EP3743397A1 - Agent dispersant servant à réduire les temps de mélange de systèmes à base de liants minéraux - Google Patents

Agent dispersant servant à réduire les temps de mélange de systèmes à base de liants minéraux

Info

Publication number
EP3743397A1
EP3743397A1 EP19700746.1A EP19700746A EP3743397A1 EP 3743397 A1 EP3743397 A1 EP 3743397A1 EP 19700746 A EP19700746 A EP 19700746A EP 3743397 A1 EP3743397 A1 EP 3743397A1
Authority
EP
European Patent Office
Prior art keywords
comb polymer
mineral binder
polymer
water
binder composition
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
EP19700746.1A
Other languages
German (de)
English (en)
Inventor
Weidmann JÜRG
Zimmermann JÖRG
Ulber FABIA
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 EP3743397A1 publication Critical patent/EP3743397A1/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
    • 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
    • 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
    • C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
    • C04B24/2658—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles 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
    • 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
    • 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
    • C04B2103/0059—Graft (co-)polymers
    • C04B2103/006—Comb 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
    • C04B2103/0061—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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00103—Self-compacting mixtures

Definitions

  • the invention relates to the use of a comb polymer as a dispersing agent in mineral binder compositions.
  • the invention further relates to a process for the production of mortar and concrete with a reduced mixing time.
  • SCC Soif Compacting Concrete
  • HPC High Performance Concrete
  • UHPC Ultra High Performance Concrete
  • HPC and UHPC are characterized by very good processability, high strength, above 60 MPa or above 80 MPa and above, and high durability.
  • High-strength and ultra high-strength concretes allow significantly smaller component dimensions, which saves space and reduces transport costs.
  • These special concretes and mortars contain a high proportion of mineral binders and fines below 0.125 mm.
  • This high proportion of flour meal that is the sum of all fines, including cement and others mineral binders, with particle sizes below 0.125 mm, is characteristic of SCC, HPC and UHPC.
  • the high proportion of fines causes a good homogeneity of the concretes and the high proportion of mineral-based binder causes high strength.
  • High-strength concretes and mortars also have little to very little water, because water that is not needed for cement hydration evaporates and leaves pores that reduce its strength.
  • the W / Z value which is the mass ratio of water to cement, is usually between 0.45 and 0.60, for HPC and UHPC the W / Z is significantly below 0.40, often below 0.30 or 0.25.
  • the W / C at SCC is also deep, because too much water can lead to inhomogeneity, bleeding of cement paste and sedimentation, which disturbs the self-compacting properties.
  • Concrete and mortar with high fines content and low water are generally sticky and difficult to process and can only be processed with the addition of particularly effective dispersants.
  • Dispersants or plasticizers are used in the construction industry as flow agents or water-reducing agents for mineral binder compositions.
  • the dispersants are generally organic polymers which are added to the make-up water or added as a solid to the binder compositions.
  • both the consistency of the binder composition during processing and the properties in the cured state advantageously to be changed.
  • polycarboxylate-based comb polymers are known. Such comb polymers have a polymer backbone with acid groups and polyether side chains. They will usually contain the acid groups by free radical copolymerization of monomers and of monomers
  • Another possibility for the preparation consists in a polymer-analogous esterification and / or amidation of polymers containing carboxyl groups with polyethers which have at one end a hydroxyl group or an amino group.
  • the acid groups and the side chains are randomly distributed along the polymer backbone.
  • Some liquefiers can partially liquefy SCC, HPC and UHPC, but also with them the concrete must be mixed for a very long time until it is homogeneous and easy to process.
  • WO2015 / 144886 describes a block copolymer as a dispersant for mineral binder compositions which is an effective
  • WO 2017/050907 describes a copolymer with gradient structure as dispersing agent for mineral binder compositions which enables effective liquefaction and good processing and maintains the effect over as long as possible.
  • the prior art does not provide a cost effective and simple solution for reducing mixing times, especially mineral binder compositions having a high content of cement and / or flour meal and a small amount of water.
  • the dispersant should also be usable with other additives.
  • the dispersant should be particularly suitable for high-strength (HPC) and ultra high-strength concrete (UHPC) and high-strength and ultra-high-strength mortar andsver sealing concrete (SCC).
  • the gist of the invention resides in the use of a comb polymer K for shortening the mixing time of a mineral binder composition with water, wherein the comb polymer K has a polymer backbone and side chains, wherein the comb polymer K comprises at least one monomer unit M1 comprising acid groups and at least one monomer unit M2 Side chains, wherein the monomer units M1 and M2 are arranged in a non-random sequence along the polymer backbone.
  • mineral binder compositions especially if they have a high content of cement and / or flour meal and a small amount of water, require a significantly shorter mixing time until they are homogeneous and fluid when using a comb polymer K with non-random sequence along the monomer units of the polymer backbone, as compositions containing conventional comb polymers.
  • mineral binder compositions are well compatible.
  • the invention relates to the use of a comb polymer K for shortening the mixing time of a mineral binder composition with water, wherein the mixing time is shortened compared to the mixing time of an identical mineral binder composition comprising a comb polymer with random sequence of the monomer units along the polymer backbone and no comb polymer K, wherein the binder together the comb polymer K has a polymer backbone and side chains, wherein the comb polymer K comprises at least one monomer unit M1 comprising acid groups and at least one monomer unit M2 comprising side chains, wherein the monomer units M1 and M2 present in a non-random sequence along the polymer backbone.
