder composition and a molded article obtainable therefrom.
  • Dispersants or flow agents are used in the construction industry as plasticizers or water reducing agents for mineral binder compositions, such as e.g. Concrete, mortar, cements, plaster and lime, used.
  • the dispersants are generally organic polymers which are added to the make-up water or added as a solid to the binder compositions. As a result, both the consistency of the binder composition during processing and the properties in the cured state can be advantageously changed.
  • Polycarboxylate-based comb polymers for example, are known as particularly effective dispersants. Such comb polymers have a polymer backbone and side chains attached thereto. Corresponding polymers are described, for example, in EP 1 138 697 A1 (Sika AG). Also known as concrete admixtures are copolymer blends as mentioned, for example, in EP 1 1 10 981 A2 (Kao). The copolymer blends are prepared by reacting ethylenically unsaturated monomers in a free radical polymerization reaction, wherein the molar Ratio of the two monomers during the polymerization process is changed at least once.
  • the object of the invention is therefore to overcome the disadvantages mentioned above.
  • an improved dispersant in particular for solid particles and in particular for mineral binder compositions should be provided.
  • the dispersant should enable effective liquefaction and good processing of mineral binder compositions.
  • the effect of the dispersant over the longest possible time should be maintained. It is further desirable that the dispersant can be produced as flexibly and as controlled as possible.
  • the core of the invention is accordingly an additive, in particular a dispersant for solid particles, in particular a dispersant for mineral binder compositions, comprising: a) a flow agent and b) a copolymer having a polymer backbone and side chains attached thereto, comprising at least one ionizable monomer unit M1 and at least one side chain-carrying monomer unit M2, wherein the copolymer in a direction along the polymer backbone a non-random distribution of Monomer units M1 and / or the monomer units M2.
  • Flow agent and copolymer differ in chemical and / or structural terms. As has been shown, such additives result in comparison with known dispersants very good liquefaction in mineral binder compositions, which also remain relatively longer maintained. In particular, in comparison with a flow agent alone or a copolymer alone, the combinations according to the invention show in some cases significantly better liquefaction performance. This shows that the flow agent and the copolymer work together functionally and synergistically. In addition, the flow agents used according to the invention and the copolymers can be prepared in a reliable manner in a wide variety of modifications in efficient processes. The additives according to the invention can be adapted to different requirements, for example by mixing the flow agents and the copolymers, and can be produced in a flexible and controlled manner.
  • a first aspect of the present invention relates to an additive, in particular a dispersant for solid particles, in particular a dispersant for mineral binder compositions, comprising: a) a flow agent and b) a copolymer 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, the copolymer having a non-random distribution of the monomer units M1 and / or the monomer units in one direction along the polymer backbone M2 has.
  • Flow agent and copolymer differ in chemical and / or structural terms. If the flow agent is a polymer, this has in particular a random or statistical monomer distribution.
  • flow agent in the present context is meant in particular a substance which is capable of improving the flowability of waterborne mortar and / or concrete compositions and / or reducing the water requirement of such a composition.
  • Such substances are also referred to as "liquefiers”.
  • the flow agent comprises at least one member selected from the group consisting of lignosulfonates, gluconates, naphthalenesulfonates, sulfonated naphthalene-formaldehyde condensates, melamine sulfonates, vinyl copolymers, sulfonated vinyl copolymers, polycarboxylates, in particular polycarboxylate ethers, or mixtures thereof.
  • the flow agent is a polycarboxylate, in particular a polycarboxylate ether.
  • a polycarboxylate ether Particularly preferred is a comb polymer which has a polycarboxylate backbone and polyether side chains, wherein the polyether side chains are bound to the polycarboxylate backbone via ester, ether, amide and / or imide groups.
  • the polycarboxylate has a random or random monomer distribution.
  • the flow agent is particularly preferably a polymer P which comprises or consists of the following structural units:
  • G 3 independently of one another represent NH 2 , -NG 5 G 6 , -OG 7 NG 8 G 9 ,
  • G 5 and G 6 independently represent a C to C 20 alkyl group, cycloalkyl group
  • -Alkylaryl group or -aryl group or for a hydroxyalkyl group or for ace- toxyethyl- (CH 3 -CO-O-CH 2 -CH 2 -) or hydroxyisopropyl- (HO-CH (CH 3 ) -CH 2 -) or an acetoxyisopropyl group (CH 3 -CO-O-CH (CH 3 ) -CH 2 -); or G 5 and G 6 together form a ring of which the nitrogen is a part to form a morpholine or imidazoline ring;
  • G 7 is a C 2 -C 4 -alkylene group
  • G 8 and G 9 are each independently a C 1 to C 20
  • a / b / c / d (0.1-0.9) / (0.1-0.9) / (0-0.8) / (0-0.8),
  • the sequence of the partial structural units S1, S2, S3 and S4 can be alternating, block-like or random. It is also possible for the one or more of the substructure units S1, S2, S3 and S4 to form a gradient structure. In principle, it is also possible that, in addition to the partial structural units S1, S2, S3 and S4, further structural units are present. In particular, the sequences of partial structural units S1, S2, S3 and S4 in polymer P are random or random.
  • the partial structural units S1, S2, S3 and S4 together preferably have a weight fraction of at least 50% by weight, in particular at least 90% by weight, very particularly preferably at least 95% by weight, of the total weight of the polymer P.
  • the preparation of the polymers P is known per se to those skilled in the art and can be carried out, for example, by free-radical polymerization of the corresponding monomers of the formula (I m ), (Um), (Ulm) or (IV m ), resulting in a polymer P having the partial structural units S1, S2, S3 and S4 leads.
  • the radicals R u , R v , G 1 , G 2 , G 3 , L, r and t are defined as described above in connection with the polymer P.
  • the polycarboxylic acid of the formula (V) is esterified or amidated with the corresponding alcohols or amines (eg HO-G 1 , H 2 NG 2 , H-G 3 ) and then at most neutralized or partially neutralized (depending on Type of residue L eg with metal hydroxides or ammonia).
