Title of Invention

COPOLYMERS BASED ON PHOSPHORUS CONTAINING MONOMERS AND PROCESSES FOR THE PREPARATION THEREOF

Abstract

The invention relates to copolymers based on phosphorous-containing monomers (A) and on macromonomers (B), to methods for the production thereof and to their use as additives for inorganic binding agent suspensions based on cement, lime, gypsum and anhydrite. The corresponding polymeric additives have, as flow agents, excellent water-reducing properties and hold the flowability of the concrete over a relatively long period of time (60 to 90 min.) to an almost unchanged level without having delayed action. In addition, the corresponding polymeric additives improve the processing and setting processes of the building materials produced with these additives by making possible earlier and higher resistances to pressure.

Full Text

Description The present invention relates to copolymers based on phosphorus-containing monomers, processes for their preparation and the use thereof as admixtures for inorganic binder suspensions based on cement, lime, gypsum and anhydrite. According to a widely accepted theory, the effectiveness of superplasticizers for cement- containing binder suspensions is based substantially on two effects. Thus, the negatively charged acid groups of the superplasticizers are adsorbed on the cement particle surface positively charged by calcium ions. The resulting electrostatic double layer (Zeta potential) leads to electrostatic repulsion between the particles. The repulsive forces caused by the Zeta potentials, however, have only short ranges [cf. H. Uchikawa, "Cem. Conor. Res." 27 (1997) 37-50]. However, the adsorption of the superplasticizer also prevents the surfaces of the cement particles from coming into direct contact with one another. With the use of corresponding comb polymers, this steric repulsion effect is drastically increased by the non-adsorbed side chains [cf. K. Yoshioka, "J. Am. Ceram. Soc." 80 (1997) 2667-71] . It is obvious that the sterically caused repulsion effect can be influenced both by the length of the side chains and by the number of side chains per main chain. On the other hand, an excessively high side chain density or length can hinder the adsorption on the cement particle surface. On the basis of this knowledge, a large number of superplasticizers based on polyethercarboxylates were developed in the last 10 years (WO 99/47 468 A1, WO 97/00 898 A1, EP 1 437 330 A1, EP 0 924 174 A1, EP 0 850 894 A1, EP 0 838 444 A1, EP 0 870 784 A1, EP 0 753 488 A1, US 6,267,814 B1, US 5,707,445 B1, US 5,703,174 B1, DE 199 26 611 A1, DE 198 34 173 A1, DE 195 13 126 Al) . The comb-like copolymers comprising poly(alkylene glycol)-containing acrylates/methacrylates are distinguished in that a random distribution of the individual monomers along the polymer chain is present. However, such a distribution along the polymer backbone does not rule out the more or less frequent existence (as a result of polymerization) of domains which are based on homopolymers of one or other monomer (or further monomers). In other words, strictly alternating copolymers are not obtainable by this method, so that greater or lesser non-uniformity of these copolymers is always present. These comb-like copolymers corresponding to the prior art have good water-reducing properties in aqueous mineral binder suspensions, but a flowability of the concrete can be kept at a constant level with these copolymers only over a comparatively short period. It was therefore the object of the present invention to develop copolymers based on phosphorus-containing monomers and the use thereof as admixtures for inorganic binder suspensions, the corresponding copolymers not having said disadvantages corresponding to the prior art but, as superplasticizers, both having good water-reducing properties (without impairing the plasticization of, for example, the concrete) and keeping the flowability of the concrete at a virtually unchanged level over as long a period as possible (6O- 90 min) without having a retarding effect (so-called slump retainer). This object was achieved, according to the invention, by using copolymers based on phosphorus-containing monomers (A) of the formulae (Ia) and/or (Ib) and macromonomers (B) of the general formula (II) as claimed in claim 1. It has in fact surprisingly been found that the corresponding copolymers are very suitable as admixtures for mineral binder suspensions, it being possible for these admixtures to be used both as excellent superplasticizers and/or as slump retainers. In addition, the corresponding