AU2006257345B2

AU2006257345B2 - Polyether-containing copolymer

Info

Publication number: AU2006257345B2
Application number: AU2006257345A
Authority: AU
Inventors: Manfred Bichler; Herbert Hommer; Konrad Wutz
Original assignee: BASF Construction Polymers GmbH
Current assignee: Master Builders Solutions Deutschland GmbH
Priority date: 2005-06-14
Filing date: 2006-06-14
Publication date: 2011-02-24
Anticipated expiration: 2026-06-14
Also published as: WO2006133933A2; ATE414728T1; DK1902085T3; PT1902085E; EP1902085A2; JP5130205B2; CY1108795T1; WO2006133933A3; DE102006027035A1; DE502006002133D1; EP1902085B1; PL1902085T3; JP2008544000A; ES2314918T3; AU2006257345A1; SI1902085T1

Abstract

Copolymers are disclosed, comprising two monomer components (A) and (B), component (A) representing an olefinically-unsaturated monocarboxylic acid or an ester or salt thereof, or an olefinically-unsaturated sulphuric acid comonomer or a salt thereof and the component (B) is an ether comonomer of formula (I). According to the invention, the copolymer shall contain the components (A) and (B) in the proportions 30 to 99 Mol. % and 70 to 1 Mol. %, comonomer component (A) being of the group acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, allylsulphonic acid, vinylsulphonic acid and suitable salts and alkyl or hydroxyalkyl esters thereof. The invention further relates to a composition, containing the claimed copolymer in addition to a hydraulic binder such as for example, cement, gypsum, lime and anhydrite. Said copolymers are of application as flow-improvers or dispersants for non-set compositions containing a hydraulic binder.

Description

POLYETHER-CONTAINING COPOLYMER DESCRIPTION [0001] This invention relates to a copolymer on a polyether basis comprising two monomer components and a method of use. [0002] Various types of organic compounds have been used to advantageously alter certain properties of not hardened hydraulic cement compositions. One class of components, which can collectively be called "superplasticizers" act dispersing and are able to fluidify or plasticize the not hardened cement compositions at certain cement/water ratios. A controlled fluidity of such masses is desired, such that the aggregate used in mortars and concretes does not segregate from the cement paste and subsequently not sediment. Alternatively, the addition of superplasticizers may allow the cement composition to be prepared using a lower water to cement ratio in order to obtain a composition having a desired consistency. Lower amounts of freshly mixed concrete often leads to a large liquefaction decrease in freshly mixed concrete and to a hardened cement composition having a higher compressive strength development after setting. [0003] A good superplasticizer should not only fluidify the not hardened cement composition to which it is added, but also maintain the level of fluidity over a desired period of time. This time should be long enough to keep the not hardened cement composition fluid, e. g. in a ready-mix truck while it is on its way to a job site. Another important aspect relates to the period for discharging the truck at the job site and the period needed for the cement composition for being worked in the desired final form. On the other side, the cement mixture cannot remain fluid for a too long time, that means the set must not greatly be retarded, because this will slow down the work on the job and show negative influences on the characteristics of the final hardened products. [0004] Conventional examples of superplasticizers are melamine sulfonate/formaldehyde condensation products, naphthalene sulfonate/formaldehyde condensation products and lignosulfonates, polysaccharides, hydroxycarboxylic acids and their salts and carbohydrates. 