  • the radicals L and the parameter s are defined as described above in connection with the polymer P. Details of the polymer-analogous reaction are disclosed, for example, in EP 1 138 697 B1 on page 7 line 20 to page 8 line 50, as well as in its examples or in EP 1 061 089 B1 on page 4, line 54 to page 5 line 38 and in its the examples.
  • the polymer in a variant thereof, as described in EP 1 348 729 A1 on page 3 to page 5 and in its examples, the polymer can be prepared in a solid state of aggregation. be put.
  • the disclosure of these cited patents is hereby incorporated by reference in particular.
  • the preparation by polymer-anlogous reaction is preferred.
  • R v is in particular hydrogen and R u is preferably hydrogen and / or a methyl group.
  • R u is a methyl group
  • a ' is a C 2 - to C 4 -alkylene.
  • G 4 in each case independently of one another, is preferably hydrogen or a methyl group.
  • a weight-average molecular weight (M w ) of the polymer P is in particular 5 ⁇ 00 - 150 ⁇ 00 g / mol, preferably 10 ⁇ 00 - 100 ⁇ 00 g / mol, especially 20 ⁇ 00 - 90 ⁇ 00 g / mol.
  • the weight average molecular weight (M w ) is determined by gel permeation chromatography (GPC) using polyethylene glycol (PEG) as a standard.
  • Corresponding flow agents or polymers P are also commercially sold by Sika Nurse AG under the trade name series ViscoCrete®.
  • the flow agent or the polymer P is advantageously used in a liquid state.
  • the flow agent or the polymer P may be the composition as a solution or dispersion. In particular as an aqueous solution or dispersion.
  • the flow agent or the polymer P it is also possible for the flow agent or the polymer P to be in the form of a melt or in a solid state, e.g. in the form of powder, pellets or flakes.
  • ionizable monomers and “ionizable monomer units” is meant in particular monomers or polymerized monomers which are present at a pH> 10, in particular at a pH> 12, in anionic form or negatively charged. These are in particular H-donor groups or acid groups. Most preferably, the ionizable groups are acid groups, such as e.g. Carboxylic acid, sulfonic acid, phosphoric acid and / or phosphonic acid groups. Preferred are carboxylic acid groups. The acid groups may also be present as anions in deprotonated form or as a salt with a counterion or cation.
  • non-random distribution is understood to mean a non-statistical distribution of the monomer units M1 and / or the monomer units M2. This means that the ionizable monomer units M1 and / or the side chain-carrying monomer units M2 in the copolymer are arranged, for example, in an alternating, block-like manner and / or in a gradient structure.
  • the structure of the copolymers can be analyzed and determined, for example, by nuclear magnetic resonance spectroscopy (NMR spectroscopy).
  • NMR spectroscopy nuclear magnetic resonance spectroscopy
  • 13 C - and 1 H-NMR spectroscopy can be determined in a conventional manner due to adjacent group effects in the copolymer and based on statistical evaluations, the sequence of the monomer units in the copolymer.
  • the ionizable monomer units M1 preferably comprise acid groups, in particular carboxylic acid, sulfonic acid, phosphoric acid and / or phosphonic acid groups.
  • the side chain-carrying monomer unit M2 contains in particular polyalkylene oxide side chains, in particular polyethylene oxide and / or polypropylene oxide side chains.
  • the ionizable monomer units M1 have a structure according to formula VI:
  • the side chain-carrying monomer units M2 preferably have a structure according to the formula VII:
  • R 1 in each case independently of one another, is -COOM, -SO 2 -OM-O-PO (OM) 2 and / or -PO (OM) 2 ,
  • R 2 , R 3 , R 5 and R 6 are H or an alkyl group having 1 to 5 carbon atoms,
  • R 4 and R 7 are H, -COOM or an alkyl group having 1 to 5 carbon atoms, or where R 1 forms a ring with R 4 to -CO-O-CO-,
  • X each independently of one another, is -O- or -NH-
  • a molar ratio of the monomer units M1 to the monomer units M2 is advantageously in the range from 0.5 to 6, in particular 0.7 to 4, preferably 0.9 to 3.8, more preferably 1 .0 to 3.7 or 2 to 3.5.
  • the copolymer can be prepared on the basis of acrylic or methacrylic acid monomers, which is interesting from an economic point of view.
  • such copolymers have a particularly good dispersing effect in the present context.
  • R 1 COOM
  • R 2 H
  • R 3 H
  • R 4 COOM
  • Corresponding copolymers can be prepared on the basis of maleic acid monomers.
  • the copolymers can be prepared, for example, starting from (meth) acrylic esters, vinyl, (meth) allyl or isoprenol ethers.
  • R 2 and R 5 are each mixtures of 40-60 mol% H and 40-60 mol% -CH 3 .
  • R 1 COOM
  • R 2 H
  • R 5 -CH 3
  • R 1 COOM
  • the radical R 8 in the side chain-carrying monomer units M2 is, based on all radicals R 8 of the monomer units, in particular at least 50 mol%, in particular at least 75 mol%, preferably at least 95 mol% or at least 99 mol%, from a polyethylene oxide.
  • a 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 in particular 100 mol%.
  • R 8 has substantially no hydrophobic groups, especially no alkylene oxides having three or more carbon atoms.
  • a 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%.
  • there are no alkylene oxides having three or more carbon atoms or their proportion is 0 mol%.
  • R a is advantageously H and / or a methyl group.
  • A C2-alkylene and R a is H or a methyl group.
  • the copolymer comprises at least one further monomer unit MS, which differs in particular from the monomer units M1 and M2 chemically.
  • the further monomer units MS can be present. This allows the Properties of the copolymer further modified and adapted, for example, with regard to specific applications.