polymeric admixtures improve the processing and hardening processes of the building materials produced using these admixtures, by permitting earlier and higher compressive strengths. The copolymers according to the invention are derived from phosphorus-containing monomers (A) and macromonomers (B) . The phosphorus-containing monomers (A) correspond to the general formulae (Ia) or (Ib) where R2 = C1-C2O-(hetero)alkylene radicals optionally having 0 or N heteroatoms, which are linear or branched and optionally also have 1 to 10 substituents selected from the group consisting of OH, OPO3M2, OPHO2M, NH2, NH-CH2PO3M2, N(CH2- PO3M2)2. CZ(PO3M2)2, and C6-C1O-arylene radicals, Y = -N(CH2-PO3M2)2, -CZ(PO3M2)2, -OPHO2M, -OPO3M2, Z = H, Hal, OH, NH2, Hal = F, Cl, Br, I, M = H, Na, K, NH4, N(R3)4, R3 = C1-C12-alkyl radicals, preferably C1-C8-alkyl radicals, and C6-C1O-aryl radicals. The corresponding monomers (A) firstly consist of an electron-poor vinylic bond based on maleic acid, itaconic acid or citraconic acid derivatives and secondly have a phosphorus-containing anionic radical based on phosphonate-, phosphite- or phosphate- containing groups. According to the general formula (Ia) , these are the monoesters (X = O, S) or monoamides (X = HN, N-R2-Y) of the corresponding dicarboxylic acid derivatives or, according to the formula (Ib), the corresponding cyclic imides. The phosphorus-containing anionic radicals are bonded to the unsaturated dicarboxylic acid derivatives via suitable (hetero)alkylene or arylene spacers (for example R2) . The relevant radicals R2 are C1-C2O-alkylene or heteroalkylene radicals (having 0 or N heteroatoms), which may be linear or branched, or are C6-C1O-arylene radicals (such as, for example, phenylene or naphthylene). In a preferred embodiment, they are C1- C1O-alkylene or heteroalkylene radicals. The C1-C2O- or C1-C1O-(hetero) alkylene radicals may optionally also have 1 to 10 substituents selected from the group consisting of OH, OPO3M2, OPHO2M, NH2, NH- CH2PO3M2, N(CH2-PO3M2)2 and CZ(PO3M2)2, Z being H, Hal, OH or NH2 and Hal being F, Cl, Br or I and M being H, Na, K, NH4 or N(R3)4(R3 = C1-C12-alkyl radicals and C6-C1O-aryl radicals). The monomers (A) can be prepared in a technically very simple manner by allowing unsaturated dicarboxylic acid derivatives of the general formula (VI) to react with phosphorus-containing compounds of the general formula (VII) HX-R2-Y (VII) (R1, R2, X and Y having the abovementioned meaning) at temperatures of from 0 to 100°C, it being possible for this reaction to be carried out both continuously and batchwise. Maleic acid, itaconic acid and citraconic acid are used as unsaturated dicarboxylic anhydride according to formula (VI). The phosphonate, phosphite and phosphate building blocks which are presented in formula (VII) are prior art and can be obtained by many variants: A) Methylphosphonation of amines (US 3,288,846, US 4,235,89O). B) Phosphonation of carboxylic acids and derivatives thereof, such as, for example, acid chlorides, acid amides or nitriles (US 4,239,695, US 4,10O,167, US 3,799,758, US 3,40O,149, DE 27 45 084, DE 25 34 391, DE 21 30 794, DE 197 37 923, DE 16 18 788, DE 11 48 551). C) Phosphation of alcohols and ethers (Houben-Weyl, volume E2 (1982), M. Regitz (editor), page 491 et seq., and literature cited therein, SU 178 819, SU 178 374). D) Phosphites of alcohols and ethers (Houben-Weyl, volume E1 (1982), M. Regitz (editor), page 313 et seq. , and literature cited therein, in particular GB 940 697). However, the solution which is of most interest in terms of process engineering is the phosphation of alcohols (SU 196 817) . According to the invention, amino-containing alcohols can also be phosphated by this procedure. Thus, the industrially most important aminoalcohols, such as aminoethanol [CAS 141-43-5], diethanolamine [CAS 111-42-2] or tris(hydroxymethyl)aminomethane (TRIS) [CAS 77-86-1], which were dissolved or suspended with 85% strength phosphoric acid in o-xylene, can be phosphated directly at the hydroxy1 group by separating off the water by means of azeotropic distillation on a water separator. However, other commercially available aminoalcohols, such as aminohexanol [CAS 4048-33-3], 2- aminoethoxyethanol [CAS 929-06-6], 4-aminobenzyl alcohol [CAS 623-04-1], N-(2- aminoethyl)diethylenolamine [CAS 3197-06-6], N-(3- aminopropyl)diethanolamine [CAS 4985-85-7], can also be phosphated in this manner with surprisingly high yields (table 1). Owing to the high oxygen affinity of phosphorus, a reaction at the amino group does not take place. The formation of