25664832.1 C:WRPonb\DCCAMT\341393 1.DOC-17/0112011 [0005] In most cases, fluidizing agents are multi-component products with copolymers based on oxyalkylenglykolalkenylethers and unsaturated dicarboxylic acid-derivatives as most important species. The European Patent EP 0 736 553 BI discloses such copolymers comprising at least three sub-units and especially one unsaturated dicarboxylic acid derivative, one oxyalkylenglykolalkenylether and additionally one hydrophobic structural unit, such as ester units. The third structural unit can also be represented by polypropylenoxid- and po lypropylenoxid-polyethylenoxid-derivatives, respectively. [0006] The German published application DE 195 43 304 Al discloses an additive for water containing mixtures for the construction field comprising a) a water-soluble sulfonic acid-, carboxylic- or sulfate group containing cellulose derivative, b) a sulfonic acid and/or carboxylic acid containing vinyl-(co)-polymer and/or a condensation product based on aminoplast-builders or acryl containing compounds and formaldehyde. This additive shall show sufficient water retention ability and rheology-modifying properties. Therefore, this additive shall be suitable for construction chemical compositions containing cement, lime, gypsum, anhydrite and other hydraulic binder components. [0007] Disclosed are also copolymers of ethylenically unsaturated ethers that can be used as plasticizers for cement containing mixtures (EP 0 537 870 Al). These copolymers contain an ether co-monomer and as additional co-monomer an olefinic unsaturated mono carboxylic acid or an ester or a salt thereof, or alternatively an olefinic unsaturated sulfuric acid. These copolymers show a very short ether side chain with 1 to 50 units. The short side chain shall cause a sufficient plasticizing effect of the copolymers in cement containing masses with a reduced slump loss of the construction chemicals mass itself. [0008] Based on the different characteristics and the availability of the superplasticizers mentioned above, it has been further desired to provide new alternative polymers with dispersing properties. In one or more aspects the present invention may provide additives for hydraulic "cement compositions" which impart to not hardened compositions excellent processability and flowability over the time. An additional aspect is an aqueous binder suspension with sufficient workability. Furthermore, the properties, the performance and effects of the provided copolymer shall be arbitrary which has only been insufficiently possible with the compounds used so far. 2 C:\RPonbr\DCC\AMT'k341390 | DOC-7l?/0/201 I [0009] In one aspect the present invention provides a copolymer consisting of two monomer components (A) and (B) wherein [0010] (A) an olefinic unsaturated mono-carboxylic acid co-monomer or an ester or salt thereof or an olefinic unsaturated sulfuric acid co-monomer or a salt thereof, and [0011] (B) a co-monomer according to the general formula (I)