  • the at least one further monomer unit MS is a monomer unit of the formula VIII:
  • R 5 , R 6 , R 7 , m 'and p' are the same as R 5 , R 6 , R 7 , m and p as described above in connection with the copolymer;
  • Y each independently, is a chemical bond or -O-;
  • Z each independently, is a chemical bond, -O- or -NH-;
  • R 9 in each case independently of one another, represents an alkyl group, cycloalkyl group, alkylaryl group, aryl group, hydroxyalkyl group or an acetoxyalkyl group, each having 1 to 20 C atoms.
  • the at least one further monomer unit MS consists of copolymerized vinyl acetate, styrene and / or hydroxyalkyl (meth) acrylate, in particular hydroxyethyl acrylate.
  • a weight average molecular weight M w of the entire copolymer is in particular in the range of 10 ⁇ 00 - 150 ⁇ 00 g / mol, advantageously 12 ⁇ 00 - 80 ⁇ 00 g / mol, especially 12 ⁇ 00 - 50 ⁇ 00 g / mol.
  • molecular weights such as weight average molecular weight Mw or number average molecular weight M n are determined by gel permeation chromatography (GPC) with polyethylene glycol (PEG) as the standard. This technique is known per se to the person skilled in the art.
  • the copolymer is a polymer of substantially linear structure. This means in particular that all monomer units of the copolymer are arranged in a single and / or unbranched polymer chain.
  • the copolymer does not have a star-shaped structure and / or the copolymer is not part of a branched polymer.
  • the copolymer is not part of a polymer in which a plurality of, in particular three or more, extending in different directions polymer chains are attached to a central molecule.
  • the copolymer has a gradient structure in at least one section AA in a direction along the polymer backbone with respect to the ionizable monomer unit M1 and / or with respect to the side chain-carrying monomer unit M2.
  • the copolymer according to the invention has a concentration gradient in at least one section AA in one direction along the polymer backbone with respect to the ionizable monomer unit M1 and / or with respect to the side chain-carrying monomer unit M2.
  • the term "gradient structure” or "concentration gradient” in the present case stands in particular for a continuous change of the local concentration of a monomer unit in at least one section in a direction along the backbone of the copolymer.
  • concentration gradient may be substantially constant, for example. This corresponds to a linear decrease or increase in the local concentration of the respective monomer unit in at least a portion AA along the direction of the backbone of the copolymer. However, it is also possible that the concentration gradient changes along the direction of the backbone of the copolymer. In this case, there is a non-linear 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. In contrast, abrupt or sudden changes in the concentration of monomers, as they occur for example in block copolymers, not referred to as concentration gradient.
  • the term "local concentration" as used herein refers to the concentration of a particular monomer at a given site of the polymer backbone.
  • the local concentration or the mean value of the local concentration can be determined, for example, by determining the monomer conversions during the production of the copolymer. In this case, the monomers reacted in a certain period of time can be determined.
  • the average local concentration corresponds in particular to the ratio of the molar fraction of a specific monomer converted in the period considered to the total molar amount of monomers reacted in the period under consideration.
  • the conversions of the monomers can be determined, for example, by means of liquid chromatography, in particular high-performance liquid chromatography (HPLC), and taking into account the amounts of monomers used, in a manner known per se.
  • HPLC high-performance liquid chromatography
  • the structure of the copolymers can also be determined as outlined above, by 13 C and 1 H NMR spectroscopy.
  • the copolymer may also have more than one section AA with a gradient structure, in particular two, three, four or even more sections AA, which may be e.g. arranged one behind the other. If present, different gradient structures or concentration gradients may exist in each of the different sections AA.
  • 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 M2 continuously decreases along the polymer backbone, or vice versa.
  • a local concentration of the ionizable monomer unit M1 at the first end of the at least one section AA is in particular lower than at the second end of the section AA, while a local concentration of the side chain-carrying monomer unit M2 at the first end of the section AA is greater than at the second end of section AA, or vice versa.
  • the average local concentration of the at least one ionizable monomer unit M1 in the respective subsections along the polymer backbone in at least 3, in particular in at least 5 or 8, successive subsections increases as the average local concentration of the at least one sidechain-bearing monomer unit M2 in the respective subsections along the polymer backbone decreases in at least 3, in particular at least 5 or 8, successive subsections, or vice versa.
  • an increase or decrease in the averaged 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 averaged local concentration of the at least one sidechain bearing monomer unit M2 in the successive subsections in FIG Is also essentially constant.
  • the at least one section AA with the gradient structure based on a total length of the polymer backbone, has a length of at least 30%, in particular at least 50%, preferably at least 75% or 90%.
  • the at least one section AA based on a total number of monomer units in the polymer backbone, a proportion of at least 30%, in particular at least 50%, preferably at least 75% or 90% of monomer units.
  • the at least one section AA based on the weight-average molecular weight of the entire copolymer, has a weight fraction of at least 30%, in particular at least 50%, preferably at least 75% or 90%.
  • section AA with the concentration gradient or the gradient structure in particular mass comes into play.
  • the at least one concentration gradient section AA advantageously comprises 5 to 70, in particular 7 to 40, preferably 10 to 25 monomer units M1 and 5 to 70, in particular 7 to 40, preferably 10 to 25, monomer units M2.
  • the copolymer consists of at least 50 mole%, especially at least 75 mole%, especially at least 90 mole% or 95 mole%, of ionizable monomer units M1 and side chain carrying monomer units M2.
  • the last two aforementioned conditions apply simultaneously.
  • the copolymer additionally lent to at least one section AA, which has a gradient structure, over a further section AB, wherein over the entire section AB is substantially a constant local concentration of the monomers and / or a random or random distribution the monomers are present.
  • Section AB may e.g. consist of monomers of a single variety or of several different monomers, which are randomly distributed. In section AB, however, in particular there is no gradient structure or no concentration gradient along the polymer backbone.
  • the copolymer may also have more than one further portion AB, e.g. two, three, four or more sections AB, which may differ chemically and / or structurally.