phosphoric acid diesters is likewise negligibly small. The phosphation of aminoalkyl/aryl alcohols with phosphoric acid is generally described (e.g. of aminoethanol, DE 930 566, GB 684 977) but, with the use of virtually equimolar amounts of concentrated phosphoric acid, such a high conversion and such little formation of phosphoric acid diesters are unknown to date (table 1). (a) Degree of phosphation (DP) = percentage amount of phosphated hydroxyl groups (b) The determination of the DP was effected with the aid of 1H-NMR (D2O). (c) The DP was determined by means of HPLC. The coupling of these phosphorus-containing compounds to vinyl-containing anhydrides - for example of maleic acid, itaconic acid or citraconic acid - is effected in particular via an esterification or amidation. The presence of at least one "free" NH, SH or OH function in these phosphorus-containing compounds corresponding to formula (VII) (X = O, S, N) is required for this purpose. The reaction of the dicarboxylic anhydrides according R12, R13 are H, C1-C2O-alkyl radicals, preferably C1- C1O-alkyl radicals, or C6-C1O-aryl radicals and r is from 0 to 10 and R10 has the abovementioned meaning. In order to vary the side chain density in the copolymer without changing the charge density on the polymer backbone, in particular alkenyl ethers, esters or alcohols are used here, methyl vinyl ether and hydroxybutyl vinyl ether preferably being used as alkenyl ethers, vinyl acetate as alkenyl esters and allyl alcohol as alkenyl alcohols. According to a preferred embodiment, the monomer (D) is used in an amount such that up to 90 mol% of the monomer (B) are replaced by the monomer (D) in the copolymer based on the monomers (A) and (B). According to a further process variant, up to 90 mol% of the monomers (A) and (B) can be replaced by the monomers (C) and (D) in the copolymer based on the monomers (A) and (B). The copolymers based on the monomers (A) , (B) and optionally (G) and (D) are distinguished in that they have a very uniform composition with respect to the monomer composition along their main chain, since they are virtually alternating copolymers. A precondition, however, is that only one electron-poor monomer (C) be reacted with an electron-rich monomer (D). If, however, corresponding mixtures of electron-rich monomers and mixtures of electron-poor monomers are used, alternating domains which may very strongly influence the properties of the copolymer as a superplasticizer may also occur along the main chain. It is also possible within the scope of the present invention to incorporate further comonomers (E) according to the general formula (V) into the copolymer based on the monomers (A) and (B) and optionally (C) and (D) , which further comonomers (E) are to be regarded neither as electron-poor nor as electron-rich monomers: in which W is CN, CO-R14, R14 is H, OM, OR1O, NHR10, N(R10)2, SR10 and R1O, R12, R13 and M have the abovementioned meaning. The α,β-unsaturated carboxylic acids (W = CO-R14; R14 = OM) , such as, for example, acrylic acid or methacrylic acid, and the water-soluble derivatives thereof, such as, for example, hydroxypropyl acrylate or hydroxyethyl methacrylate, are particularly preferably used here. The copolymer based on the monomers (A) , (B) and optionally (C) and (D) preferably contains the monomer (E) in an amount of up to 10 mol equivalents, based on the sum of the monomers (A) and (B) and optionally (C) and (D). With the use of such comonomers (E) , the alternating composition of the copolymers comprising the monomers (A) and (B) and optionally (C) and (D) may be lost, which, however, need not be a disadvantage. On the contrary, it has been found that the use of the monomers (E) can substantially improve the monomer conversions of (A) and (B) and optionally (C) and (D) (and hence the polymer yields as a whole) . Comonomers of the type (E) modify the side chain and charge density of the copolymers and very particularly, when they are used as superplasticizers, can combine the properties of a slump retainer and water reducer in one polymeric admixture. The polymerization of the phosphorus-containing monomers (A) according to the invention with the comonomers (B) and optionally (C) , (D) and (E) is effected in principle by free radical initiation methods which are known to the person skilled in the art in the area of polymerization. The generation of free radicals can be effected either (a) by thermal decomposition of suitable peroxo or azo initiators, (b) photochemically or (d) by use of a redox system. Water-soluble azo initiators, such as, for example, 