(-CH

2 -CR 2_) (CH2)p-O-R' and R' is represented by -(CmH 2 mO) x(CnH 2 nOXc(CH2- H-O)z-R* R 3 and whereby R 2 = hydrogen or an aliphatic hydrocarbon group having from I to 5 C-atoms, R 3 is a non-substituted or substituted aryl group and preferably phenyl, and R 4 = hydrogen or an aliphatic hydrocarbon group having from I to 20 C-atoms, a cycloaliphatic hydrocarbon group having from 5 to 8 C-atoms, a substituted aryl group having from 6 to 14 C-atoms or a compound selected from the group 0 0 0 0 -0--C-R -C-OH , -0-C-(NH)R wherein R and R may each be an alkyl, aryl, aralkyl or alkaryl group and R 6 may be an alkyliden, aryliden, aralkyliden or alkaryliden group and p = 0 to 3, m, n = 2 to 4, x and y are independently from 55 to 350, and z= 0 to 200. In one embodiment z is 0, in a further preferred embodiment z is 1 to 200, preferably 10 to 100. 3 The terms "alkyl" and "alkyliden" as used herein, determine hydrocarbon groups with preferably 1 to 20 C-atoms, preferably with 1 to 6 C-atoms. The terms "aryl", "aralkyl", "alkaryl", "aryliden", "aralkyliden" and "alkaryliden" represent hydrocarbon groups with preferably 5 to 20, more preferably 5 to 10 C-atoms. [0012] Surprisingly, these polymers according to the invention based on their dispersing properties show excellent plasticizing effects over the desired time and additionally can be prepared by using usual preparation methods. Therefore, under economic aspects, these co-polymers show significant improvements over the prior art. Another aspect may be that the claimed copolymers show their plasticizing effect not only together with specific hydraulic components, but can also be used in the field of cementitious mortar and concrete and in the field of gypsum. Additionally, the improved effect of the copolymers can be selectively chosen based on the broad variety of the ether co-monomer and especially based on the broad scope of the side chain length. [0013] As used herein, the term "cement composition" refers to any not hardened mixture, such as pasty compounds, mortars, grouts, concretes, floors and mixtures or mixtures applied in oil- and natural gas exploration. In this connection, an important role is to be played by the various types of hydraulic binders, such as cements (especially Portland cement), but also including fly ashes, blast furnace slags, micro silicas, puzzolanic components and the various types of gypsum. [0014] The term "gypsum" according to this invention is also known as calcium sulfate, whereby calcium sulfate can be used in its various anhydrous and hydrate forms with or without crystal water. Natural gypsum is represented by calcium sulfate dihydrate and the natural crystal water free form of calcium sulfate is represented by the term "anhydrite". Besides the natural forms, calcium sulfate is a typical by-product of technical processes characterized by the term synthetic gypsum. One example of such technical processes is the flue gas desulfurization. Synthetic gypsum may also be a by-product of phosphorous acid and hydrogen fluoride production methods for gaining semi-hydrate forms (CaSO 4 x '2 H 2 0). Gypsum (CaSO 4 x 2H 2 0) is to be calcinated by driving off of the water of hydration. Products of the various calcinating procedures are alpha or beta hemi-hydrate. Beta calcium sulfate hemi-hydrate results from a rapid heating in open units by a rapid 25664832.1 4 evaporation of water and by forming cavities. Alpha hemi-hydrate is produced by a de watering of gypsum in closed autoclaves. The crystal form in this case is dense and therefore, this binder needs less amounts of water than beta hemi-hydrate. [0015] On the other side, gypsum hemi-hydrate re-hydrates with water to dihydrate crystals. Usually, the hydration of gypsum needs some minutes to hours indicating a clearly shortened workability period in contrast to cements that hydrate in periods over hours or days. These characteristics make gypsum an attractive alternative to cement as hydraulic binder in various fields of application, because hardened final gypsum products show a characteristic hardness and compressive strength. [0016] Calcium sulfate hemi-hydrate can produce at least two crystal forms, whereby a calcined gypsum is usually de-watered (de-hydrated) in closed autoclaves. For various fields of application, B-calcined gypsum may be selected due to its availability under economical aspects. However, these advantages may be reversed because B-calcined gypsum needs higher water amounts for workability and for making slurries of a given fluidity. Hardened or dried gypsum tends to a certain weakening based on the remained water in its crystal matrix. Therefore, products thereof show less strength than gypsum products