  • the at least one section AA connects directly to the further section AB.
  • the further section AB comprises ionizable monomer units M1 and / or side chain-carrying monomer units M2.
  • the further section AB in one embodiment of the invention comprises, 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 mole% ionizable monomer units M1.
  • a possibly existing proportion of side-chain-carrying monomer units M2 in the further section AB is in particular less than 25 mol%, especially less than 10 mol% or less than 5 mol%, based on all monomer units M1 in the further section. In particular, there are no side chain-carrying monomer units M2 in the further section AB.
  • the further section AB comprises, based on all the 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 mole percent, side chain bearing monomer units M2.
  • an optional proportion of ionizable monomer units M1 in the further section AB is in particular 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 FROM.
  • no ionizable monomer units M1 are present in the further section AB.
  • the further section AB comprises a total of 5 to 70, in particular 7 to 40, preferably 10 to 25 monomer units. These are, in particular, ionizable monomer units M1 and / or side chain-carrying monomer units M2.
  • a ratio of the number of monomer units in the at least one section AA with gradient structure to the number of monomer units in the at least one further section AB with the substantially constant local concentration is advantageously in the range from 99: 1 to 1:99, in particular 10:90 to 90:10 , preferably 80:20 - 20:80, especially 70:30 - 30:70.
  • the at least one further monomer unit MS may be part of the at least one section AA and / or the further section AB. 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 further monomer units MS can be present in the different sections. If present in at least one section AA, the at least one further monomer unit MS in the at least one section AA advantageously has a proportion of 0.001-80 mol%, preferably 20-75 mol%, especially 30-70 mol%, based on all monomer units in the first section AA, on.
  • the at least one further monomer unit MS in the further section AB has 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 AB, on.
  • the copolymer consists of the at least one section AA.
  • the copolymer consists of the at least one section AA and the further section AB. Especially in the latter case, very good and long-lasting liquefaction effects result. However, it is also possible, for example, for the copolymer to contain at least two different sections AA and / or at least two different further sections AB.
  • a particularly advantageous copolymer has at least one or more of the following characteristics: 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-carrying monomer units M2; ii) the copolymer comprises or consists of at least a section AA and a further section AB; iii) The further section AB comprises side chain-carrying monomer units M2, in particular at least 50 mol%, preferably at least 75 In particular at least 90 mol% or at least 95 mol%, based on all the monomer units contained in section AB.
  • a possibly existing proportion of ionizable monomer units M1 in the further section AB 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 AB.
  • a molar ratio of the monomer units M1 to the monomer units M2 in the copolymer is in the range of 0.5-6, preferably 0.8-3.5;
  • R 1 is COOM;
  • R 2 and R 5 are H or CH 3 , preferably CH 3 ;
  • a copolymer consisting of sections AA and AB which has at least all of the features (i) - (iv). Further preferred is a copolymer which has all the features (i) - (xi). Even more preferred is a copolymer which realizes all features (i) - (xi) in the respectively preferred embodiments.
  • a copolymer comprising at least one first block A and at least one second block B, where the first block A has an ionizable monomer unit M1 of the formula VI and the second block B has a side chain-carrying monomer unit M2 of the formula VII.
  • an optional fraction of monomer units M2 in the first block A is less than 25 mol%, in particular less than or equal to 10 mol%, based on all monomer units M1 in the first block A and a if present, proportion of monomer units M1 in the second block B is less than 25 mol%, in particular less than or equal to 10 mol%, based on all monomer units M2 in the second block B.
  • the monomer units M1 and any further monomer units in the first block A are distributed in particular statistically or randomly.
  • the monomer units M2 and any further monomer units are present in the second block B in particular statistically or randomly distributed.
  • the at least one block A and / or the at least one block B is preferably present in each case as a partial polymer with random monomer distribution.
  • the at least one first block A advantageously comprises 5 to 70, in particular 7 to 40, preferably 10 to 25, monomer units M1 and / or the at least one second block B comprises 5 to 70, in particular 7 to 50, preferably 20 40, monomer units M2.
  • any fraction of monomer units M2 present in the first block A is less than 15 mol%, in particular less than 10 mol%, especially less than 5 mol% or less than 1 mol%, based on all monomer units M1 in the first block A.
  • an optional fraction of monomer units M1 in the second block B is advantageously less than 15 mol%, in particular less than 10 mol%, especially less than 5 mol% or less than 1 mol%, based on all monomer units M2 in the second block B.
  • both conditions are fulfilled at the same time.
  • a fraction of monomer units M2 in the first block A which is possibly present is particularly advantageously less than 15 mol% (based on all monomer units M1 in the first block A) and a possibly present fraction of monomer units M1 in the second block B is less than 10 mol%. %, (based on all monomer units M2 in the second block B).
  • the monomer units M1 and M2 are essentially spatially separated, which benefits the dispersing effect of the block copolymer and is advantageous in view of the delay problem.
  • the first block A is based on all monomer units in the first block A in particular at least 20 mol%, in particular at least 50 mol%, especially at least 75 mol% or at least 90 mol% of ionizable monomer units M1 of formula VI.
  • the second block B is based on all monomer units in the second block B advantageously at least 20 mol%, in particular at least 50 mol%, especially at least 75 mol% or at least 90 mol% of side chain-carrying monomer units M2 of formula VII ,
  • a molar ratio of the monomer units M1 to the monomer units M2 in the block copolymer is in particular in the range from 0.5 to 6, in particular 0.7 to 4, preferably 0.9 to 3.8, more preferably 1 .0 to 3.7 or 2 to 3.5. This achieves an optimum dispersing effect in mineral binder compositions.
  • copolymer having a block structure may also comprise at least one further monomer unit MS as described above.
  • further monomer units MS can be present.
  • properties of the copolymer can be further modified and adapted, for example, with regard to specific applications.