  • mixing time in the present document is understood to mean the time interval between the addition of the water to the dry mineral binder composition and the achievement of a homogeneous mixture lies.
  • homogeneous mixture is understood as meaning a mixture which is free of non-wetted powders, tubers and other material packs. In particular, the homogeneous mixture is flowable.
  • the time of reaching a homogeneous mixture can be determined by different methods.
  • a skilled practitioner can determine whether or not it is homogenous by looking at the mixed binder composition. The person can still estimate by mixing a blade by hand through the mixture their mixing resistance and flow behavior and thereby assess the completeness or incompleteness of the mixing.
  • a mixing tool can be equipped with a power meter.
  • the required power increases for a given number of revolutions and then drops to a relatively stable value as soon as the mixture is homogeneous and the mixing process is complete.
  • mineral binder composition in the present document is meant a composition containing at least one mineral binder.
  • flour meal the fines of a mineral's binder composition.
  • the flour meal contains cement, fly ash, blastfurnace slag, metakaolin, silica fume, quartz powder, fine calcium carbonate and / or inert rock flour and further, in the binder composition existing fine mineral powder with a
  • non-statistical sequence of the monomer units is understood in the present document, a distribution of the monomer units, which is not obtained randomly. That is, it is not obtained under the usual conditions of a free radical copolymerization or a polymer-analogous reaction. At least one monomer unit is enriched in the non-random sequence in at least a portion of the polymer backbone.
  • Such copolymers are, for example, block copolymers or else
  • a "statistical sequence of the monomer units” is correspondingly understood to mean a distribution of the monomer units which arises statistically, corresponding to the reactivities of the monomers.
  • a statistical sequence of the monomer units is obtained under the usual conditions of a free radical copolymerization or a polymer-analogous reaction.
  • the use of the comb polymer K allows a shortened mixing time of a mineral binder composition with water.
  • the mixing time is, in particular compared to a comparative mixture containing a comb polymer with random sequence of the monomer units and no comb polymer K, shortened.
  • the mineral binder composition tion containing the comb polymer K and the comparison mixture at the end of the mixing time on a comparable good workability.
  • the mixing time is reduced by at least 20%, preferably at least 25%, especially at least 30%, as compared to a mixing time of the mineral binder composition comprising a comb polymer having a random sequence of the monomer units along the polymer backbone and no comb polymer K; Binder compositions mixed with water were identical except for the comb polymer
  • the use of the comb polymer K is particularly effective when the comparative blend containing a comb polymer having a random sequence of the monomer units along the polymer backbone has a mixing time greater than 3 minutes, especially greater than 4 minutes.
  • a comparable good processability is given when the flow, measured as slump flow according to J IS A 1 150, the mineral binder compositions after the end of the mixing time is at least 55 cm, and the difference in the flow mass of the binder compositions is at most 12 cm, both mixtures having the same water content.
  • the fluidity is adjusted in particular by a dosage of the comb polymer.
  • the mineral binder composition contains at least one mineral binder.
  • a suitable mineral binder is in particular a mineral binder which reacts in the presence of water in a Flydratationsre force to solid hydrates or hydrate phases.
  • This may in particular a hydraulic binder, which is hardenable with water under water, in particular cement or a latent hydraulic binder, which sets under the action of additives with water, such as in particular blastfurnace slag, or a pozzolanic binder, in particular fly ash or silica fume, his.
  • a hydraulic binder which is hardenable with water under water, in particular cement or a latent hydraulic binder, which sets under the action of additives with water, such as in particular blastfurnace slag, or a pozzolanic binder, in particular fly ash or silica fume, his.
  • the mineral binder composition preferably comprises at least one hydraulic binder, preferably a cementitious binder.
  • cements classified under DIN EN 197-1 Portland cement (CEM I), Portland cement cement (CEM II), blast-furnace cement (CEM III), pozzolana cement (CEM IV) and composite cement (CEM V), or cements classified in Japanese Standard JIS, especially in JIS R 5210, JIS R 521 1, JIS R 5212 or JIS R 5213.
  • CEM I Portland cement
  • CEM II Portland cement cement
  • CEM III blast-furnace cement
  • CEM IV pozzolana cement
  • CEM V composite cement
  • cements classified in Japanese Standard JIS especially in JIS R 5210, JIS R 521 1, JIS R 5212 or JIS R 5213.
  • cements produced according to an alternative standard such as the ASTM standard or the Indian Standard, are equally suitable.
  • Special cements such as calcium sulfoaluminate cement and calcium aluminate cement, or mixtures thereof, optionally in a mixture with calcium sulfate, are also suitable.
  • Portland cement or a cement containing portland cement according to DIN EN 197-1.
  • Portland cement is particularly readily available and allows concrete and mortar with good properties.
  • a Portland cement with a lower proportion of C3S and C3A is advantageous. Such cements cure slower and thus produced components, especially those with a large volume, are less hot during curing, which is advantageous because excessive heat can lead to cracks.
  • a proportion of the hydraulic binder in the total mineral binder is preferably at least 5% by weight, in particular at least 20% by weight, more preferably at least 35% by weight, in particular at least 65% by weight with a maximum content of 100% by weight.