2,2'-azobis(2-methylpropionamidine) dihydrochloride [CAS 2997-92-4] , 2,2'-azobis[2-(2-imidazolin-2- yl)propane] dihydrochloride [CAS 27776-21-2] ox 4,4'- azobis[4-cyanopentanoic acid] [CAS 2638-94-0], are preferably used, without their being any claim to completeness. These azo initiators are also distinguished in that higher temperatures (T > 60°C) are required for free radical formation. Polymerizations at room temperature require photochemical excitation for decomposition in the case of such azo initiators. However, the use of a redox system consisting of hydrogen peroxide, iron(II) sulfate and a reducing agent has proven particularly useful in the initiation of free radical polymerizations in the range T = O-30°C (fig. 1). Depending on the pH, products from Bruggemann have proven to be useful reducing agents (RA) (e.g. Rongalite®: sodium salt of hydroxymethylsulfonate-2H2O or Briiggolit®: 5O-60% of disodium salt of 2-hydroxy-2- sulfinatoacetic acid, 3O-35% sodium sulfite, 1O-15% of disodium salt of 2-hydroxy-2-sulfonatoacetic acid). Figure 1: Initiator system: FeSO4/H2O2/reducing agent (RA) In an aqueous system, the polymerization temperatures may be from -10°C to 100°C. In the case of the photochemical or redox free radical production, the temperatures are preferably from 0°C to 30°C. Depending on the reactivity, the monomers can either be completely initially introduced before the beginning of the polymerization or metered in in the course of the polymerization. The preferred solvent for the polymerization is water. However, it is also possible to use other media (protic or aprotic solvents, melts, supercritical liquids). The polymeric admixtures proposed according to the invention are outstandingly suitable as superplasticizers (water reducers) or slump retainers for inorganic binder suspensions based on cement, lime, gypsum and anhydrite, it being used in an amount of from 0.01 to 10% by weight, in particular from 0.05 to 5% by weight, based on the weight of the inorganic binder. Here, the polymeric admixture has excellent water-reducing properties and imparts constant flowability to the concrete over a relatively long period. The following examples are intended to illustrate the invention in more detail. Examples A) General methods for the synthesis of phosphorus- containing maleic anhydride monomers A.l) Phosphation of aminoalkyl/aryl alcohols with 85% strength phosphoric acid 1.0 mol of the aminoalcohol as an approx. 20% strength solution in o-xylene is stirred with 1.1 mol of 85% strength phosphoric acid and heated under nitrogen until azeotropic distillation of the water occurs. As the reaction progresses, the aminoalkyl/aryl phosphoric acid ester which is insoluble in o-xylene separates out as a viscous, syrupy residue. The reaction is complete when the theoretical amount of H2O has been collected by means of a water separator. The isolation or purification of the product can be effected by two methods: A) After the o-xylene has been decanted, the viscous syrupy product can be converted with H2O/EtOH into a crystalline form. B) With addition of water, the syrupy product can be dissolved and can be separated from the xylene by extraction by shaking. Conversions (degree of phosphation) and analytical data are summarized in table 3. (a) The yield corresponds to the degree of phosphation (DP) and was determined with the aid of 1H-NMR (D2O) . The residual aminoalcohol was not separated from the phosphated product. (b) The phosphation of the OH groups shows a typical deep field shift of the proton signal CH2O-P compared with the signal CH2OH of the free hydroxyl group of about 0.3 ± 0.03 ppm. Owing to long-range PH couplings, the signal CH2O-P is additionally split. (c) TRIS = tris(hydroxymethyl)aminomethane. A.2) Phosphonate formation from carboxylic acids and carboxylic acid derivatives with aminoalkyl/aryl radicals The phosphonate formation from carboxylic acids or nitriles is achieved at high temperatures (14O-150°C) with pure phosphorous acid or with the aid of phosphorus halides (POC13, PC13, PBr3) or HC1 gas. Corresponding preparation processes are known (e.g. US 4,239,695, US 4,10O,167, US 3,799,758, US 3,40O,149, DE 21 30 794). Table 4 lists examples of industrially very particularly interesting phosphonate products which still have a free amino group. A. 3) Amidation of maleic anhydride (MAA) with phosphorus-containing aminoalkyl/aryl compounds 1 mol of an aminoalkyl/aryl phosphoric acid ester dissolved in 300 ml of water is adjusted to pH 5.5 with NaOH, and 1.O-2.5 mol of maleic anhydride (MAA), dissolved in 300 ml