  • the at least one further monomer unit MS may be part of the first block A and / or the second block B. It is also possible that the at least one further monomer unit MS is part of an additional block of the copolymer. In particular, different monomer units MS can be present in the various blocks.
  • the at least one further monomer unit MS in the first block A advantageously has a proportion of 0.001-80 mol%, preferably 20-75 mol%, especially 30-70 mol%, based on all monomer units in the first block A, up.
  • the at least one further monomer unit MS in the second block B has 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 second block B, on.
  • the at least one further monomer unit MS has a proportion of 20-75 mol%, especially 30-70 mol%, based on all monomer units in the respective block , available.
  • At least one further block C is arranged, which differs chemically and / or structurally from the first and from the second block.
  • the at least one further block C comprises monomer units MS as described above or consists thereof.
  • monomer units MS as described above or consists thereof.
  • further monomer units it is also possible for further monomer units to be present.
  • the at least one further block C comprises at least 50 mol%, in particular at least 75 mol%, preferably at least 90 mol% or at least 95 mol% of monomer units MS as described above.
  • the copolymer according to the invention is a diblock copolymer consisting of a block A and a block B.
  • block copolymers containing at least two blocks of the first block A and / or at least two blocks of the second block B are block copolymers which contain the first block A twice and the second block B once or block copolymers which contain the first block A once and the second block B twice.
  • block copolymers are in particular triblock copolymers, tetrablock copolymers or pentablock copolymers, preferably triblock copolymers.
  • tetrablock copolymers and the pentablockcopo are present, for example Block C blocks as described above.
  • a diblock copolymer consisting of blocks A and B, which has at least all features (i) - (iv). Further preferred is a diblock copolymer which has all the features (i) - (xi). Even more preferred is a diblock copolymer which realizes all features (i) - (xi) in the respectively preferred embodiments.
  • Block C advantageously comprises monomer units MS as described above or block C consists thereof.
  • block A and B additionally contain a further monomer unit MS as described above, in particular a further monomer unit MS of the formula VIII.
  • a further aspect of the present invention relates to a process for the preparation of a copolymer, in particular a copolymer as described above, wherein ionizable monomers m1 and side chain-carrying monomers m2 to form a non-random distribution of the ionizable monomers m1 and / or the Side chain-bearing monomers m2 polymerized together.
  • the ionizable monomers m1 correspond to the abovementioned ionizable monomer units M1 of the copolymer.
  • the side-chain-carrying monomers m2 correspond after polymerization to the side-chain-carrying monomer units M2 described above.
  • the side-chain-carrying monomers m2 include in particular polyalkylene oxide side chains, preferably polyethylene oxide and / or polypropylene oxide side chains.
  • the ionizable monomers m1 preferably comprise acid groups, in particular carboxylic acid, sulfonic acid, phosphoric acid and / or phosphonic acid groups.
  • the ionizable monomers m1 have a structure according to the formula IX:
  • the side chain-carrying monomers m2 preferably have a structure according to the formula X:
  • At least one further monomer ms is present during the polymerization, which is polymerized, which is in particular a monomer of the formula XI:
  • R 5 , R 6 , R 7 , R 9 , Y, Z, m 'and p' are as defined above.
  • the preparation of the copolymer takes place in particular by a living free radical polymerization.
  • Radical polymerization can basically be divided into three steps: initiation, growth, and termination.
  • 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 is used for chain growth processes in which essentially no chain termination reactions (transfer and termination) take place.
  • the living free radical polymerization thus takes place essentially in the absence of irreversible transfer or termination reactions.
  • These criteria can be met, for example, if the polymerization initiator is consumed very early in the polymerization and there is an exchange between the different reactive species that proceeds at least as fast as the chain propagation itself.
  • the number of active chain ends remains during the polymerization especially substantially constant. This allows a substantially contemporaneous growth of the chains throughout the polymerization process. This results in a corresponding narrow molecular weight distribution or polydispersity.
  • controlled radical polymerization or living-radical polymerization is characterized in particular by reversible or even absent termination or transfer reactions. After initiation, the active sites are thus retained throughout the reaction. All polymer chains are formed (initiated) simultaneously and grow continuously over the entire time. The radical functionality of the active center is ideally 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 the sequential addition of various monomers.
  • the "living free radical polymerization” clearly differs from the conventional "free radical polymerization” or the non-living or uncontrolled carried out free polymerization.
  • the polymerization is carried out by reversible addition-fragmentation chain transfer polymerization (RAFT), nitroxide mediated polymerization (NMP) and / or atom transfer radical polymerization (ATRP).
  • RAFT reversible addition-fragmentation chain transfer polymerization
  • NMP nitroxide mediated polymerization
  • ATRP atom transfer radical polymerization
  • the control of the polymerization is achieved by a reversible chain transfer reaction.
  • a growing radical chain adds a so-called RAFT agent, resulting in the formation of an intermediate radical.
  • the RAFT agent then fragments, re-forming a RAFT agent and a radical available for propagation. In this way, the propagation probability is distributed equally over all chains.
  • the average chain length of the polymer formed is proportional to the RAFT agent concentration as well as the reaction conversion.
  • organic sulfur compounds are used as RAFT agents. Particularly suitable are dithioesters, dithiocarbamates, trithiocarbonates and / or xanthates.
  • the initiation of the polymerization can be carried out conventionally by means of initiators or thermal self-initiation.
  • nitroxides react reversibly with the active chain end to form a so-called dormant species.
  • the equilibrium between active and inactive chain ends is strongly on the side of the dormant species, whereby the concentration of active species is very low. The probability that two active chains meet and cancel is thus minimized.
  • Suitable as NMP agent is e.g. 2,2,6,6-tetramethylpiperidine N-oxide (TEMPO).
  • the free radical concentration is reduced by the addition of a transition metal complex and a controlling agent (halogen-based) to the extent that chain termination reactions, such as disproportionation or recombination, are largely suppressed.
  • the reversible addition fragmentation chain transfer polymerization has been found to be particularly preferred.