that have been made with smaller amounts of water. [0017] In general, the workability of gypsum, but also of other hydraulic binders, can be improved under hydraulic aspects by adding dispersants. In this connection, the copolymers according to this invention represent suitable dispersants because of their dispersing properties. [0018] The copolymer of this invention shows more advantageous properties when it comprises the co-monomer component (A) in amounts of from 30 to 99 mol-% and the ether component (B) from 70 to 1 mol-%. [0019] As used herein, the mentioned co-monomers and any possible structures thereof are to be interpreted as structural units of the claimed copolymer after its polymerisation. [0020] The invention comprises an alternative characterized in that on the one hand the mol-% of the co-monomer component (A) and the co-monomer (B) is from 40 to 90 and 25664832.1 5 from 60 to 10, respectively, and whereby on the other hand the ether component (B) with p = 0 or I may contain an allyl or vinyl group and additionally contains a polyether as RI; additionally, the co-monomer component (A) is in this alternative an acrylic acid or a salt thereof [0021] In general, according to this invention, the co-monomer component (A) is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, allyl sulfonic acid, vinyl sulfonic acid and their suitable salts or their alkyl or hydroxyalkyl esters. [0022] Alternatively, other co-monomers, such as styrene or/and acrylamides may be additionally co-polymerized with the ether component (B) and the co-monomer component (A). Alternatively, there also may be used components with hydrophobic properties. Compounds with ester structural units, polypropylene oxide or polypropylene oxide/polyethylene oxide (PO/PE)-units are preferred. The corresponding structural units should be represented in the copolymer of the invention in amounts up to 5 mol-%; amounts from 0.05 to 3 mol-% are preferred and 0.1 to 1.0 mol-% are especially preferred. Compounds as disclosed by the European Patents EP 0 736 553 B 1 and EP 1 189 955 B 1 as structural units c) and any related and in these both documents disclosed species of compounds are more preferred. Regarding the structure of the additional co-monomer EP 0 736 553 BI and EP 1 189 955 BI are incorporated into this application and therefore are to be seen as disclosed herein. [0023] An additional preferred alternative of the copolymers according to this invention is to be seen in formula (I) representing an allyl or vinyl group containing polyether. [0024] As already mentioned, the copolymers of this invention can be produced by relatively simple methods and especially when the polymerisation is carried out in an oxygen-depleted or oxygen-free atmosphere. There also may be added appropriate amounts of solvents to make the ether component soluble. In the case that co-monomer (B) is a poly-alcoholic group or an alkylen oxide derivatived poly-alcohol group, and R 2 of the ether component is hydrogen, respectively, water is the solvent to be preferred. Alternatively, a mixture of water and alcohol, such as isopropanol, may be used as a 25664832.1 6 solvent. In the case that R2 is other than hydrogen, then organic solvents and especially toluene is to be seen as preferred. [0025] For starting the polymerisation reaction, the basic mixture is heated to ambient temperature or smoothly cooled down. Another suitable alternative may be the addition of a redox system as initiator component. This redox system may comprise reducing and oxydizing agents and preferably Rongalite T M or Bruggolite and additionally a peroxide or a persulfate like H 2 0 2 or ammonia persulfate. These reagents may be preferably used in systems with water as solvent. [0026] In principal, two alternatives may be selected to produce optimal copolymers: Alternative A: [0027] The co-monomer mixture and the reducing agent containing mixture are to be added to the ether containing mixture stepwise or simultaneously; the temperatures range from 0 to 50'C. Alternative B: [0028] The mixture containing the oxidizing agent is to be added stepwise to the complete monomer mixture. [0029] Then the reaction mixture is usually stirred until all the peroxide has reacted. In the case that organic solvents are to be used, these will be distilled. The reaction product will then be cooled down and the resulting copolymer is to be neutralized by using a base (such as alkaline or alkaline earth metals, amines or alkanol amines). The addition of an aqueous solution comprising sodium or calcium hydroxide is a preferred alternative. [0030] This disclosed process represents an example for producing the copolymer according to this invention. [003 1] Finally, this invention covers a preferred alternative with the copolymers in powdery form. The powder is to be achieved by a final drying step and more preferably, by spray drying. 25664832.1 7 [0032] In contrast to the state of the art this method produces beneficial powdery copolymers to be added to hydraulic mixtures in any selected dilution. [0033] Besides the copolymer itself this invention also covers a hydraulic binder containing composition that comprises additionally to the hydraulic component the copolymer of this invention. In this connection a composition is preferred whose hydraulic binder is selected from the group consisting of cement, gypsum, lime, anhydrite or any other calcium sulfate based binder. [0034] Also claimed by this invention is a method of use of the copolymer according to this invention as superplasticizer (dispersant) for any non-hardened (not hardened) and a hydraulic binder containing composition. In this connection the copolymer is preferably used in amounts from 0.01 to 10.0 % by weight und more preferably in amounts from 0.05 to 5.0 % by weight, each amount relating to the weight of the binder component. [0035] Another aspect of the claimed method of use is directed to the alternative to use the copolymer according to the invention in combination with a defoaming component. This alternative may be realized by an addition of the copolymer and the defoaming agent to the corresponding construction material composition in separated form depending from the specific application. This invention additionally claims the alternative that the claimed copolymer comprises the defoaming component as third structural group in copolymerized form. [0036] In the case that the defoaming component is added to the composition in separated form then representatives of the following group are to be seen as preferred: non-ionic tensides like copolymers comprising ethylene oxide/propylene oxide-(EO-PO)-units TM (Dowfax of the Dow company) or EO-PO-EO or PO-EO-PO block polymers, respectively (Pluronic of BASF). Additionally defoamer on a mineral oil basis can also be used; such defoamers can be used in powder form such as Agitan types of the Milnzing Chemie company. [0037] In the case that the defoaming agent represents an additional chemical structural group of the copolymer the already mentioned structural units c) of the European patents EP 0 736 553 Bl and EP 1 189 955 BI maybe used. 25664832.1 8 [0038] The claimed copolymers and especially their application as superplasticizer or dispersant in hydraulic binder containing compositions represents a clear improvement of the state of the art because the claimed copolymers induce a uniform plasticizing effect over time and a reduced tendency of the negative slump loss in the not hardened construction chemicals mass. In sum, the claimed copolymer shows a typical retention effect. Additionally, the pumpability and workability of the not hardened hydraulic binder containing composition is significantly improved. [0039] The following examples underline the advantages of the claimed copolymer and its use. Examples Preparation Examples Preparation Example 1 [0040] To a I liter four necked glass flask with a temperature controller, a reflux condenser and two dropping funnels 350 g water, 350 g (0.06 mol) of polyethylene glycol 5800-monovinylether and 4 g of a propylene oxide/ethylene oxide(PO-EO)-block polymer with a molecular mass of 2,000 g/mol ("defoamer") and 25 g NaOH (20 %) have been added. A mixture comprising 45 g (0.63 mol) of acrylic acid in 17 g water has been produced separately and 15 g of this mixture has been added to the polyethylene glycol 5800-monovinylether solution in the flask; the pH decreased to 8.0. Then 40 mg iron(II)sulfate-heptahydrate ("green vitriol") and 3.6 g of a 50 % hydrogen peroxide have been added. Within 20 minutes the remaining acrylic acid mixture and 34 g of a 10 % Rongalite solution containing 6 g of mercaptoethanol have been added under a constant but differing mass flow. The temperature rose from 23 to 35 'C. After the final addition the reaction mixture showed a pH of 4.8. The solution has been stirred at ambient temperature for 10 minutes and subsequently has been neutralized with 50 g of a 20 % sodium hydroxide solution. The product was a yellow colored, clear and aqueous polymer solution with a solid concentration of 45 % by weight. 25664832.1 9 Preparation Example 2 [0041] To the flask according to Example 1 450 g water, 450 g (0.06 mol) polyethylene glycol-7500-monovinylether and 14 g NaOH (20 %) have been added. A mixture of 41.8 g (0.58 mol) of acrylic acid in 40 g water has been produced separately and added to the flask containing polyethylene glycol-7500-monovinylether solution; the pH decreased to 5.5. Then 40 mg iron(II)sulfate-heptahydrate ("green vitriol") and 4 g Rongalite TM and 2 g mercaptoethanol have been added. Within 20 minutes a solution comprising 3.6 g 50 % hydrogen peroxide in 34 g water have also been added. The temperature rose from 20 to 31 'C. After the final addition, the reaction mixture showed a pH of 5.4. The solution has been stirred for 10 minutes at ambient temperature and subsequently has been neutralized with 60 g of a 20 % sodium hydroxide solution. The product was a light yellow colored, clear and aqueous polymer solution with a solid concentration of 43 % by weight. Preparation Example 3 [0042] To the flask according to Example 1 490 g water, 350 g (0.06 mol) polyethylene glycol-5800-monovinylether and 10 g NaOH (20 %) have been added. A mixture comprising 26 g (0.36 mol) of acrylic acid in 40 g water has been produced separately and added to the polyethylene glycol-monovinylether-solution; the pH decreased to 5.3. Then 40 mg iron(II)sulfate-heptahydrate ("green vitriol") and 4 g Rongalite TM and 1.5 g mercaptoethanol have been added. After a short period of stirring 3.6 g 50 % hydrogen peroxide have been added. The temperature rose from 20 to 29 *C. Then the solution has been stirred for 10 minutes at ambient temperature and subsequently has been neutralized with 37 g of a 20 % sodium hydroxide solution. The product was a light yellow colored, clear and aqueous polymer solution with a solid concentration of 40 % by weight. Application Examples [0043] The comparative Examples 1 and 2 given in the following application testings are related to the corresponding examples 1 (comparison 1), respectively, 3 (comparison 2) as described in EP 0 537 870 Al. 25664832.1 10 Application Testing 1: Concrete [0044] In a standardized manner a concrete recipe corresponding to 400 kg/m 3 "Portland Cement" of type CEM 1 42,5 R and 1755 kg/m 3 of fine and coarse aggregate (grading 0 to 16), 40 kg/m 3 fly ash and 168 kg/m 3 water (water from the polymer solution taken into account, w/c ratio 0,42) were mixed. The aqueous solutions of the copolymers according to the present invention, respectively, of the comparative examples were added as superplasticizers and the spread value was determined 4, 30 and 60 min after the polymer addition in accordance to DIN 1048. Plasticizer Dosage Spread in cm after [% bwc] 4 min 30 min 60 min Comparison 1 * 0.22 51 49 42 Preparation Example 1 0.22 65 59 50 Preparation Example 2 * 0.22 64 61 58 Preparation Example 3 * 0.22 65 63 60 *) defoamer component addition (based on a polygylcol), dosage 1.0 % by weight by weight of active polymer component Application Testing 2: Mortar Standard Guide Recipe: Portland Cement (different types) 900 g Standard Quartz sand (0-2 mm, EN 196-1) 1350 g Defoamer (Agitan P 800) 0.45 g Dispersant (Plasticizer) 0.3 % Mixing water accordingly Mixing Procedure and Methods of Measurement: (0045] The mortar was mixed according to DIN EN 196-1, paragraph 6.3. The flowability was tested with a flow channel according to the machinery grout guide lines published by the Deutsche Betonverein eV (issued Sept. 1990, updated 1996) after 5, 30 and 60 min. 25664832.1 11 For each type of cement the flowability was adjusted by varying the w/c ratio of Comparison I to be in a range of 60 - 75 cm accordingly. 1. Cement type Milke (CEM I 42,5 R) Plasticizer W/C Flowability in cm after 4 min 30 min 60 min Comparison 1 0.24 72 58 0 Comparison 2 0.24 70 49 0 Preparation Example 3 0.24 73 69 39 2. Cement type Karlstadt (CEM I 42,5 R) Plasticizer W/C Flowability in cm after 4 min 30 min 60 min Comparison 1 0.31 60 68 68 Comparison 2 0.31 52 50 55 Preparation Example 3 0.31 85 85 85 3. Cement type Mergelstetten (CEM I 42,5 R) Plasticizer W/C Flowability in cm after 4 min 30 min 60 min Comparison 1 0.26 64 0 0 Comparison 2 0.26 62 0 0 Preparation Example 3 0.26 78 59 26 4. Cement type Ube Kosan normal OPC-Cement Plasticizer W/C Flowability in cm after 4 min 30 min 60 min Comparison 1 0.245 74 14 0 Comparison 2 0.245 74 12 0 Preparation Example 3 0.245 77 72 42 25664832.1 12 C.\NRIonblD)CC\AM1XUJI -I DOC-17/1/2011 Application Testing 3: Gypsum Standard Guide recipe Stucco gypsum 400 g Water (W/G = 0.35) 140 g Plasticizer 0.35 % [0046] The gypsum is sifted into water within 15 see and afterwards mixed with a Hobart mixer for 60 sec at high speed. After 105 see the flow value was measured with a cylinder (height: 10 cm, diameter: 5 cm). Flow in Set times in Plasticizer cm mmn:sec Comparison 1 12 27 :20 Comparison 2 13 30 :00 Preparation Example 2 20 5 :10 Preparation Example 3 23 4 : 40 Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates. 13

Claims

1. A copolymer consisting of two monomer components (A) and (B) wherein (A)is an olefinic unsaturated monocarboxylic acid comonomer or an ester or a salt thereof or an olefinic unsaturated sulfuric acid comonomer or a salt thereof, and (B) is a comonomer of the general formula (I) (-CH 2 -CR 2 -) (CH2)p-0-R' and R' is represented by -(CmH 2 mO) x(CH 2 nO)y-(CH2-T H-0)z,-R R 3 and whereby R 2 = hydrogen, R 3 is a non-substituted or substituted aryl group and preferably phenyl, and R 4 = hydrogen or an aliphatic hydrocarbon group having from 1 to 20 C-atoms, a cycloaliphatic hydrocarbon group having from 5 to 8 C-atoms, a substituted aryl group having from 6 to 14 C-atoms or a compound selected from the group 0 0 0 0 -O-C-R , -0-C-R -C-OH , -O-C-(NH)R wherein R and R7 may each be an alkyl, aryl, aralkyl or alkaryl group and R 6 may be an alkyliden, aryliden, aralkyliden or alkaryliden group p = 0, m, n = 2 to 4, x and y are independently from 55 to 350, and z = 0 to 200. 14 C:\NRPortbl\DCC\AM1'34fl39X1 LDOC-19/01/2011

2. - Copolymer of claim 1, comprising from 30 to 99 mol-% of comonomer component (A) and from 70 to I mol-% of said comonomer component (B).

3. Copolymer of claim I or claim 2, wherein the amount of the said comonomer component (A) is from 40 to 90 mol-% and the amount of the said comonomer component (B) is from 60 to 10 mol-%.

4. Copolymer of any one of claims I to 3, wherein the said comonomer component (A) is an acrylic acid or a salt thereof and the comonomer component (B) with p = 0 contains an allyl or vinyl group and contains a polyether as R'.

5. Copolymer of any one of claims I to 4, wherein the said comonomer component (A) is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, allylsulfonic acid, vinylsulfonic acid and appropriate salts thereof and alkyl or hydroxyalkyl esters thereof.

6. Copolymer of any one of claims I to 5, wherein the copolymer comprises additional structural groups in copolymerized form.

7. Copolymer of claim 6, wherein the additional structural group is a styrene and/or acrylamide and/or a hydrophobic compound.

8. Copolymer of claim 7, wherein the hydrophobic compound contains an ester structural unit, polypropylene oxide and polypropylene oxide/polyethylene oxide unit.

9. Copolymer of claim 7 or claim 8, wherein the additional structural group is contained in amounts up to 5 mol-%.

10. Copolymer of claim 9, wherein the additional structural group is contained in amounts from 0.05 to 3.0 mol-%. H1. Copolymer of claim 10, wherein the additional structural group is contained in amounts 0.1 to 1.0 mol-%.

12. Copolymer of any one of claims I to 11, wherein formula (I) represents an allyl or vinyl group containing polyether. 15 C kNRPorbl\DCC\AMT\3419xI I DOC-2Il/2)II

13. Copolymer of any one of claims I to 12, wherein the copolymer is a powder.

14. Copolymer of claim 13, wherein the copolymer is a powder that has been produced by spray drying.

15. Copolymer of claim 1, substantially as hereinbefore described.

16. A hydraulic binder containing composition comprising a copolymer of any one of claims I to 15 and a hydraulic binder.

17. Composition of claim 16, wherein the hydraulic binder is selected from cement, gypsum, lime, anhydrite or any other calcium sulfate based binder.

18. Composition of claim 16, substantially as hereinbefore described.

19. Use of the copolymer of any one of claims I to 15 as plasticizer for a non-hardened and a hydraulic binder containing composition.

20. Use of claim 19, wherein the copolymer is added as plasticizer in amounts from 0.0 1 to 10.0% by weight, wherein the amounts are relating to the weight of the binder component.

21. Use of claim 20, wherein the copolymer is added as plastizer in amounts from 0.05 to 5.0% by weight, wherein the amounts are relating to the weight of the binder compartment.

22. Use of any one of claims 19 to 21, wherein the copolymer is used in combination with a defoaming component.

23. Use of claim 22, wherein the defoaming component is comprised by the copolymer as third structural unit.

24. Use of claim 19, substantially as hereinbefore described. 16