of dry acetone, are added with stirring. The rate of the MAA addition is chosen so that the pH of the reaction solution remains at 5.5-6.5 and the reaction temperature at 25°C. The pH is regulated with an NaOH solution. After the MAA addition, stirring is effected for a further 2 h at room temperature or - depending on reactivity and steric requirement of the amine - at a higher temperature. After the end of the reaction, the acetone is eliminated under reduced pressure and the solution is filtered. The aqueous monomer solution now present can be used directly for the copolymerization. Examples of these novel phosphorus-containing MAA monomers, their yields and 1H-NMR data are summarized in table 5. (a) The yield corresponds to the content of amidated MAA in comparison with unconverted amine and was determined with the aid of 1H-NMR (D2O) . (b) The amidation of the MAA gives a typical splitting of the vinylic protons of the MAA (5.96 (s) , 2H, CH=CH). In addition, a typical deep field shift of the proton signal CH2N(C=O) in comparison with the signal CH2NH of a free amino group of about 0.27 ± 0.07 ppm is obtained. B.1) General method for the copolymerization based on phosphorus-containing MAA monomers, poly(alkylene oxide)-containing alkenyl ethers and further comonomers In a thermostattable double-walled reactor, 1.0 mol of as concentrated an aqueous solution as possible of vinyloxybutyl poly(ethylene glycol) ether (VOBPEG, e.g. Mw = 500 g/mol) is initially taken and mixed with 1.O- 1.7 mol of a 25% strength solution of phosphorus- containing MAA derivative (e.g. MAA-AEP) at pH > 5 with stirring. Catalytic amounts of FeSO4•7H2O (0.05-0.5 mmol) and a 30% strength hydrogen peroxide solution (3O-100 mmol) are added under nitrogen at 15°C. The polymerization is effected at pH > 5 by uniform addition of a 3-10% strength solution of the reducing agent Bruggolit® (pH 5.O-6.3, from Bruggemann). The peroxide content is monitored and the polymerization is complete when the hydrogen peroxide has been completely consumed by the Bruggolit® (scheme 5) . The composition and molar mass of this copolymer 1 (AEP-5) is shown in table 6. The copolymerization can be varied and extended on the basis of the following examples: (1) The poly(alkylene glycol)-containing alkenyl ethers may have different chain lengths (e.g. VOBPEG: 50O, 110O, 2000 or 5800 g/mol) or may be mixtures of different chain length. Examples: Polymer 1, 2, 3, 4, 5, 10 (2) It is possible to use further phosphorus- containing MAA monomers, as described, for example, in tables 4 and 5. Examples: Polymer 1, 12, 14, 16, 17 (3) A variety of combinations of points (1) and (2) are possible. Examples: Polymer 13, 15, 18, 19, 20 (4) The poly(alkylene glycol)-containing alkenyl ethers can be substituted to a degree of O-100 mol% by low molecular weight alkenyl ethers (e.g. n-hydroxybutyl monovinyl ether HBVE) and esters (e.g. vinyl acetate). Examples: Polymer 21, 22, 23, 24, 25, 26 (5) The phosphorus-containing MAA monomers can be substituted to a degree of O-100 mol% by MAA and other MAA derivatives (e.g. N- hydroxyethylmaleimide MAI-HE). Examples: Polymer 27, 28, 29, 30 (6) Points (4) and (5) can likewise be combined. Examples: Polymer 31, 32 (7) It is possible to use O-100 mol eq. of further comonomers which may be both neutrally charged, such as, for example, a, P-unsaturated hydroxyalkyl esters, such as hydroxypropyl acrylate (HPA) or hydroxyethyl methacrylate (HEMA), and of an ionic nature (anionic: e.g. acrylic acid, or cationic: e.g. vinyl-containing quaternary ammonium compounds). Examples: Polymer 6, 7, 8, 9, 11 (8) Points (3) and (6) can of course also be combined with point (7) . The composition and molar masses of the phosphorus-containing copolymers mentioned are summarized in tables 6 and 7. To emphasize the essential importance of the anionic phosphorus-containing groups in the polymers with regard to their use as cement- containing superplasticizers, copolymers of N- hydroxyethylmaleamide (MAA-AE) and VOBPEG, which have exclusively carboxylate charges on the polymer backbone, were synthesized, cf. examples; Polymer 33, 34 Table 6 Synthesis of virtually alternating copolymers by the polymerization of virtually equimolar amounts of phosphorus-containing MAA monomers and PEG-containing vinyl ethers and the synthesis of phosphorus-containing polymers by the copolymerization of phosphorus- containing MAA derivatives and PEG-containing vinyl ethers with water-soluble esters of the a,O-unsaturated carboxylic acids (a) VOBPEG = vinyloxybutylpoly(ethylene) glycol (b) MAA-AE-P = N-(aminoethylphosphate)maleamide (c) MAA-AEE-P = N-(2- aminoethoxyethylphosphate)maleamide (d) MAA-AH-P = N-(aminohexylphosphate)maleamide (e) MAA-ABA-P = N-(aminobenzyl alcohol phosphate)maleamide (f) MAA-DEA-P2 = N-(diethanolamine diphosphate)maleamide (g) HPA = hydroxypropyl acrylate (h) HEMA = hydroxyethyl methacrylate (a) VOBPEG = vinyloxybutylpoly(ethylene glycol) ether (b) MAA-AE-P = N-(aminoethyl phosphate)maleamide (c) HBVE = hydroxybutyl vinyl ether (d) MAA-DEA-P2 = N-(diethanolamine diphosphate)maleamide (e) TEGVE = triethylene glycol methyl vinyl ether (f) MAI-HE = N-hydroxyethylmaleimide (g) MAA-AE = N-aminoethylmaleamide C) The use of the phosphorus-containing polymers as water reducers (superplasticizers) Determination of water-reducing power, retention of flowability and compressive strengths in mortar mixes The tests were carried out according to the concrete standards DIN EN 206-1, DIN EN 1235O-2 and DIN EN 1235O-5. The cement used was a CEM I 42.5 R (Karlstadt). The aggregates for the mortar and concrete mixes are shown in table 8. Mixing sequence for mortar mix: 600 g of cement powder are homogenized in dry form and introduced into an RILEM mixer. Thereafter, the amount of water required for a W/C value is added and mixing is eff ected for 30 sec at 140 rpm (speed I) . The sand mixture is then added with the aid of a funnel with the mixer running, and mixing is effected for a further 30 sec at 140 rpm (speed I). After a pause of 1.5 min in mixing and after the edges of the mixer have been cleaned, a corresponding amount of superplasticizer is added. Mixing is effected for a further 60 sec at 285 rpm (speed II) and the slump is then determined by tapping 10 times on a slump table with a Hagermann cone. Mixing sequence for concrete mix: A 30 1 mixer is used for the concrete mixes. 4.8 kg of cement and the corresponding amount of aggregates are premixed in dry form for 10 sec. Thereafter, 300 ml of the specified water are added, followed after a further 2 min of mixing by the amount of residual water required for the W/C value used. After a further 60 sec, the dissolved superplasticizer (0.2% by weight solid/cement) is added to the concrete mix and the mixing process is terminated after 60 sec with the determination of the slump. (a) S/C value = sand/cement value = Σ sand [g] - cement [g] (b) S/G value = sand/sand-gravel value = S sand [g] 4- (S sand [g] + S gravel [g]) (c) Origin of cement: Karlstadt (Germany) (d) 0.2% by mass of solid, based on cement (e) The required amount of water is dependent on the set W/C value(f) corresponding to the superplasticizer used (tab. 9 and 1O). W/C value = water/cement value = S water [g] 4- cement [g] amount of water required for producing a flowable mortar at a constant amount of cement. (c) Slump, determined after O, 3O, 60 and 90 min. (d) Purified sample: ultrafiltration using a 10 kDa membrane (e) Unfiltered sample: at a solids content of 100%, about 79% of polymeric product and 21% of low molecular weight constituents as, for example, residual monomers, salts, etc. are present after the polymerization. Table 10 Concrete tests (water-reducing power, slump retention and compressive strengths): a) ordered according to the best water-reducing power (W/C value) and b) the retention of flowability as a function of time (slump retention) (a) Dos. = dose [% by mass of polymer, based on cement] (b) Slump, determined after O, 1O, 4O, 60 and 90 min. (c) Purified sample: ultrafiltration using a 10 kDa membrane (d) Unfiltered sample: at a solids content of 100%, about 79% of polymeric product and 21% of low molecular weight constituents as, for example, residual monomers, salts, etc., are present after the polymerization. WE CLAIM 1. A copolymer based on phosphorus-containing monomers (A) of unsaturated dicarboxylic acid derivatives of the general formulae (Ia)and/or (Ib) where R2 = C1-C2O-(hetero) alkylene radicals optionally having O or N heteroatoms, which are linear or branched and optionally also have 1 to 10 substituents selected from the group consisting of OH, OPO3M2, OPHO2M, NH2 NH-CH2PO3M2, N(CH2-PO3M2)2, CZ(PO3M2)2, and C6-C1O- arylene radicals, Y = -N (CH2-PO3M2)2, -CZ (PO3M2)2 -OPHO2M, -OPO3M2, Z = H, Hal, OH, NH2, Hal = F, CI, Br, I, M = H, Na, K, NH4, N(R3)4, R3 = C1-C12-alkyl radicals, and C6-C10-aryl radicals, and macromonomers (B) of the general formula (II) where R4 = H, C1-C20-alkyl radicals, R5 = H, CH3, R6 = alkylene radicals having 0 to 20 C atoms, R7 = C1-C20-alkylene radicals; R8 = H, C1-C20 alkyl radicals, R9 = H, C1-C20-alkyl radicals, C6-C10-ar radicals, COR3, NO2M, SO3M, PO3M2, m = 0 to 10, n = 1 to 30O, p = 0 to 30O, and R3 and M having the abovementioned meaning. 