  • the initiator used for the polymerization is particularly preferably an azo compound and / or a peroxide radical initiator, which is at least one member selected from the group consisting of dibenzoyl peroxide (DBPO), di-tert-butyl peroxide, diacetyl peroxide and azobisisobutyronitrile (AIBN), ⁇ , ⁇ '-azodiisobutyramidine dihydrochloride (AAPH) and / or azo-bis-isobutyramidine (AIBA).
  • DBPO dibenzoyl peroxide
  • AIBN azobisisobutyronitrile
  • AAPH ⁇ , ⁇ '-azodiisobutyramidine dihydrochloride
  • AIBA azo-bis-isobutyramidine
  • ⁇ , ⁇ '-azodiisobutyramidine dihydrochloride is advantageously used as the initiator.
  • One or more representatives from the group consisting of dithioester, dithiocarbamates, trithiocarbonates and / or xanthates are used to control the polymerization.
  • the polymerization takes place at least partially, preferably completely, in an aqueous solution.
  • a molar ratio of free ionizable monomers m1 to free side chain-carrying monomers m2 is changed at least temporarily during the polymerization.
  • the change in molar ratio involves a gradual and / or continuous change.
  • a block structure and / or a concentration gradient or a gradient structure can be formed in a manner which is easy to control.
  • both a continuous change and a stepwise change in the molar ratio of the free ionizable monomers m1 to the free side chain-carrying monomers m2 occurs.
  • This stepwise change takes place in particular in time before the continuous change is carried out.
  • a copolymer comprises two or more sections of different structure.
  • the ionizable monomers m1 and the side chain-carrying monomers m2 are preferably added at least partially offset in time.
  • a part of the ionizable monomers m1 is reacted or polymerized and, after reaching a predetermined conversion in a second step b), the unreacted ionizable monomers m1 together with the side chains bearing monomers m2 polymerized.
  • Step a) takes place in this case in particular essentially in the absence of side-chain-carrying monomers m2.
  • a copolymer having a section which consists essentially of polymerized ionizable monomers m1 and a subsequent section having a gradient structure can be produced in a simple and cost-effective manner.
  • Step a) in the polymerization in a first step a) a part of the side chain-carrying monomers m2 reacted 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 polymerized.
  • Step a) is carried out in particular substantially in the absence of ionizable monomers m1.
  • steps a) and b) are advantageous to carry out steps a) and b) directly following one another. As a result, the polymerization reaction in steps a) and b) can be maintained as best as possible.
  • step a) The polymerization in step a) is carried out in particular until 0.1-100 mol%, in particular 1-95 mol%, preferably 10-90 mol%, in particular 25-85 mol%, of the ionizable monomers m1 or the side chain-carrying monomers m2 are reacted or polymerized.
  • the conversion of the monomers m1 and m2 or the progress of the polymerization can be carried out, for example, with the aid of liquid chromatography, in particular high-performance liquid chromatography (HPLC), are controlled in a conventional manner.
  • HPLC high-performance liquid chromatography
  • the copolymer is at least 50 mole%, especially at least 75 mole%, especially at least 90 mole% or 95 mole%, of polymerized ionizable monomers m1 and polymerized sidechain-bearing monomers m2.
  • the copolymer can be prepared in liquid or solid form.
  • the copolymer is particularly preferably present as a constituent of a solution or dispersion, with a proportion of the copolymer being in particular 10 to 90% by weight, preferably 25 to 65% by weight.
  • the copolymer can be added very well to binder compositions. If the copolymer is prepared in solution, in particular in aqueous solution, it is also possible to dispense with further preparation.
  • a copolymer is prepared in a solid state, in particular in the form of a powder, in the form of pellets and / or plates.
  • Solutions or dispersions of the copolymers may e.g. be converted by spray drying in the solid state.
  • polymers of predetermined or well-defined structure can be prepared in a controlled manner with the process according to the invention.
  • Block structure copolymers and / or graded-structure copolymers are available.
  • Step a) it is also possible in a first step a) to react or polymerize at least a portion of the ionizable monomers m1 and after reaching a predetermined conversion in a second step b) the side chain-bearing monomers m2, optionally together with possibly not yet reacted ionizable monomers m1, to polymerize.
  • Step a) takes place in particular in the absence of ionizable monomers m2.
  • copolymers having a portion consisting essentially of polymerized side chain-carrying monomer monomers m2 and having a subsequent gradient-type portion can be produced in an efficient and inexpensive manner.
  • step a) the polymerization in step a) is carried out in particular 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-carrying monomers m2 or of the ionizable monomers m1 are reacted or polymerized.
  • step a) and / or in step b) there is at least one further polymerizable monomer ms of the formula XI as described above.
  • the at least one further polymerizable monomer ms is polymerized in this case, in particular together with the monomer m1 and / or the monomer m2.
  • step a) and step b) it is also possible, in addition to step a) and step b), to provide a further step c) of the polymerization of the at least one further polymerizable monomer ms.
  • a copolymer having an additional portion C can be prepared.
  • step c) can be performed in time between step a) and step b).
  • the additional section C is spatially located between sections AA and AB.
  • step c) before or after the steps a) and b).
  • the additional section C can be arranged after section AA or before section AB.
  • a) At least a portion of the side chain-carrying monomers m2 are reacted or polymerized and after reaching a predetermined conversion in a second step b) the ionizable monomers m1, optionally together with possibly not yet reacted side chain-bearing monomers m2, polymerized.
  • Step a) takes place in particular in the absence of ionizable monomers m1.
  • step a) The polymerization in step a) is carried out in particular until 75-95 mol%, preferably 85-95 mol%, in particular 86-92 mol%, of the initially charged monomers m2 have been reacted or polymerized.
  • step b) the polymerization in step b) is carried out correspondingly until 75 to 95 mol%, in particular 80 to 92 mol%, of the originally introduced monomers m1 are reacted or polymerized.
  • steps a) and b) can, however, in principle also be exchanged.
  • a block copolymer having an additional block C can be produced.
  • step c) is performed temporally between step a) and step b).
  • the additional block C is spatially arranged between the blocks A and B.
  • the additive comprises a flow agent in the form of a polymer P as described above and a copolymer as described above, in particular with a block or gradient structure.
  • this is a block or gradient polymer having ionizable monomer units M1 of the formula VI and side chain-carrying monomer unit M2 of the formula VII.
  • the ionizable monomer units M1 of the copolymer preferably comprise acid groups, in particular carboxylic acid, sulfonic acid, phosphoric acid and / or phosphonic acid groups.
  • the side chain-carrying monomer unit M2 includes in particular polyalkylene oxide side chains, in particular polyethylene oxide and / or polypropylene oxide side chains.
  • the copolymer has a gradient structure in at least one section AA and one, several or all of the following features are fulfilled:
  • the copolymer consists of at least 75 mol%, especially at least 90 mol% or 95 mol%, of ionizable monomer units M1 and side chain-carrying monomer units M2;
  • the copolymer comprises or consists of at least one section AA and a further section AB;
  • the further section AB comprises side chain-carrying 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 the monomer units contained in section AB.
  • a possibly existing proportion of ionizable monomer units M1 in the further section AB 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 AB.
  • a molar ratio of the monomer units M1 to the monomer units M2 in the copolymer is in the range from 0.5 to 6, preferably 0.8 to 3.5;
  • R a H or -CH 3 , preferably CH 3 . Also very particularly preferred is an additive with a flow agent in the form of a polymer P as described above
  • the copolymer is a block copolymer and comprises at least a first block A and at least one second block B, wherein the first block A has an ionizable monomer unit M1 of the formula VI and the second block B has a side-chain-carrying monomer unit M2 of the formula VII and a possibly present proportion of monomer units M2 in the first block A is less than 25 mol%, in particular smaller equal to 10 mol%, based on all monomer units M1 in the first block A and wherein a possibly present proportion of monomer units M1 in the second block B is less than 25 mol%, in particular less than or equal to 10 mol%, based on all monomer units M2 im second block B, and wherein at least one, several or all of the following features are fulfilled: ⁇ Block A has 7 -
  • the first block A is based on all monomer units in the first block A to at least 75 mol%, preferably at least 90 mol% of ionizable monomer units M1 of formula VI;
  • the second block B based on all the monomer units in the second block B, comprises at least 75 mol%, preferably at least 90 mol%, of side chain-carrying monomer units M2 of the formula VII;
  • a molar ratio of the monomer units M1 to the monomer units M2 in the block copolymer is in the range from 0.5 to 6, preferably 0.8 to 3.5;
  • R 1 stands for COOM;
  • R 2 and R 5 are H or CH 3, preferably CH 3;
  • X -O-.
  • R a H or -CH 3 , preferably CH 3 .
  • the weight ratio of eluant to copolymer in the additive is in particular 99: 1 - 10:90, preferably 90:10 - 20:80, especially 80:20 - 50:50.
  • the weight fraction of the flow agent in the additive is greater than the weight fraction of the copolymer.
  • a proportion of the flow agent is in particular 10 to 99% by weight, preferably 40 to 90% by weight, in particular 50 to 80% by weight, based on the total weight of the additive.
  • the proportion of the copolymer in the additive is in particular 1 to 90% by weight, 10 to 60% by weight, especially 20 to 50% by weight, based on the total weight of the additive.
  • the additive can be prepared in liquid or solid form.
  • the additive is in the form of a solution or dispersion, with a proportion of the copolymer and the flow agent together being in particular 10 to 90% by weight, preferably 25 to 65% by weight.
  • the copolymer can be added very well to binder compositions.
  • the additive is prepared in a solid state, in particular in the form of a powder, in the form of pellets and / or plates.
  • Solutions or dispersions of the additive may be e.g. be converted by spray drying in the solid state. It is also possible, for example, flow agents in solid state, e.g. in the form of a powder, as well as copolymers in a solid state, for example, also in the form of a powder to mix together.
  • the present invention relates to the use of an additive as described above as a dispersant for solid particles.
  • solid particles stands for particles of inorganic and / or organic materials. In particular, these are inorganic and / or mineral particles.
  • the additive is used as a dispersant for mineral binder compositions.
  • the additive can be used in particular for liquefaction, for water reduction and / or for improving the processability of a mineral binder composition.
  • the additive can be used to extend the processability of a mineral binder composition.
  • the present invention further relates to a mineral binder composition containing at least one additive as described above.
  • the mineral binder composition contains at least one mineral binder.
  • mineral binder is meant in particular a binder which reacts in the presence of water in a hydration reaction to solid hydrates or hydrate phases. This may be, for example, a hydraulic binder (e.g., cement or hydraulic lime), a latent hydraulic binder (e.g., slag), a pozzolanic binder (e.g., fly ash), or a nonhydraulic binder (gypsum or white lime).
  • a hydraulic binder e.g., cement or hydraulic lime
  • latent hydraulic binder e.g., slag
  • a pozzolanic binder e.g., fly ash
  • nonhydraulic binder gypsum or white lime
  • the mineral binder or the binder composition contains a hydraulic binder, preferably cement.
  • a hydraulic binder preferably cement.
  • Particularly preferred is a cement having a cement clinker content of> 35 wt .-%.
  • the cement is of the type CEM I, CEM II, CEM III, CEM IV or CEM V (according to standard EN 197-1).
  • a 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 .-%, in particular at least 65 wt .-%.
  • the mineral binder to ⁇ 95 wt .-% of hydraulic binder, in particular cement or cement clinker.
  • 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 may contain inert substances such as limestone, quartz flours and / or pigments.
  • the mineral binder contains from 5 to 95% by weight, in particular from 5 to 65% by weight, particularly preferably from 15 to 35% by weight, of latently hydraulic and / or pozzolanic binders.
  • Advantageous latent hydraulic and / or pozzolanic binders are slag and / or fly ash.
  • 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 latent hydraulic and / or pozzolanic binder is particularly preferably 5 to 65 wt .-%, particularly preferably 15 to 35 wt .-%, while at least 35 wt .-%, in particular at least 65 wt .-%, of the hydraulic Binder present.
  • the mineral binder composition is preferably a mortar or concrete composition.
  • the mineral binder composition is a processable and / or waterborne mineral binder composition.
  • a weight ratio of water to binder in the mineral binder composition is preferably in the range from 0.25 to 0.7, in particular 0.26 to 0.65, preferably 0.27 to 0.60, in particular 0.28 to 0.55.
  • the additive is advantageously used in a proportion of 0.01-10% by weight, in particular 0.1-7% by weight or 0.2-5% by weight, based on the binder content.
  • the proportion of the additive refers to the total weight of the additive.
  • An additional aspect of the present invention relates to a molded article, in particular a component of a building, obtainable by curing a mineral binder binder as described above.
  • a building can be eg a bridge, a building, a tunnel, a roadway, or a runway.
  • FIG. 1 shows the time course of the monomer conversions in the preparation of a novel copolymer (CP3);
  • Fig. 2 A schematic representation of a possible structure of a
  • Copolymer which can be derived from the sales according to FIG. 1.
  • the raw materials used for this purpose are commercially available from various suppliers.
  • the structure of the polymer thus produced corresponds to the previously described polymer P with the partial structural units S1, S2 and S3, where:
  • R u and R v are hydrogen
  • the molar ratio of PEGI OOO-OCH3 to PEG3000-OCH3 is 0.205 / 0.153.
  • the molecular weight of the comb polymer (M w ) is about 60 ⁇ 00 g / mol.
  • Viscocrete® Such polymers are also commercially available from Sika Nurse AG under the name Viscocrete®.
  • the copolymer thus obtained is referred to as polymer CP1 and has a block structure in which the side chain-carrying monomer units (methoxy-polyethylene glycol methacrylate) in a first block and the ionizable monomer units (methacrylic acid) are substantially spatially separated in a second block.
  • copolymer CP3 After the substance has completely dissolved, 67 mg of AIBN (0.41 mmol) are added. From now on, the turnover is determined regularly by HPLC. As soon as the reaction, based on methoxy-polyethylene glycol methacrylate, is 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. What remains is a clear, slightly reddish, aqueous solution with a solids content of around 35%. The gradient structure copolymer thus obtained is referred to as copolymer CP3
  • Fig. 1 the time course of the monomer conversions in the preparation of the copolymer CP3 is shown.
  • the monomer conversions were determined by high performance liquid chromatography (HPLC) in a manner known per se at the times indicated in Figure 1 during the preparation of the copolymer.
  • HPLC high performance liquid chromatography
  • copolymer CP3 comprises a first section AA with gradient structure and a further section AB, consisting essentially of side chain-carrying monomer units.
  • additives were prepared by mixing the above-described fluid FM and the copolymers CP1 or CP2. Table 2 gives an overview of the compositions of the prepared additives.
  • the additives are aqueous solutions or dispersions.
  • the cement pastes used for test purposes are based on cement (CEM I 42.5 N, Normo 4, available from Holcim Switzerland) and water.
  • Table 3 gives an overview of the cement paste tests carried out and the results obtained. Experiment V1 is a comparative experiment carried out without addition of a polymer. Table 3: Results of cement branch tests

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Abstract

La présente invention concerne un additif, notamment un agent dispersant pour particules solides, notamment un agent dispersant pour compositions de liant minéral, comprenant : a) un fluidifiant et b) un copolymère présentant une chaîne polymère principale et des chaînes latérales qui s'y rattachent, comprenant au moins une unité monomère M1 ionisable et au moins une unité monomère M2 porteuse de chaînes latérales, le copolymère présentant dans une direction qui s'étend le long de la chaîne polymère principale, une répartition non aléatoire des unités monomères M1 et/ou des unités monomères M2, et le fluidifiant et le copolymère se différenciant d'un point de vue chimique et/ou structural.
EP16775136.1A 2015-09-24 2016-09-22 Additif contenant un fluidifiant et un copolymère Pending EP3353136A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15186763 2015-09-24
PCT/EP2016/072547 WO2017050898A1 (fr) 2015-09-24 2016-09-22 Additif contenant un fluidifiant et un copolymère

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Publication Number Publication Date
EP3353136A1 true EP3353136A1 (fr) 2018-08-01

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EP16775136.1A Pending EP3353136A1 (fr) 2015-09-24 2016-09-22 Additif contenant un fluidifiant et un copolymère

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US (1) US10689303B2 (fr)
EP (1) EP3353136A1 (fr)
JP (1) JP6863971B2 (fr)
CN (1) CN108349825B (fr)
BR (1) BR112018005717B1 (fr)
CO (1) CO2018004250A2 (fr)
MX (1) MX2018003600A (fr)
WO (1) WO2017050898A1 (fr)

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CN111747671A (zh) * 2019-03-26 2020-10-09 Sika技术股份公司 用于干燥砂浆的高减水粉末制剂

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CN108911786B (zh) * 2018-08-21 2021-07-13 西安龙宾立强环保科技有限公司 一种混凝土内养护剂及其制备方法

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JP2018529617A (ja) 2018-10-11
US20190233338A1 (en) 2019-08-01
CN108349825A (zh) 2018-07-31
JP6863971B2 (ja) 2021-04-21
BR112018005717B1 (pt) 2022-07-12
BR112018005717A2 (fr) 2018-10-02
US10689303B2 (en) 2020-06-23
MX2018003600A (es) 2018-08-01
CO2018004250A2 (es) 2018-08-21
WO2017050898A1 (fr) 2017-03-30
CN108349825B (zh) 2021-10-26

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