  • the mineral-specific binder consists of 95 to 100% by weight of hydraulic binder, in particular of cement clinker.
  • the binder composition contains other binders in addition to or instead of a hydraulic binder.
  • binders in particular latent hydraulic binders and / or pozzolanic binders.
  • Suitable latent-hydraulic and / or pozzolanic binders are, in particular, granulated blastfurnace, fly ash and / or silica fume.
  • the mineral binder contains from 5 to 95% by weight, in particular from 10 to 65% by weight, particularly preferably from 15 to 40% by weight, of latently hydraulic and / or pozzolanic binders.
  • Advantageous latent hydraulic and / or pozzolanic binders are granulated slag, silica fume 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 granulated slag, silica fume and / or fly ash.
  • the proportion of the latently hydraulic and / or pozzolanic binder is preferably 5 to 65% by weight, more preferably 15 to 40% by weight, while at least 35% by weight, in particular at least 60% by weight, of the hydraulic binder.
  • Special concretes, such as SCC or high-strength and ultra-high-strength concretes and mortars are known to the person skilled in the art. They preferably have a high content of mineral binder, in particular more than 350 kg / m 3 . Thus, good homogeneity, processing properties and / or high strengths can be achieved.
  • the mineral binder composition mixed with water preferably has a content of mineral binder in the range from 450 to 1,600 kg / m 3 , preferably 500 to 1,500 kg / m 3 .
  • the content of mineral binder is in the range of 450 to 800 kg / m 3 , preferably 500 to 700 kg / m 3 , in particular 550 to 650 kg / m 3 .
  • Binder compositions having such levels of mineral binder are especially suitable for SCC concrete.
  • a content of mineral binder in the range of 550 to 1500 kg / m 3 , more preferably 650 to 1400 kg / m 3 , in particular 700 to 1300 kg / m 3 , in particular 750 to 1200 kg / m 3 .
  • Binder compositions containing such levels of mineral binder are especially suitable for high strength (HPC) and ultra high strength concrete (UHPC) and high strength and ultra high strength mortar.
  • the mineral binder composition preferably contains fine additives.
  • Suitable additives are chemically inert or reactive fine-grained mineral substances such as ground minerals, fly ash, silica fume, blastfurnace slag, fibers or colored pigments.
  • the mineral binder composition further preferably contains aggregate.
  • aggregate are in particular chemically inert solid particulate materials and are offered in various shapes, sizes and as different materials that vary from sand particles to large coarse stones. In principle, all sands and gravels are the usual way to be used for concrete and mortar.
  • the particle size depends on the application, whereby particle sizes up to 32 mm and more are suitable.
  • Such particle sizes are especially suitable for concrete.
  • the maximum particle size may also be smaller, preferably not more than 4 mm, in particular 3 mm or 2 mm. Such particle sizes are especially suitable for mortar.
  • Fine additives and aggregates of different particle sizes are preferably mixed to optimally adjust the properties of the mineral binder composition. Such mixtures are known in the art.
  • the mineral binder composition preferably contains a level of flour meal of 450 to 2000 kg / m 3 , more preferably 500 to 1800 kg / m 3 , even more preferably 550 to 1600 kg / m 3 .
  • the proportion of mineral binding agent in the flour meal is preferably at least 60% by weight, in particular special at least 80% by weight, with a maximum proportion of 100% by weight.
  • the flour meal has a Blaine fineness of at least 1 ⁇ 00 cm 2 / g, in particular at least 1 '500 cm 2 / g, preferably at least 2'500 cm 2 / g, even more preferably at least 3500 cm 2 / g or at least 5 ⁇ 00 cm 2 / g, on.
  • the mineral binder composition may contain, in addition to the comb polymer K, at least one additive, for example a concrete additive and / or a mortar additive and / or process chemicals.
  • the at least one additive comprises a dispersant, defoamer, wetting agent, dye, preservative, flow agent, retarder, accelerator, polymer, air entrainer, rheology aid, viscosity modifier Pumping aid, a shrinkage reducer or a corrosion inhibitor, or combinations thereof.
  • the mineral binder composition is preferably a mortar or concrete composition, in particular self-compacting concrete, high-strength or ultrahigh-strength concrete or high-strength or ultra-high-strength mortar.
  • the mineral binder composition is a processable and waterborne mineral binder composition.
  • the amount of water with which the mineral binder composition is mixed is preferably as low as possible, because too much water the
  • the weight ratio of water to mineral binder is advantageously in the range from 0.10 to 0.40, preferably 0.1 to 0.35, more preferably 0.12 to 0.32, in particular 0.13 to 0.30, in particular 0.14 to 0.28.
  • Such water to binder ratios are especially well suited to obtain high to very high strength in concrete.
  • the weight ratio of water to a quantity of flour meal contained in the binder composition is preferably in the range from 0.12 to 0.35, preferably 0.13 to 0.30, in particular 0.14 to 0.25.
  • the water-mixed mineral binder composition is a high-strength (HPC) or ultra-high-strength concrete (UHPC) or a high-strength or ultra-high-strength mortar.
  • HPC high-strength
  • UHPC ultra-high-strength concrete
  • the mineral binder composition mixed with water is a self-compacting concrete (SCC).
  • SCC self-compacting concrete
  • the comb polymer K is advantageously in a proportion of 0.01 to 10
  • % By weight, in particular 0.1 to 7% by weight or 0.2 to 5% by weight, based on the content of mineral binder used.
  • the comb polymer K comprises a polymer backbone and side chains.
  • the polymer backbone is substantially linear and has virtually no branching.
  • the monomer unit M1 comprises acid groups, in particular carboxylic acid, sulfonic acid, phosphoric acid and / or phosphonic acid groups.
  • the side chain-carrying monomer unit M2 preferably comprises polyalkylene oxide side chains, in particular polyethylene oxide and / or polypropylene oxide side chains and / or side chains which are composed of ethylene oxide and propylene oxide.
  • the monomer unit M1 preferably has the formula I,
  • R 1 in each case independently of one another, is -COOM, -SO 2 -OM, -O-PO (O) 2 and / or -PO (OM) 2,
  • R 2 and R 5 are H, -CH 2 COOM or an alkyl group having 1 to 5 carbon atoms,
  • R 3 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,
  • M independently 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;
  • X each independently of one another, represents -O-, NH- or -NR 8 -,
  • R 8 each independently of one another, represents a group of the formula - [AOjn-R a ,
  • A is C 2 -C 4 -alkylene
  • R a is H, a C 1 - to C 20 -alkyl group, -cyclohexyl group or -alkylaryl group
  • n 2 to 250, in particular 10 to 200.
  • the comb polymer K can be produced on the basis of acrylic or methacrylic acid monomers, which is interesting from an economic point of view.
  • the comb polymers in the present context results in a short mixing time with good dispersing effect and little delay in the setting time.
  • Such comb polymers can be produced on the basis of maleic acid monomers.
  • R 5 H or -CH 3
  • X -O-.
  • Such comb polymers can be prepared, for example, starting from acrylic acid or methacrylic acid esters, vinyl, methallyl, allyl or isoprenol ethers.
  • R 2 and R 5 are each mixtures of 40 to 60 mol% H and 40 to 60 mol% -CH 3.
  • R 1 -COOM
  • R 2 H
  • R 5 -CHs
  • R 1 -COOM
  • the group - [AO] n - in monomer unit M2 is, based on all groups - [AO] n - in comb polymer K, preferably at least 50 mol%, in particular at least 75 mol%, preferably at least 95 mol% or at least 99 mole%, of a polyethylene oxide.
  • a proportion of ethylene oxide units based on all alkylene oxide units in the comb polymer K is in particular more than 75 mol%, in particular more than 90 mol%, preferably more than 95 mol% and in particular 100 mol%.
  • the group - [AO] n - has essentially no hydrophobic groups, in particular 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
  • n 10 to 150
  • n 15 to 100
  • n 17 to 70
  • n 19 to 45
  • n 20 to 25.
  • n 10 to 150
  • n 15 to 100
  • n 17 to 70
  • n 19 to 45
  • R 1 COOM
  • R 2 H or -CHs
  • R 5 H or -CHs
  • comb polymers of this kind can be produced with a polyethylene oxide terminated on one side with a methoxy group.
  • Monomers having this structure are well suited to prepare comb polymers with non-random distribution of the monomers, with suitable polymerization methods.
  • the comb polymer K comprises at least one further monomer unit MS, which differs in particular from the monomer units M1 and M2 chemically.
  • several different further monomer units MS can be present.
  • the properties of the comb polymer K can be 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 III:
  • R 5 ' , R 6' , R 7 ' , m' and p ' are defined as R 5 , R 6 , R 7 , m and p;
  • Y each independently, is a chemical bond or -O-;
  • Z each independently, is a chemical bond, -O- or -NH-;
  • R 9 each independently of one another, is H, 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.
  • the monomer unit MS is advantageously present in 0 to 50 mol%, preferably 1 to 40 mol%, especially 2 to 30 mol%, in particular 5 to 20 mol%, based on the sum of all monomer units in the comb polymer K.
  • the comb polymer K is at least 50 mol%, more preferably at least 75 mol%, especially at least 90 mol% or 95 mol%, of monomer units M1 and monomer units M2.
  • a plurality of different monomer units M1 of the formula I and / or a plurality of different monomer units M2 of the formula II can be present.
  • the comb polymer K preferably has a polydispersity of less than 1.5, preferably in the range from 1.0 to 1.4, in particular in the range from 1.1 to 1.3.
  • polydispersity is meant the ratio of weight average molecular weight Mw to number average molecular weight Mn, both in g / mol.
  • the weight-average molecular weight Mw of the entire comb polymer K is in particular in the range from 8 ⁇ 00 to 100 ⁇ 00 g / mol, advantageously 10 ⁇ 00 to 80 ⁇ 00 g / mol, in particular 12 ⁇ 00 to 50 ⁇ 00 g / mol.
  • molecular weights such as weight average molecular weight Mw and number average molecular weight Mn are determined by gel permeation chromatography (GPC) with polyethylene glycol (PEG) as a standard.
  • the monomer units M1 and M2 are arranged in a non-statistical sequence along the polymer backbone.
  • At least one monomer unit M1 or M2 is enriched in at least one section of the polymer chain.
  • the comb polymer K consists of at least one section A, whereby the monomer unit M1 or the monomer unit M2 occurs enriched in the section A.
  • the monomer unit M1 comprising acid groups is enriched in at least one section.
  • the comb polymer K has a high charge density in this section, which is especially advantageous for a short mixing time.
  • the monomer unit M2 comprising side chains is enriched in at least one section. This can locally a high density of side chains can be achieved, which can bring about a particularly good steric dispersing effect.
  • the comb polymer K comprises a portion A in FIG.
  • section A at least 30 mol%, more preferably at least 40 mol%, in particular at least 50 mol%, in particular at least 60 mol% of all monomer units M2
  • both the monomer unit M1 and the monomer unit M2 is enriched in at least one section.
  • the comb polymer K consists of the at least one section A, wherein the monomer unit M1 occurs enriched in the section A and from a further section B, wherein the monomer unit M2 enriched in the section B occurs.
  • the comb polymer K contains at least two different sections A and / or at least two under different further sections B.
  • the comb polymer K monomer units MS wherein the monomer unit MS may be present in each section of the comb polymer K. Preferably, it is statistically installed in the respective section.
  • the monomer unit MS is enriched in a section, for example, sections in which either the Monomer unit M1 and / or the monomer unit M2 enriched each present spatially separated from each other.
  • the structure of copolymers can be analyzed and determined by nuclear magnetic resonance (NMR) spectroscopy.
  • NMR nuclear magnetic resonance
  • 13 C-NMR and 1 H NMR spectroscopy can be determined in a conventional manner due to neighboring group effects in the copolymer and based on statistical evaluations, the sequence of the monomer units in the copolymer.
  • the comb polymer K is a block copolymer or a gradient structure copolymer.
  • Exemplary block copolymers are described in WO2015 / 144886 and exemplary gradient polymers in WO 2017/050907.
  • the comb polymer K is a block copolymer and comprises
  • any existing proportion of monomer units M2 in the first section A 'is smaller is 25 mol%, in particular less than or equal to 10 mol%, based on all monomer units M1 in the first section A 'and where any existing proportion of monomer units M1 in the second section B' is less than 25 mol%, in particular less than or equal to 10 mol%, based on all monomer units M2 in the second section B '.
  • the sections A 'and B' may comprise the same or different number of monomer units.
  • the sections A 'and B' are not the same size.
  • the comb polymer can be selectively varied in its structure.
  • the monomer units M1 and any further monomer units in the first section A ' are present in particular randomly or randomly distributed.
  • the monomer units M2 and any further monomer units are present in the second section B 'in particular randomly or randomly distributed.
  • the at least one section A 'and / or the at least one section B' is preferably present in each case as a partial polymer with random monomer distribution.
  • the first section A ' comprises 25 to 35 monomer units M1 and / or the at least one second section B' comprises 10 to 20 monomer units M2.
  • the comb polymer K is a gradient polymer and has a gradient structure in at least one section A "in a direction along the polymer backbone with respect to the monomer unit M1 and / or the monomer unit M2.
  • the gradient polymer is at least one
  • Section A in a direction along the polymer backbone with respect to the monomer unit M1 and / or with respect to the monomer unit M2 a concentration gradient ago.
  • 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 is “concentration gradient”.
  • a local concentration of the at least one monomer unit M1 continuously increases along the polymer backbone, while a local concentration of the at least one monomer unit M2 continuously decreases along the polymer backbone, or vice versa.
  • a local concentration of the monomer unit M1 at the first end of the at least one section A is in particular lower than at the second end of the section A", while a local concentration of the monomer unit M2 at the first end of the section A "is greater than at the second end of the section A ", or vice versa.
  • the at least one section A " based on a total number of monomer units in the polymer backbone, has a proportion of at least 30%, in particular at least 50%, preferably at least 75% or 90%, of monomer units.
  • the comb polymer K preferably has, in addition to the at least one section A ", which has a gradient structure over a further section B", over the entire section B "essentially a constant local concentration of the monomers and / or a random or random distribution of the monomers is present.
  • Section B may e.g. consist of mono mers of a single variety or of several different monomers, which are statistically distributed. In section B ", however, in particular there is no gradient structure or no concentration gradient along the polymer backbone.
  • the comb polymer K may also have more than one further portion B ", e.g. two, three, four or even more sections B ", which may differ chemically and / or structurally.
  • the at least one section A "connects directly to the further section B".
  • the comb polymer K can advantageously be prepared by a controlled free radical polymerization and / or by a living free radical polymerization of corresponding monomers m1, m2 and ms, which form the monomer units M1, M2 and MS in the polymer.
  • the techniques for controlled free radical polymerization and / or living free radical polymerization include nitroxide mediated polymerization (NMP), atom transfer radical polymerization (ATRP) or Reversible Addition Fragmentation Chain Transfer Polymerization (RAFT). Preference is given to the RAFT polymerization.
  • NMP nitroxide mediated polymerization
  • ATRP atom transfer radical polymerization
  • RAFT Reversible Addition Fragmentation Chain Transfer Polymerization
  • Suitable preparation methods and exemplary comb polymers K are described in WO2015 / 144886 and WO 2017/050907.
  • Living free radical polymerization occurs essentially in the absence of irreversible transfer or termination reactions.
  • the number of active chain ends is low and remains substantially constant during the polymerization. This is achieved, for example, in RAFT polymerization by the use of a RAFT agent and only a small amount of initiator. This allows substantially simultaneous growth of the chains throughout the polymerization process. This gives rise to the possibility of preparing block or gradient polymers with this process, and correspondingly results in a narrow molecular weight distribution or polydispersity of the polymer.
  • a) the monomer m1 or the monomer m2 is reacted with an initiator, in particular azobisisobutyronitrile (AIBN), s, s'-azodiisobutyramidine dihydrochloride (AAPH) or azo-bis-isobutyramidine (AIBA), in the presence a RAFT agent, in particular a dithioester, dithiocarbamate, trithiocarbonate or xanthate, polymerized in water under inert gas atmosphere at 70 to 95 ° C to a reaction conversion of 60 to 80 mol% and ansch manend in a further step b) the corresponding other Monomer, m2 or m1, respectively.
  • an initiator in particular azobisisobutyronitrile (AIBN), s, s'-azodiisobutyramidine dihydrochloride (AAPH) or azo-bis-isobutyramidine (AIBA)
  • AIBN azobisisobutyroni
  • the addition of the other monomer can be carried out in one step or continuously over a period of time or in stages.
  • a comb polymer K consisting of a portion containing the monomer unit M1 and no monomer units M2 or vice versa is obtained, and another portion containing the second monomer enriched and in which both monomers are randomly or in gradient form ,
  • advantageous comb polymers K which contain only monomer unit M1 or M2 in a section at one end of the polymer chain can be obtained.
  • the optional monomer ms can already in the first reaction step a), together with monomer m1 or the monomer m2, or in the further reaction step b), together with the second monomer m2 or m1, or in a reaction step c), between Reaction step a) and reaction step b), or subsequently to reaction step b), in a reaction step c ') are added.
  • the reaction conversion can in this case, for example by means of high-performance liquid chromatography (HPLC) on the decrease in the monomer concentrations in the polymerization be determined.
  • HPLC high-performance liquid chromatography
  • a preferred comb polymer K can be prepared, for example, by living free radical polymerization, in particular by RAFT polymerization, of acrylic acid and / or methacrylic acid as monomer m1 with methoxy-polyethylene glycol methacrylate as monomer m2 and optionally hydroxyethyl acrylate or hydroxyethyl methacrylate as monomer ms.
  • the methoxy-polyethylene glycol methacrylate preferably contains 10 to 15 oxyethylene units.
  • the molar ratio of m1: m2: ms in the reaction is preferably 1.5-4: 1: 0-3.
  • the reaction is preferably carried out in water under a protective gas atmosphere, in particular under N 2 or Ar, at a temperature of 70 ° C. to 95 ° C.
  • the mineral binder composition contains, in addition to the comb polymer K, at least one further dispersant.
  • further properties of the mineral binder composition such as, for example, the processability and processing time, can be set in a targeted manner. Also, such blends are economically useful.
  • the at least one further dispersant is preferably a flow agent for concrete or mortar.
  • suitable flow agents are lignosulfonates, sulfonated naphthalene-formaldehyde condensates, sulfonated melamine-formaldehyde condensates, phenol condensates containing polyalkylene oxide chains and acid groups, sulfonated vinyl copolymers, polyalkylene glycols having phosphonate groups, polyalkylene glycols having phosphate groups, polycarboxylates or comb polymers anionic groups and polyether side chains.
  • the at least one further dispersant is a further comb polymer.
  • the further comb polymer has anionic groups and polyalkylene oxide side chains, wherein the anionic groups are selected from carboxylate groups, sulfonate groups, phosphonate groups or phosphate groups, and wherein the
  • Monomer units of the further comb polymer are arranged purely statistically along the polymer backbone.
  • a preferred further comb polymer is a comb polymer prepared by conventional free-radical copolymerization or by polymer-analogous esterification / amidation and which comprises carboxylate groups and side chains of polyethylene oxide attached to the polymer backbone via ester, ether, imide and / or amide groups ,
  • the mineral binder composition preferably also contains a dispersant, preferably a further comb polymer, wherein the monomer units of the further comb polymer are present randomly distributed along the polymer backbone.
  • the comb polymer K and the further dispersant are present in a blend prior to being added to the mineral binder composition.
  • a greatly shortened mixing time can be achieved with very good processability.
  • the mixing ratio of comb polymer K to the further dispersing agent is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, in particular 3.5: 1 to 1: 3.5, based on dry polymers.
  • the comb polymer K may be in liquid or solid form.
  • the comb polymer K is particularly preferably present as constituent of a solution or dispersion, with a proportion of the comb polymer K being in particular 10 to 90% by weight, preferably 20 to 65% by weight, or 25 to 50% by weight.
  • the comb polymer K for example, can be added very well to binder compositions.
  • a solution or dispersion may comprise 20 wt% comb polymer K and 5 to 10 wt% further dispersant, or 15 wt% comb polymer K and 30 wt% further dispersant, or 10 wt% comb polymer K and 10 to 20% by weight of further dispersing medium.
  • the comb polymer K is in solid state, in particular in the form of a powder, in the form of pellets or in the form of plates.
  • the powder may be added to the dry binder composition, the wet binder composition or the make-up water.
  • the comb polymer K may advantageously be present in admixture with the further dispersant.
  • the comb polymer K may be added as a powder to a dry concrete or mortar ready mix.
  • Such polymer powders are by drying, in particular spray drying, an aqueous polymer solution or dispersion or by grinding a solidified polymer melt available.
  • additives such as, for example, stabilizers, in particular oxidation stabilizers, or carrier material, can be added to the polymer, which increase the storage stability of the powder.
  • the invention relates to a process for producing a concrete or mortar by mixing a dry mineral binder composition with water and a
  • Comb polymer K as described above, characterized in that the mixing time of the binder composition containing the comb polymer K, in comparison to the mixing time of a mineral binder composition tion containing a comb polymer with random sequence of
  • Monomer units along the polymer backbone and no comb polymer K is reduced, preferably by at least 20%, in particular by at least 25%, in particular by at least 30%, the water-mixed binder compositions except for the comb polymer having an identical composition and comparable good processability End of the mixing time exhibit.
  • the mixing of a dry mineral binder composition with water and a comb polymer K, as described above, can be continuous or discontinuous. Suitable mixing units are known per se to the person skilled in the art. Mixing units can contain dynamic and / or static mixing elements. In a preferred
  • Embodiment static mixer are used.
  • dynamic mixing units are used.
  • suitable mixing units are horizontal single shaft mixers, twin shaft mixers, vertical mixers, ribbon mixers, rotary mixers,
  • the weight ratio of water to mineral binder is in the range of 0.10 to 0.40, preferably 0.1 to 0.35, more preferably 0.12 to 0.32, especially 0.13 to 0.30, in particular 0.14 to 0.28 , and / or the weight ratio of water to a amount of flour meal contained in the binder composition in the range of 0.12 to 0.35, preferably 0.13 to 0.30, in particular 0.14 to 0.25.
  • Binder composition has a content of mineral binder of more than 350 kg / m 3 , preferably 450 to 1600 kg / m 3 , a content of flour meal of 450 to 2000 kg / m 3 and a weight ratio of water to
  • the invention relates to a water-blended mineral binder composition, particularly a self compacting concrete (SCC), a high strength concrete (HPC), an ultra high strength concrete (UHPC), or a high strength or ultra high strength mortar containing at least one as above described, comb polymer K.
  • SCC self compacting concrete
  • HPC high strength concrete
  • UHPC ultra high strength concrete
  • mortar containing at least one as above described, comb polymer K.
  • 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 composition as described above.
  • a building can be eg a bridge, a building, a tunnel, a roadway, or a runway. From the following embodiments, there are more
  • the weight average molecular weight Mw and the polydispersity of the polymers were determined by gel permeation chromatography (GPC)
  • Polyethylene glycol determined as standard.
  • RI detector 2414 from Waters, USA
  • the solids content of the polymer solutions was determined using a halogen dryer type HG 63 from Mettler Toledo, Switzerland.
  • the molar ratio of methacrylic acid to methoxy-polyethylene glycol methacrylate is 3.7.
  • the molecular weight M w of the polymer is 24 ⁇ 00 g / mol and the polydispersity 1.2.
  • Thermometer and inlet nozzle for the solutions were charged to 100 g of water and heated to 90 ° C. With stirring and heating to 85-90 ° C, the solutions were added from the feed containers by means of metering pumps via separate inputs simultaneously and evenly within 4 hours. After completion of the dosing, the reaction mixture was stirred for a further 30 minutes at 85-90 ° C. After cooling, the pH of the Solution is adjusted to 5 by adding a 30% by weight NaOH solution. The solid content of the solution was adjusted to 30% by weight by adding water.
  • the molar ratio of acid monomer to methoxy-polyethylene glycol methacrylate is 5.9.
  • the molecular weight M w of the polymer is 32 ⁇ 00 g / mol and the polydispersity 2.4.
  • Copolymer P3 was obtained by polymer-analogous esterification of a copolymer of acrylic acid and methacrylic acid (average molecular weight Mw of about 4 ⁇ 00) with methoxy-polyethylene glycol-3000 (one-sided with a methoxy group-terminated polyethylene glycol having an average molecular weight Mw of 3000). The solid content of the solution was adjusted to 30% by weight by adding water.
  • the molar ratio of acid groups to polyethylene glycol chains in the polymer is 4.5.
  • the molecular weight M w of the polymer is 48 ⁇ 00 g / mol and the polydispersity 2.4.
  • Copolymer P4 was prepared by polymer-analogous esterification of a copolymer of acrylic acid and methacrylic acid (average molecular weight Mw of about 4 ⁇ 00) with methoxy-polyethylene glycol-1000 (one-sided with a methoxy group-terminated polyethylene glycol having an average molecular weight Mw of 1000) and methoxy-polyethylene glycol-3000 (one-sided with a methoxy group-terminated polyethylene glycol having an average molecular weight Mw of 3,000). The solid content of the solution was adjusted to 20% by weight by adding water.
  • the molar ratio of acid groups to polyethylene glycol chains in the polymer is about 1.6.
  • the molecular weight M w of the polymer is 30 ⁇ 00 g / mol and the polydispersity 2.6. 3. Tests in concrete mixtures
  • the mixing time was determined as follows:
  • the mixing time is the time interval between the addition of water and the achievement of a homogeneous, soft and flowable consistency of the concrete, with only the pure mixing time is counted without the stop times.
  • the air content of the concrete mixture was determined according to J IS A 1 128.
  • the flow was determined as slump flow according to J IS A 1 150.
  • the 50 cm flow time is determined together with the slump flow and is the time required for the concrete to reach a diameter of 50 cm after lifting the slump cone.
  • the L-Flow test indicates the flow rate of the concrete and is a measure of the concrete viscosity. It was measured according to JSCE-F-514.
  • the concrete mixture used for test purposes in test series 1 has the composition described in Table 1.
  • Table 1 The concrete mixture used for test purposes in test series 1 has the composition described in Table 1.
  • Table 2 shows the comb polymers used and their dosage as well as the mixing times required for a homogeneous mixture and the fresh concrete properties of the concrete mixtures.
  • Table 4 shows the comb polymers used and their dosage, as well as the mixing times required for a homogeneous mixture and the fresh concrete properties of the concrete mixtures.
  • Concrete production Cement, blastfurnace slag, silica fume and sand were mixed in a compulsory mixer for 30 seconds and then the water in which the polymer was dissolved was added. The concrete was then mixed according to Table 6, 6 or 3 minutes. Subsequently, the fresh concrete properties were determined. All concrete mixtures were prepared with the same concrete mixer.
  • the slump flow was determined according to DIN EN 12350-2 immediately after mixing and after 30 minutes.
  • the homogeneity of the mixture after the predetermined mixing time was assessed visually and rated grades between 1 and 5, with 1 being inhomogeneous and 5 being completely homogeneous.
  • the concrete mixture used for test purposes in test series 3 has the composition described in Table 5.
  • Table 6 shows the comb polymers used and their dosage, as well as the mixing times and the fresh concrete properties of the concrete mixtures. Table 6

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Graft Or Block Polymers (AREA)
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Abstract

L'invention concerne l'utilisation d'un polymère en peigne K pour réduire le temps de mélange d'une composition à base de liant minéral avec l'eau, le polymère en peigne K possédant un squelette et des chaînes latérales, ledit polymère en peigne K comprenant au moins un motif monomère M1, portant des groupes acide, ainsi qu'au moins un motif monomère M2, possédant des chaînes latérales, lesdits motifs monomères M1 et M2 étant disposés en une séquence non statistique le long du squelette du polymère.
EP19700746.1A 2018-01-24 2019-01-22 Agent dispersant servant à réduire les temps de mélange de systèmes à base de liants minéraux Pending EP3743397A1 (fr)

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EP1138696A1 (fr) 2000-03-29 2001-10-04 Sika AG, vorm. Kaspar Winkler & Co. Polymères pour compositions dispersantes pour ciment
DE10237286A1 (de) 2002-08-14 2004-02-26 Degussa Construction Chemicals Gmbh Verwendung von Blockcopolymeren als Dilpergiermittel für wässrige Feststoff-Suspensionen
FR2894998A1 (fr) * 2005-12-16 2007-06-22 Coatex Sas Procede de fabrication de sauces de couchage a la retention d'eau et a la viscosite brookfield ameliorees mettant en oeuvre un polymere peigne avec au moins une fonction greffee oxyde de polyalkylene.
JP5305746B2 (ja) 2008-06-12 2013-10-02 花王株式会社 水硬性組成物
EP2522680B1 (fr) 2011-05-10 2013-08-07 Sika Technology AG Polymère composé d'acide maléique, allylester et (méth-)acryle, sa fabrication et son utilisation
EP2535362A1 (fr) * 2011-06-17 2012-12-19 Sika Technology AG Utilisation de polymères en peigne comme agent dispersant pour un liant activé de manière alcaline
EP2567988B1 (fr) * 2011-09-06 2016-06-15 Sika Technology AG Polyme en formede peigne avec hydrolyse alcaline retardée
EP2574636B1 (fr) * 2011-09-30 2014-04-16 BASF Construction Solutions GmbH Composition sous forme de poudre pouvant être rapidement mise en suspension
US9458060B2 (en) * 2012-11-05 2016-10-04 Sika Technology Ag Grinding aid for cement clinker based on polycarboxylate ethers and/or lignosulfonates
US9789628B2 (en) * 2013-10-18 2017-10-17 Gcp Applied Technologies Inc. Fast response time in slump monitoring systems
EP3122794B1 (fr) 2014-03-27 2020-03-04 Sika Technology AG Polymère séquence
US9316097B2 (en) * 2014-09-08 2016-04-19 Suncor Energy Inc. In situ gravity drainage system and method for extracting bitumen from alternative pay regions
US9919968B2 (en) * 2014-09-30 2018-03-20 Gcp Applied Technologies Inc. Low-to-mid-range water reduction using polycarboxylate comb polymers
EP3018108A1 (fr) * 2014-11-10 2016-05-11 Basf Se Polymère équipé de chaînes latérales de polyéther
FR3029524B1 (fr) * 2014-12-08 2018-03-02 Coatex Procede continu d'esterification et ou d'amidification, sans solvant organique, d'un homopolymere ou copolymere acide
CN108025971B (zh) * 2015-09-24 2021-04-02 Sika技术股份公司 作为碱活化粘结剂的分散剂的嵌段共聚物
BR112018005624B1 (pt) * 2015-09-24 2022-12-20 Sika Technology Ag Copolímero, processo para a preparação de um copolímero, uso de um copolímero, composição de ligante mineral e corpo moldado
US20180265615A1 (en) * 2015-09-24 2018-09-20 Sika Technology Ag Production of dispersants by living radical polymerization

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US20210040000A1 (en) 2021-02-11

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