2. The copolymer as claimed in claim 1, wherein the copolymers based on the monomers (A) and (B) also contain building blocks based on the monomers (C) according to the general formulae (IIIa) and (IlIb) in which X' is O, S, NH, NR10, R10 is H, C1-C2O- (hetero) alkyl radicals optionally having O or N heteroatoms, which are linear or branched and optionally have 1 to 10 OH and/or NH2 groups, and C6-C1O- aryl radicals and R1 and M have the abovementioned meaning. 3. The copolymer as claimed in claim 1, wherein the copolymers based on the monomers (A) and (B) and optionally (C) also contain building blocks based on the monomers (D) according to the general formula (IV) in which R11 is H, R10, (CH2)rOR10, 0 (C=O) R10, R12, R13 are H, C1-C2O-alkyl radicals or C6-C1O-aryl radicals and r is from 0 to 10 and R10 has the abovementioned meaning. 4. The copolymer as claimed in any of claims 1 to 3, wherein the copolymers based on the monomers (A) and (B) and optionally (C) and (D) also contain building blocks based on the monomers (E) according to the general formula (V) in which W is CN, CO-R14, R14 is H, OM, OR10, NHR10, N(R1O)2/,SR10 and R10, R12, R13 and M have the abovemention meaning. 5. The copolymer as claimed in any of claims 1 to 4, wherein the molar ratio of monomer (A) to monomer (B) in the copolymer is from 2 : 1 to 1 : 2. 6. The copolymer as claimed in any of claims 1 to 5, wherein, in the copolymer based on the monomers (A) and (B), up to 90 mol% of monomer (A) are replaced by monomer (C). 7. The copolymer as claimed in any of claims 1 to 6, wherein, in the copolymer based on the monomers (A) and (B), up to 90 mol% of the monomers (A) and (B) are replaced by the monomer (D). 8. The copolymer as claimed in any of claims 1 to 7, wherein, in the copolymer based on the monomers (A) and (B), up to 90 mol% of the monomers (A) and (B) are replaced by the monomers (C) and (D). 9. The copolymer as claimed in any of claims 1 to 8, wherein the copolymer based on the monomers (A) and (B) and optionally (C) and (D) also contains up to 10 mol equivalents of one or more monomers (E), based on the sum of the monomers (A) and (B) and optionally (C) and (D). 10. A process for the preparation of the copolymers as claimed in any of claims 1 to 9. wherein the monomers (A) and (B) and optionally (C) and (D) are subjected to a free radical polymerization. 11.The process as claimed in claim 10, wherein the free radical polymerization is carried out in an aqueous system in the temperature range from -10 to 100°C. 12.The process as claimed in claim 10 or 11, wherein the free radicals are produced by thermal decomposition of suitable peroxo or azo initiators, photochemically or by use of a redox system. 13.The process as claimed in claim 12, wherein water-soluble azo initiators are used. 14.The process as claimed in any of claims 10 to 13, wherein the free radical polymerization is carried out with the aid of a redox system consisting of hydrogen peroxide, iron (II) sulfate and a reducing agent in the temperature range from 0 to 30°C. 15.The process as claimed in any of claims 10 to 14, wherein the photochemical or redox free radical production is effected at temperatures from 0 to 30°C. 16. The copolymer as claimed in any of claims 1 to 9 wherein the copolymer is used as an additive for inorganic binder suspensions based on cement, lime, gypsum or anhydrite. 17. The copolymer as claimed in claim 16, wherein the copolymer is used in an amount from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, based on the weight of the inorganic binder. 18. The copolymer as claimed in claim 16 or 17, wherein the copolymer is used as a superplasticizer or water reducer. ABSTRACT COPOLYMERS BASED ON PHOSPHORUS CONTAINING MONOMERS AND PROCESSES FOR THE PREPARATION THEREOF The invention relates to copolymers based on phosphorous-containing monomers (A) and on macromonomers (B), to methods for the production thereof and to their use as additives for inorganic binding agent suspensions based on cement, lime, gypsum and anhydrite. The corresponding polymeric additives have, as flow agents, excellent water-reducing properties and hold the flowability of the concrete over a relatively long period of time (60 to 90 min.) to an almost unchanged level without having delayed action. In addition, the corresponding polymeric additives improve the processing and setting processes of the building materials produced with these additives by making possible earlier and higher resistances to pressure.

Documents:

04752-kolnp-2007-abstract.pdf

04752-kolnp-2007-claims.pdf

04752-KOLNP-2007-CORRESPONDENCE 1.1.pdf

04752-kolnp-2007-correspondence others.pdf

04752-kolnp-2007-description complete.pdf

04752-kolnp-2007-form 1.pdf

04752-kolnp-2007-form 2.pdf

04752-kolnp-2007-form 3.pdf

04752-kolnp-2007-form 5.pdf

04752-KOLNP-2007-INTERNATIONAL PRELIMINARY REPORT.pdf

04752-kolnp-2007-international publication.pdf

04752-KOLNP-2007-INTERNATIONAL SEARCH AUTHORITY REPORT-1.1.pdf

04752-kolnp-2007-international search report.pdf

04752-kolnp-2007-pct request form.pdf

04752-kolnp-2007-translated copy of priority document.pdf

4752-KOLNP-2007-(29-11-2011)-ABSTRACT.pdf

4752-KOLNP-2007-(29-11-2011)-AMANDED CLAIMS.pdf

4752-KOLNP-2007-(29-11-2011)-CORRESPONDENCE.pdf

4752-KOLNP-2007-(29-11-2011)-DESCRIPTION (COMPLETE).pdf

4752-KOLNP-2007-(29-11-2011)-EXAMINATION REPORT REPLY RECEIVED.pdf

4752-KOLNP-2007-(29-11-2011)-FORM-1.pdf

4752-KOLNP-2007-(29-11-2011)-FORM-2.pdf

4752-KOLNP-2007-(29-11-2011)-FORM-3.pdf

4752-KOLNP-2007-(29-11-2011)-OTHER PATENT DOCUMENT.pdf

4752-KOLNP-2007-(29-11-2011)-OTHERS.pdf

4752-KOLNP-2007-(29-11-2011)-PA.pdf

4752-KOLNP-2007-CORRESPONDENCE 1.3.pdf

4752-KOLNP-2007-CORRESPONDENCE 1.5.pdf

4752-KOLNP-2007-CORRESPONDENCE OTHERS 1.2.pdf

4752-KOLNP-2007-CORRESPONDENCE-1.4.pdf

4752-KOLNP-2007-EXAMINATION REPORT.pdf

4752-KOLNP-2007-FORM 18 1.1.pdf

4752-kolnp-2007-form 18.pdf

4752-KOLNP-2007-FORM 26.pdf

4752-KOLNP-2007-FORM 3.pdf

4752-KOLNP-2007-FORM 5.pdf

4752-KOLNP-2007-GRANTED-ABSTRACT.pdf

4752-KOLNP-2007-GRANTED-CLAIMS.pdf

4752-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

4752-KOLNP-2007-GRANTED-FORM 1.pdf

4752-KOLNP-2007-GRANTED-FORM 2.pdf

4752-KOLNP-2007-GRANTED-SPECIFICATION.pdf

4752-KOLNP-2007-OTHERS 1.1.pdf

4752-KOLNP-2007-OTHERS.pdf

4752-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf

4752-KOLNP-2007-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf