MXPA06010461A - Polymer comprising amide and ester groups method for production and use thereof - Google Patents

Abstract

The invention relates to a method for the production of a polymer (P) comprising amide and ester groups, whereby, in a first step, a homo- or co-polymer (P1) of (meth)acrylic acid is reacted with a monohydroxy compound (E) at a temperature of up to 200°C, such that, in addition to ester groups, anhydride groups are formed and, in a second step, the anhydride groups formed in the first stepare reacted with a monoamine compound (A) at temperatures significantly below 100°C. The invention further relates to polymers produced by the above method, the use thereof in hydraulic-setting compositions and said hydraulic-setting compositions before and after hardening by addition of water.

Description

POLYMER COMPRISING AMIDA AND ESTER GROUPS, METHOD FOR THEIR PRODUCTION AND USE THEREOF Technical Field The present invention relates to the group of amides and esters of polymers of α, β-unsaturated acids. STATE OF THE ART Polymers of α, β-unsaturated carboxylic acids having polyalkylene glycol side chains have already been used for some time in concrete technology as plasticizers due to their high degree of water reduction. These polymers have a comb-like polymer structure. There are a number of these comb-type polymers that in addition to ester groups and carboxylic acids. It also has amide groups. For the preparation of these polymers, essentially two processes are used. Either the polymers are prepared from the functional monomers-particular carboxylic acid, -ester and -amide, by radical polymerization or in an analogous reaction of polymer from a polycarboxyl polymer and the particular alcohols and amines. The route by radical polymerization is the most common method, but it is complicated for specific compounds by the commercial availability of the corresponding monomers and their toxicity, and requires complicated process control. The analogous polymer reaction has the great advantage that it is possible to obtain very different comb polymers with very different properties in a simple and reliable way by varying the amount, type and proportion of commercially available polymers of carboxylic acids to alcohol and amine. , ß unsaturated, especially from poly (meth) acrylic acids. In the analogous polymer reaction, as a result of the use of commercially available poly (meth) acrylic acids, the step of radical polymerization which is critical from a safety standpoint can be omitted. These analogous polymer reactions are described, for example in EP 0 889 860, EP 0 739 320 and DE 100 15 135. The analogous polymer reaction was carried out according to the current state of the art, in an acid-catalyzed reaction of carboxyl-containing polymers with amine-terminated derivatives or hydroxyl monofunctional, at temperatures from at least 140 degrees C to 200 degrees C. These reaction conditions give rise to various restrictions that make a primary or secondary low-boiling amine reaction impossible or lead to entanglement in the case of compounds that , in addition to the primary or secondary amino group also have hydroxyl functions. First, it is known to those skilled in the art that, in an analogous reaction of polymers containing carboxylic groups, the addition of compounds having more than one primary or secondary amine group or compounds, which in addition to the primary amine group or secondary, also has hydroxyl functions, inevitably lead to entanglement of carboxyl-containing polymers. However, this entanglement is undesirable since it leads to at least a reduction in the plasticizing action. In the extreme case, the entanglement can also lead to the fusion-entanglement reaction, so greatly that more than one reactor can not be removed. Entanglement can not be suppressed even by the use of solvents.

Secondly, many primary or secondary amine have a very low boiling point and are classified as an explosion risk in the classification of risks, since they can lead to explosions with air in certain mixing proportions and at certain ignition temperatures. All reactions known to date in an analogous polymer reaction are carried out either at high temperatures of at least 140 degrees C and in some cases also using reduced pressure, or introducing or passing a stream of air or nitrogen through or over the reaction mixture. These drastic conditions are required to remove the water formed in a condensation reaction and therefore allow a complete reaction. Nevertheless, the reaction of primary or secondary low boiling amines in an analogous polymer reaction becomes impossible or is made more complicated and costly by these conditions, since the high temperatures required, are usually above the ignition temperatures of the amines . Still further, the use of reduced pressure leads to being reduced to the boiling points of primary or secondary amines which are already low boiling, and these being undesirably removed from the reaction by the reduced pressure. The use of a gas stream for the removal of water from the reaction also leads to undesirable discharge of the amine from the reaction vessel. The observed result is an incomplete reaction, increased contamination of the distilled water and an increased contamination of the waste gas and waste air filter. Description of the Invention Therefore, an object of the present invention is to provide a process wherein the disadvantages of the prior art are overcome and primary or secondary low boiling compounds or amine which, in addition to the secondary primary amine group also have hydroxyl groups, can be used. It has surprisingly been found that this can be achieved by a process according to claim 1. This process allows polymers having amide and ester groups to be obtained only in incomplete form or with reduced quality, and in fact it happens with analogous processes. of typical polymer, that are prepared in a reliable way. This process allows a reaction of primary or secondary low boiling amines or compounds which, in addition to the primary or secondary amine group also has hydroxyl groups, and is extremely advantageous from ecological aspects with respect to exhaust gases and distillation water, and also aspects of process technology. The comb polymers prepared by the present process are highly suitable as plasticizers for hydraulic setting compositions. Still further, it has been found that surprisingly thanks to the process according to the invention, there is the possibility of achieving a high side chain density and also that the comb polymers thus prepared, in use in hydraulic setting compositions lead to reduced retardation. of the hardening operation and longer processing time. When the reduction in ion density in the usual polymer analogue process is attempted to control the properties of the polymer, for example by increasing the ester group content, there is steric hindrance from a certain degree of esterification which complicates the greater reaction or even makes it impossible. The resultant increased heat stress additionally increases the risk of cleavage of the polyester, which leads to entanglement of the unwanted polymers.

The invention encompasses the polymers prepared by this process, their use in hydraulic setting compositions and these hydraulic setting compositions before and after curing by water. Further advantageous embodiments of the invention are apparent from the subclaims. MODES OF CARRYING OUT THE INVENTION The present invention first relates to a process for preparing a polymer P having amide and ester groups, wherein in a first step, a homo- or co-polymer P1 of (meth) acrylic acid is reacted with a monohydroxy compound E at a temperature of up to 200 degrees C to form anhydride groups in addition to ester groups, and in a second step, the anhydride groups formed in the first step, are reacted with a monoamine A compound at temperatures significantly lower than 100. C. "Monohydroxy Compound" is understood herein and below to mean a substance having only one free hydroxyl group. "Monoamine compound" is understood herein and below to mean ammonia as a gas or as an aqueous solution or as a substance having only a free primary or secondary amino group. "(Meth) acrylic acid" is understood throughout this document to mean both acrylic acid and methacrylic acid. The homo- or co-polymer P1 of (meth) acrylic acid can be present here as a free acid, as a full or partial salt, the term "salt" here and below not only covers the classical salts which are obtained by neutralization with a base but also complexes between metal ions and the carboxylate or carboxyl groups as ligands.

The homo- or co-polymer P1 of (meth) acrylic acid is advantageously a homo- or co-polymer of methacrylic acid and / or acrylic acid and / or methacrylic salt and / or acrylic salt. The homo- or co-polymer P1 is preferably obtained from a homopolymerization of (meth) acrylic acid or a co-polymerization of (meth) acrylic acid with at least one additional monomer selected from the group comprising: carboxylic acids a , unsaturated ß, α, ß unsaturated carboxylates, α, ß-unsaturated carboxylates, styrene, ethylene, propylene, vinyl acetate and their mixtures. The additional monomer is preferably chosen from a group comprising methacrylic acid, acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and the salts, esters and mixtures thereof. A preferred copolymer P1 is a copolymer of acrylic acid and methacrylic acid and also its salts or partial salts. The salts or partial salts are typically obtained here by radical polymerization. A preferred homopolymer P1 is polymethacrylic acid or polyacrylic acid, especially polymethacrylic acid, its salts or partial salts. The salts or partial salts are here typically obtained by radical polymerization. P1 is preferably a homopolymer. The homo- or co-polymer P1 of (meth) acrylic acid is obtained by radical polymerization by customary processes. It can be carried out in a solvent, preferably in water or in bulk. This radical polymerization is preferably carried out in the presence of at least one molecular weight regulator, in particular an inorganic or organic sulfur compound, for example mercaptans, or a phosphorus compound. The polymerization is advantageously carried out under conditions such that the homo- or co-polymers P1 formed, are formed from 10 to 250, preferably 20 to 100, more preferably 25 to 80 monomer units. These homo- or copolymers P1 of (meth) acrylic acid are commercially available. The monohydroxy compound E is preferably a C6- to C20-alkyl alcohol or has the formula (I) HO - [(EO) x- (PO) y- (BuO) j-R1 (I).

In this formula, the indices x, y, z each independently have values of 0-250 and their sum x + y + z is from 3 to 250. In addition, in formula (I), EO = ethyleneoxy , PO = propyleneoxy, BuO = butyleneoxy or isobutyleneoxy. The sequence of the EO, PO, BuO units can be present in any possible sequence. Finally, the substituent R1 means an alkyl group having 1-20 carbon atoms or an alkylaryl group having 7-20 carbon atoms. Preference is given to monohydric compounds E of the formula (I), especially having a methyl, ethyl, i-propyl or n-butyl group as the substituent R and with z = 0. E preferably comprises copolymers of EO / PO, more preferably polyethylene glycol terminated at one end. Mixtures of a plurality of different compounds of group E are equally possible. For example, it is possible to mix polyethylene glycols terminated at one end and having different molecular weights, or it is possible for example to use mixtures of polyethylene glycol end-terminated with end-terminated ethylene oxide and propylene oxide copolymers or end-terminated propylene glycols. Also, for example, mixtures of C6- to C20-alkyl alcohols and end-terminated polyethylene glycols are also possible.

In a preferred embodiment, the monohydroxy compound E is a poly-alkylene glycol which is terminated at one end and has a molecular weight Mw from 300 to 10,000 g / mol, especially from 500 to 5000 g / mol, preferably 800 to 3000 g / mol In a first step, the homo- or co-polymer P1 is reacted with the monohydroxy compound E at a temperature of up to 200 degrees C. The temperature for this reaction is preferably between 140 degrees C and 200 degrees C. However, the Reaction is also possible at temperatures between 150 degrees C and 175 degrees C. This high temperature is required to obtain efficient esterification. In a preferred embodiment, this first step was carried out in the presence of a styration catalyst, especially an acid. This acid is preferably sulfuric acid, p-toluenesulfonic acid, benzensulfonic acid, methanesulfonic acid, phosphoric acid or phosphorous acids. Preference is given to sulfuric acid. The water can be removed from the reaction mixture under atmospheric pressure or otherwise under reduced pressure. It is also possible for the gas stream to be conducted on or through the reaction mixture. The gas stream used can be air or oxygen. In one embodiment, in the first step as a monoamine compound A "is further used the monohydroxy compound E. As a result, not only ester and anhydride groups are formed, but also amide groups as early as the first stage. It has a boiling point and an instantaneous flash point which are higher than the reaction temperature of the first stage.Furthermore, the monoamine compound A "must not contain hydroxyl groups.

Typical examples of these monoamine compounds A 'can be illustrated by the formula (II1). R2NH-R3 '(II') First, R2 'and R3' together can form a ring that optionally contains oxygen, sulfur or additional nitrogen atoms. Examples of these monoamine compounds A 'are 9H-carbazole, indoline or imidazole. Second, R2 'and R3' can each independently be an alkyl group having from 8 to 20 carbon atoms, a cycloalkyl group having from 5 to 9 carbon atoms, an adalkyl group having from 7 to 12 carbon atoms, a compound in (III '), (IV) or (V) or H -R' -X (R5 ') V (ill') - [(EO) x- (PO) y- (BuO) z] -R1 (V) R4 'here is a C1- to C4-alkylene group. R5 'is a C to C4-alkyl group. X = S, O or N, and v = 1 when X = S or 0, ov = 2 when X = N. R6 'is an alkylene group that optionally has heteroatoms and forms a ring of 5-8 with the nitrogen atom - members, in particular a 6-member ring. The substituent R1 and the indices x, y and z each are as defined for the compound of the formula (I). Examples of these monoamine compounds A "are dioctylamine, distearylamine, di (tallow fat) amine, fatty amines such as stearylamine, coconut fat amine, octadecylamine, pig fat amine, oleylamine; 3-butoxypropylamine, bis (2) -methoxyethyl) amine, α-methoxy-α-amino-polyoxyethylene, α-methoxy-α-amino-polyoxy-propylene, α-methoxy-α-amino-oxyethylene-oxypropylene copolymer of α-methoxy-cy-amino-oxyethylene oxypropylene The monoamine compound A 'is preferably a primary monoamine Particularly preferred monoamine compounds A "are compounds of the formula (II') wherein R2 is of the formula (V) and R3 'is H; especially copolymers of α-methoxy-? -amino-oxyethylene-oxypropylene or α-methoxy-? -amino-polyoxyethylenes. More are preferred to -methoxy-? -amino-polyoxyethylenes. These monoamine compounds A "are, for example, obtained from a polymerization initiated by alcohols of ethylene oxide and / or propylene oxide, followed by conversion of the terminal alcohol group to an amine group.The homo- or co-polymer P1 is reacted with the monohydroxy compound E typically such that the monohydroxy compound E is added to the homo- or co-polymer P1 with stirring and the mixture is heated to the reaction temperature.The mixture is stirred at the reaction temperature described above and reacts , possibly under reduced pressure or when passing a stream of gas over or through the reaction mixture If monoamine compound A "is used it can be added simultaneously with the monohydroxy compound E or otherwise at a later time during the first stage of reaction. After the reaction, which can be monitored by measuring the acid number, the reaction product is either further processed or stored. The storage can be carried out either in heated containers or at room temperature. In the latter case, the reaction product can be heated again before further use, for example until it melts.

In the first step, in addition to the esters between the homo- or copolymers P1 and the monohydroxy compound E - and if appropriate in addition to the amides between the homo- or co-polymer P1 and the monoamine compound A '- anhydride groups can also be form. The existence of these anhydride groups can be demonstrated in a very simple way by infrared spectroscopy, since the anhydride group is known to have a very intense double band in the region of -1800 cm "1 and -1760 cm" 1. Preference is given to not using amines A 'in the first stage. In a second step, the product that is formed in the first stage and has anhydride groups in addition to ester groups and optionally amide groups, is reacted with a monoamine compound A at temperatures significantly lower than 100 degrees O This reaction is preferably carried out lower at 60 degrees C, especially below 40 degrees C. The reaction preferably takes place between 10 degrees C and 60 degrees C, more preferably between 15 and 40 degrees C. This reaction can be achieved under slight conditions and does not require reduced pressure, in such a way that it is also possible to use monoamine A compounds with a low boiling point or otherwise composed of monoamine A which in addition to the amino group also contain hydroxyl groups. The monoamine compound A preferably has the formula (II) R2NH-R3 (II).

First, R2 and R3 together can form a ring that optionally contains oxygen, sulfur or additionally nitrogen atoms.

Examples of these monoamine A compounds in particular are piperidine, morpholine, pyrrolidine, 1,3-thiazolidine, 2,3-dihydro-l, 3-thiazole, imidazole. Morpholine is particularly convenient. Secondly, R2 and R3 each independently can be an alkyl group having from 1 to 12 carbon atoms, a cycloalkyl group having from 5 to 9 carbon atoms, an aralkyl group having from 7 to 12 carbon atoms, a hydroxyalkyl group, a compound of the formula (III), (IV) or (V) or H-R4-X (R5) V (III) - [(EO) x- (PO) y- (BuO) J-R1 (V) R4 is a C1- to C4-amino group. R is a C to C -alkyl group. X = S, 0 or N, and v = 1 when X = S or 0, ov = 2 when X = N. R6 is an alkylene group that optionally has heteroatoms and, with the nitrogen atom forms a ring of 5-8 -Members, especially a 6-member ring. The substituent R1 and the indices x, y and z, each are as defined by the compound of the formula (I). A preferred hydroxyalkyl group is the group -CH 2 CH 2 -OH or -CH 2 CH (OH) CH 3. Suitable monoamine compounds A are, for example, ammonia, butylamine, hexylamine, octylamine, decylamine, diethylamine, dibutylamine, dihexylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine and cyclooctylamine, dicyclohexylamine; 2-phenylethylamine, benzylamine, xylylamine; N, N-dimethylethylenediamine, N, N-diethylethylenediamine, 3,3'-iminobis (N, N-dimethyl-propylamine), N, N-dimethyl-1,3-propanediamine, N, N-diethyl- 1,3-propanediamine, NNN'-trimethylethylene diamine, 2-methoxyethylamine, 3-methoxypropylamine; ethanolamine, isopropanolamine, 2-aminopropanol, diethanolamine, diisopropanolamine, N-isopropylethanol-amine, N-ethylethanolamine, N-butylethanolamine, N-methylethanolamine, 2- (2-aminoethoxy) ethanol; 1- (2-aminoethyl) piperazine, 2-morpholinoethylamine, 3-morpholinopropylamine. The monoamine compound A more preferably is selected from the group comprising ammonia, morpholine, 2-morpholine-4-yletylamine, 2-morpholine-4-ylpropylamine, N, N-dimethylaminopropylamine, ethanolamine, diethanol-amine, 2- (2 -aminoethoxy) ethanol, dicyclohexylamine, benzylamine, 2-phenylethylamine and mixtures thereof. Ammonia can be used as a gas or in an aqueous solution. Due to the operating and operational advantages, it is preferred to employ ammonia as an aqueous solution. The monoamine compound A can also be a monoamine compound A ', although this is not preferred. For the reaction in the second stage, preference is given to using a solvent. Preferred solvents are for example, hexane, toluene, xylene, methylcyclohexane, cyclohexane or dioxane, and also alcohols, especially ethanol or isopropanol, and water, with water being the most preferred solvent. In a preferred embodiment, the second step is carried out by initially charging the amine in a solvent, preferably water, and adding the product of the first reaction step with stirring as a polymer melt or otherwise in solid form, for example as a powder or in the form of bed or flakes or a granule. Preference is given to addition as a polymer melt. In a further preferred embodiment, the second step is performed by adding the mixture or solution of amine and solvent, preferably water, to the polymer melt cooled to below 100 degrees C. This second reaction step can follow the first stage of reaction directly, where the product is already present as a fusion or otherwise at a later time. When solvent is used in the second stage, the solvent can, if desired, be again removed for example by applying reduced pressure and / or heating or it can be further divided. In the second step, in addition to the amide formation, amine salts can also be formed. In order to reduce this amine salt formulation and increase the amidation yield, alkali metal hydroxides or alkaline earth metal hydroxides may be added preferably to the monoamine compound A. The process according to the invention allows polymers P having amide and ester are obtained, which can be obtained by the typical polymer analogue process only with poor quality, if the amines required for the amide groups are very highly volatile or have a very low instantaneous evaporation point or in addition to the Amide group also has hydroxyl groups. Furthermore, this process allows the content of carboxylic acid groups, and hence the density of ions in the polymer backbone, to be reduced in a very simple manner without increased stress or thermal stress and therefore without the risk of Polyester cleavage which can lead to undesirable entanglement of the polymers. When attempts are made to reduce the ion density in analogous processes of customary polymers, for example by increasing the ester groups, there is hindered esterification from a certain degree of esterification, which complicates the greater reaction or even makes it impossible. Depending on the amount and type of monoamine A compounds, different properties of the final product can be achieved. Therefore, an additional advantage of the process according to the invention is that starting from an intermediate, ie the reaction product of the present step, it is possible in a simple and cost-efficient way to use different monoamine compounds or different amounts of the monoamine compound A to prepare several different polymers P having amide and ester groups. This has great logistical and financial advantages. In a preferred embodiment, the polymer P having amide and ester groups, essentially has the structure of the formula (VI) b2 b1 c M here is a cation, in particular H + Na +, Ca ++ / 2, Mg + 72, NH4 + or an organic ammonium. It is clear to the person skilled in the art that, in the case of polyvalent ions, an additional counterion must be present which, among others, may also be a carboxylate of the same molecule or another polymer molecule The organic ammonium compounds in particular are organic tetraalkylammonium in particular are tetraalkylammonium or otherwise HR3N + wherein R is an alkyl group especially a C1 to C6-alkyl group, preferably ethyl or butyl. Organic ammonium ions are obtained in particular by neutralizing the carboxyl group with commercial tertiary amines.

Each of the R7 substituents independently is an H or methyl. Methyl is preferred as the substituent R7. The substituents R2 and R3 have already been described for the monoamine compound A of the formula (II). The substituents R2 'and R3' have already been described for the monoamine compound A 'of the formula (II'). The substituents R1, EO, PO, BuO and the indices x, y and z have already been described for the monohydroxy compound E of the formula (I). The indices n, m, m 'and p each are integers where the sum of n + m + m' + p = 10-250, preferably 20-100, in particular 25-80, and n > 0, m > 0 and p > 0 and m '> 0. The sequence of the three units a, b1, b2 and c can be in blocks or random, except that, as a result of the anhydride mechanism of the amide formation, unit b2 must be adjacent to / or close to, especially adjacent to , to. The ratio of a: bl: b2: c here is (0.1-0.9) :( 0-0.06) :( 0.001- 0.4) :( 0.099-0.899), with the following boundary conditions: that the sum a + bl + b2 + c forms the value 1 and the proportion b2 / a is > 0 and < 1. In a preferred embodiment, a polymethacrylic acid is esterified with a polyethylene glycol which is terminated at one end with a methoxy group and then gently selected with mono- or diethanolamine. Polymer P having amide and ester groups finds use in various fields, especially in concrete and cement technology. In particular, the polymer P having amide and ester groups can be used as a plasticizer for hydraulic setting compositions, especially concrete and mortar. In this case, the polymer P having amide and ester groups can be mixed with a dry mixture comprising at least one hydraulic setting substance. The hydraulic setting substance can in principle be any substances known to the person skilled in the concrete art. In particular, they are cements, for example Portland cements or alumina melting cements and their respective mixtures with fly ash, fumed silica, slag, slag sands and lime filling. In addition, hydraulic setting substances are gypsum, in the form of anhydrite or hemihydrate or calcined lime. A preferred hydraulic setting substance is cement. In addition, additives such as sand, gravel, rocks, quartz flour, chalk, and customary constituents as additives, such as other concrete plasticizers, for example lignosulfonates, formaldehyde-sulfonated naphthalene condensates, formaldehyde-sulphonated melamine or polycarboxylate ethers condensates. , accelerators, corrosion inhibitors, retarders, shrinkage reducers, defoamers, dust formers are possible. If the polymer P having amide and ester groups is present in anhydrous form, the polymer P having amide and ester groups can be a constituent of a hydraulic setting composition, known as dry mix, which is stored over a prolonged period and typically It is packed in sacks or stored in silos and used. The polymer P having amide and ester groups can also be added to a conventional hydraulic setting composition with or just before or just after the addition of water. It has been found to be particularly convenient to add the polymer P. having amide and ester groups in the form of an aqueous solution or dispersion, especially as mixing water or as part of the mixing water.

The polymer P having amide or ester groups is useful as a plasticizer for hydraulic setting compositions, especially cementitious compositions, ie the resulting mixture in the water / cement (W / C) proportions in cement and concrete technology has a significantly higher flow performance compared to a composition without the plasticizer.

Flow performance is typically measured by the spread of dispersion. On the other hand, mixtures can be achieved which, in the same flow performance, require significantly less water, so that the mechanical properties of the cured hydraulically set composition are greatly increased. The polymer P having amide and ester groups can also be used as a dispersant. Examples Seríes de Éiemplos 1 1st stage: Esterification / amidation and anhydride formation A reaction vessel with stirrer, thermometer, vacuum connection and distillation unit is initially charged with 960 g of a 40% aqueous solution and a polymethacrylic acid that it has an average molecular weight of 5000 g / mol. With stirring, 10 g of 50% sulfuric acid and 16 g of a copolymer of ethylene oxide and propylene oxide in an EO / PO composition of 70:30 having a molecular weight Mw of 2000 g / mol, having a methoxy group at one end and a primary amino group at the other end, are added. 1200 g of a polyethylene glycol terminated at the end with a methoxy group at one end and having an average molecular weight of 1100 g / mol, is added as a melt and the clearest reaction is heated to 160 degrees C slowly with stirring. In the course of this, water is continuously distilled. As soon as the reaction mixture has reached 160 degrees C, the mixture is stirred at this temperature for 30 minutes and the water is still subjected to distillation. 16 g of 50% NaOH are then added and the temperature is increased to 165 degrees C. The esterification is carried out under reduced pressure (80 mbar) for 3 hours. The direct acid number is determined as 1.04 mmoles of COOH / g of polymer. The molten polymer is transferred and stored in an oven at 60 degrees C. Designation: BP1. Some of the polymer is dissolved in water to prepare a 40% solution which is designated as comparative polymer solution CP1-0. Second stage: light amidation 60 g of an aqueous ammonia solution at about 20-25 degrees C having the concentration specified in Table 1, are initially charged into a flask, and 40 g of the polymer melt BP1 at a temperature of approximately 60 degrees C, they are added with agitation. The mixture is stirred, dissolved and amidated for two hours.

Table I - Examples of the invention based on the reaction product BP1 of the first stage.

Series of examples 2 First stage: Esterification and anhydride formation A reaction vessel with stirrer, thermometer, vacuum connection and distillation unit is initially charged with 480 g of a 40% aqueous solution of polymethacrylic acid having an average molecular weight of 5000 g / mol. g of 50% sulfuric acid are added by stirring. 300 g of a polyethylene glycol is terminated at one end with a methoxy group and having an average molecular weight of 1100 g / mol and 600 g of a polyethylene glycol terminated at one end with a methoxy group having an average molecular weight of 3000 g / mol, is added as a melt and the reaction mixture is heated to 170 degrees C slowly with stirring. In the course of this, water is continuously distilled off. As soon as the reaction mixture has reached 170 degrees C, it is stirred at this temperature for 30 min. Subsequently, esterification is carried out additionally under reduced pressure (80-100 mbar) for 3.5 hours. The direct acid number at the end of the reaction time is determined as 0.67 mmol COOH / g polymer. The molten polymer is transferred and stored at 60 degrees C. Designation: BP2 Some of the polymer is dissolved in water to prepare a 40% solution which is designated as comparative polymer solution CP2-0. 2nd stage: Light amination a) Reaction with ethanolamine Ethanolamine is mixed with 50 g of water at about 20 degrees O Subsequently, the appropriate amount of polymer melt BP2 is mixed and dissolved with stirring. The solution is stirred at room temperature for 24 hours and diluted to a solids content of 40%.

Table 2. Examples of the invention based on the reaction product BP2 of the first stage and ethanolamine. b) Reaction with dicyclohexylamine Dicyclohexylamine is mixed with 50 g of water at about 40 degrees C. Subsequently, the appropriate amount of polymer melt BP2 is mixed and dissolved with stirring. The solution is stirred at room temperature for 24 hours and diluted to a solids content of 40%.

Table 3. Examples of the invention based on the reaction product BP2 of the first stage and dicyclohexylamine. c) Reaction with 2-phenylethylamine 2-phenylethylamine is mixed with 50 g of water at about 40 degrees C. Subsequently, this mixture is prepared in the appropriate amount of polymer melt BP2 having a temperature of 80 degrees C with stirring. The mixture is stirred for 5 hours and a clear solution is obtained. The solution is diluted to a solids content of 40%.

Table 4. Example of the invention based on the reaction product BP2 in the first stage and 2-phenylethylamine. You will be example 3 1st stage: Esterification and anhydride formation A reaction vessel with stirrer, thermometer, vacuum connection and distillation unit is initially charged with 383 g of a 50% aqueous solution of a polyacrylic acid having a weight molecular average of 4000 and a pH of 3.4. 17 g of 50% sulfuric acid are added with stirring. 6000 g of polyethylene glycol end-capped with a methoxy group and having an average molecular weight of 1000 g / mol is added as a melt and the reaction mixture is heated to 170 degrees C slowly with stirring. In the course of this, water is continuously distilled off. As soon as the reaction mixture has reached 170 degrees C, it is stirred at this temperature for 30 minutes. Subsequently, further esterification is effected under reduced pressure (100-200 mbar) at 175 degrees C for 3 hours. The direct acid number at the end of the reaction time is determined as 1.9 mmol of COOH / g of polymer. The molten polymer is transferred and stored at 60 degrees C. Designation: BP3.

Some of the polymer is dissolved in water to prepare a 40% solution that is designated as a CP3-0 comparative polymer solution. 2nd stage: Light amidation Ethanolamine in an amount according to Table 5 is mixed with 50 g of water at about 20 degrees O Subsequently, the appropriate amount of polymer melt BP3 is mixed and dissolved with stirring. The solution is stirred at 40 degrees C for 2 hours.

Table 5. Examples of the invention based on reaction product BP3 of the first stage and ethanolamine. Comparative example in which the ethanolamine is added in the first reaction step The reaction is carried out analogously to the first stage of the series of examples 2, except that 37 g of ethanolamine is added simultaneously with the addition of polyethylene glycols terminated in a extreme. During the heating and removal of water by distillation, the reaction mixture becomes inhomogeneous and viscous; the mixture gels at 120 degrees O The reaction stops. A homogeneous solution of the polymer can not be prepared.

Comparative examples: Salt formation The polymer melt is dissolved in 70 g of water and left to stand at 60 degrees C for two days. Subsequently, an amount of the articular amine is added according to Table 5.

Table 6 Comparative examples based on reaction product BP2 or BP3 of the first stage. Exemplary hydraulic setting compositions Effectiveness of the polymers of the invention is tested in mortar.

Mortar mix 1: MM1 (maximum grain size 8 mm) Quantity Cement (Schweizer CEM I 42.5) 750 g Lime filler 141 g 0-1 mm sand 738 g 1-4 mm sand 1107 g Table 7. Composition of the mortar mixtures used. The sands, the filling and the cement were mixed dry in a Hobart mixer for 1 minute. In 30 seconds, the mixing water where the polymer dissolves, it is added and mixing is continued for 2.5 more minutes. The total mixing time of the wet mix is 3 minutes. All polymer solutions were provided with the same amount of a defoamer before the mortar test. Test methods and results - Direct acid number Approximately 1 g of polymer melt is dissolved in approximately 30 ml of deionized water and mixed with 3 drops of a phenolphthalein solution (1% in ethanol). 0.1 N NaOH is used to titrate until the color change. Acid number in mmol of COOH / g = V / (1 O x m) V = 0.1 N NaOH consumption in ml and m = weight of the polymer melt in g. - Flow chart dispersion The dispersion of the flow chart of the mortar is determined by EN 1015-3. - Air content The air content of the mortar is determined in accordance with EN 196-1. - End of setting The setting time is determined by the evolution of temperature in a Styropor container filled with mortar with an approximate capacity of 1 I. The end of setting is defined as the time in which the temperature curve has the maximum value. - Pressure resistance The pressure resistance of hardened mortar prisms is determined in accordance with EN 196-1. Results Table 8 clearly shows the advantage of the polymers of the invention compared to the comparative example, while the processability of the mortar comprising the polymer of the comparative example deteriorates significantly with time (decreases the dispersion of the flow chart), that of the mortars comprising the polymers of the invention scarcely decrease in 90 minutes; on the contrary, it even increases over time for some. This can be clearly for the low value, in some cases even negative for? 0-9o- Tables 9 and 10 also show the excellent maintenance of processability during 90 minutes of mortars comprising the polymers of the invention, while mortars comprising the comparative polymers lose a significant degree of processability. The 24 hour pressure resistance of mortar prisms comprising the polymers of the invention is the same as that of the mortar prisms comprising the comparative polymers even though the dose of the comparative polymers is lower. This means that the polymers of the invention delay the setting of the mortars in a smaller proportion than the comparative polymers. These examples clearly show that the polymers of the invention have long processability of mortar or concrete mixtures required in many applications without having the disadvantage of a reduced 24 hour strength that is often found in these polymers. Furthermore, these mortar results show that the amidation is carried out in the reaction in the second reaction stage. The properties of the polymers of the invention differ with respect to the processability maintenance of the mortar mixtures, significantly from those of the starting polymers and the amine salts. Table 8. Results of series of Example 1 of mortar mixtures MM1.

Table 8 (continued) Table 9. Results of the Example 2 series of MM1 mortar mixtures. Table 9 (continued) ?? Table 10. Series results of Examples 3 of mortar mixtures MM1. Table 10 (continued) Table 10. Mixing results of MM2 mortars comprising polymer P having ether and amide groups and comparative experiment.

Table 11 (continued)

Claims (24)

1. CLAIMS 1. A process for preparing a polymer P having amide and ether groups, characterized in that: in a first step a homo- or copolymer P1 of (meth) acrylic acid is reacted with a monohydroxy compound E at a temperature of up to 200 degrees C, to form anhydride groups in addition to ester groups, and in a second step, the anhydride groups formed in the first step are reacted with a monoamine compound A at temperatures significantly lower than 100 degrees C to give the amide.
2. 2. The process according to claim 1, characterized in that the first step is carried out in the presence of an acid, especially sulfuric acid, p-toluenesulfonic acid, benzensulfonic acid, methanesulfonic acid, phosphoric acid or phosphorous acid, preferably sulfuric acid .
3. 3. The process according to claim 1 or 2, characterized in that the monohydroxy compound E is a C6- to C20-alkyl alcohol or has the formula (I) HO - [(EO) x- (POV (BuO) J -R1 (I) where x, y and z each independently have the values of 0-250 and x + y + z = 3-250; EO = ethyleneoxy, PO = propyleneoxy, BuO = butyleneoxy or isobutyleneoxy, with a sequence of EO units , PO, BuO in any possible sequence, and R1 = alkyl group having 1-20 carbon atoms or alkylaryl group having 7-20 carbon atoms 4.
4. The process according to claim 3, characterized in that z = 0 and R1 = methyl, ethyl, i-propyl or n-butyl group 5.
5. The process according to claim 3 or 4, characterized in that the monohydroxy compound E is a polyalkylene glycol that is end-terminated and has a molecular weight.
6. Mw from about 300 to 10 000 g / mol, especially from 500 to 5000 g / mol, preferably from 800 to 3000 g / mol. according to one of claims 1 to 5, characterized in that the homo- or copolymer P1 of (meth) acrylic acid is prepared by homopolymerization of (meth) acrylic acid or by acid copolymerization. (meth) acrylic with at least one additional monomer selected from the group comprising α, β-unsaturated carboxylic acids, α, β-unsaturated carboxylates, β-unsaturated carboxylates, styrene, ethylene, propylene, vinyl acetate and mixtures thereof.
7. The process according to claim 6, characterized in that the additional monomer is selected from the group consisting of methacrylic acid, acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and its salts, esters and mixtures.
8. The process according to one of the preceding claims, characterized in that the copolymer P1 is a copolymer of acrylic acid and methacrylic acid and its salts or partial salts; or the homopolymer P1 is a polymethacrylic acid or polyacrylic acid, preferably a polymethacrylic acid, its salts or partial salts.
9. The process according to one of the preceding claims, characterized in that the homo- or copolymer P1 of (meth) acrylic acid is prepared by radical polymerization in the presence of at least one molecular weight regulator, especially one compound of sulfur or a phosphorus compound.
10. 10. The process according to one of the preceding claims, characterized in that the homo- or copolymer P1 is a homo- or copolymer which is formed from 10 to 250, preferably from 20 to 100, in particular from 25 to 80 monomer units. .
11. The process according to one of the preceding claims, characterized in that the monoamine compound A is an amine of the formula (II) R2NH-R3 (II) wherein R2 and R3 together form a ring that optionally comprises oxygen, sulfur or additional nitrogen atoms; or wherein R2 and R3 are independently an alkyl group having 1 or 2 carbon atoms, a cycloalkyl group having from 5 to 9 carbon atoms, an aralkyl group having from 7 to 12 carbon atoms, a group hydroxyalkyl, especially -CH2CH2-OH or -CH2CH (OH) CH3, a compound of the formula (III), (IV) or (V) or H-R4-X (R5) V (III) - [(EO) x- (PO) y- (BuO) z] -R1 (V) wherein R 4 is an alkylene group and R 5 is a d- to C 4 -alkyl group, and X is an S, O or N, and v = 1 when X = S or O, or v = 2 when X = N; and R6 is an alkylene group optionally having heteroatoms; x, y, z, each independently has the values of 0-250 and x + y + z = 3-250; 5 EO = ethyleneoxy, PO = propyleneoxy, BuO = butyleneoxy or isobutyleneoxy, with a sequence of units EO, PO, BuO in any possible sequence; and R1 = alkyl group having 1-20 carbon atoms or alkylaryl group having 7-20 carbon atoms.
12. The process according to claim 11, characterized in that the compound A is selected from the group comprising ammonia, morpholine, 2-morpholine-4-ylethylamine, 2-morpholine-4-ylpropylamine, N, N-dimethylaminopropylamine, ethanolamine, diethanol-amine, 2- (2-aminoethoxy) ethanol, dicyclohexyl-amine, benzylamine, 2-phenylethylamine and mixtures thereof.
13. The process according to one of the preceding claims, characterized in that a monoamine compound A 'is used in the first stage in addition to the monohydroxy compound E.
14. 14. The process according to claim 13, characterized in that the monoamine compound A 'is an amine of the formula (II1) R2NH-R3' (II ') wherein R2' and R3 'together form a ring optionally comprising oxygen, sulfur or additional nitrogen atoms; or wherein R2 'and R3', each independently is an alkyl group having from 8 to 20 carbon atoms, a cycloalkyl group having from 5 to 9 carbon atoms, an aralkyl group having from 7 to 12 carbon atoms; carbon, a compound of the formula (III '), (IV) or (Y) or H -R4'-X (R5 ') V (lll') - [(EO) x- (PO) y- (BuO) z] -R1 (V) wherein R 4 'is an alkylene group and R 5' is a C to C 4 -alkyl group, and X is an S, O or N, and v = 1 when X = S or O, or v = 2 when X = N; and R6 'is an alkylene group which optionally has heteroatoms, x, y, z each independently has the values of 0-250 and x + y + z = 3-250; EO = ethyleneoxy, PO = propyleneoxy, BuO = butyleneoxy or isobutyleneoxy, with a sequence of the units EO, PO, BuO in any possible sequence; and R1 = alkyl group having 1-20 carbon atoms or an alkylaryl group having 7-20 carbon atoms.
15. 15. The process according to claim 14, characterized in that the substituents R2 of the formula (V) and R3 'in the compound A' of the formula or (II ') each are H, and the compound A' is in in particular a copolymer of α-methoxy-? -amino-oxyethylene-oxypropylene or an α-methoxy-? -amino-polyoxyethylene, preferably to -methoxy-? -amino-polyoxyethylene.
16. The process according to one of the preceding claims, characterized in that the second step is carried out in a solvent, especially hexane, toluene, xylene, methylcyclohexane, cyclohexane or dioxane, or alcohols or water, preferably water.
17. The process according to one of the preceding claims, characterized in that the temperature of the first stage is between 140 degrees C and 200 degrees C, and the temperature of the second stage is between 10 0 degrees C and 60 degrees C, preference between 15 degrees C and 40 degrees O
18. 18. The process according to one of the preceding claims, characterized in that the polymer P having amide and ester groups has the formula (VI) b2 b1 c wherein M = cation, especially H + Na +, Ca ++ / 2, Mg ++ / 2, NH4 ++ or an organic ammonium; R7 each independently are an H or methyl, especially methyl; and R2 and R3 together form a ring optionally comprising additional oxygen, sulfur or nitrogen atoms; or R2 and R3 independently are an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having from 5 to 9 carbon atoms, an aralkyl group having from 7 to 12 carbon atoms, a hydroxyalkyl group, especially -CH2CH2-OH or -CH2CH (OH) CH3, a compound of the formula (III), (IV) or (V) or H-R4-X (R5) V (III) - [(EO) x- (PO) y- (BuO) J-R1 (V) and R2 'and R3' together form a ring optionally comprising additional oxygen, sulfur or nitrogen atoms; or R2 'and R3' each independently are an alkyl group having from 8 to 20 carbon atoms, a cycloalkyl group having from 5 to 9 carbon atoms, an aralkyl group having from 7 to 12 carbon atoms, an composed of the formula (III '), (IV) or (V) or H -R4-X (R5) V (III') - [(EOMPO ÍBuOy-R1 (V) and n + m + m '+ p = 10-250, preferably 20-100, and n > 0, m > 0, p > 0 and m ': > 0, and wherein R4 and R4 are each an alkylene group, R5 and R5 'are each a C to C4-alkyl group, R6 and R6' each are an alkylene group that optionally has heteroatoms, X is an S, 0 or N, v = 1 when X = S or 0, ov = 2 when X = N, x, y, z each independently have the values of 0-250 and x + y + z = 3-250; EO = ethyleneoxy, PO = propyleneoxy, BuO = butyleneoxy or isobutyleneoxy, with a sequence of the EO, PO, BuO units in any possible sequence; and R1 = alkyl group having 1-20 carbon atoms or alkylaryl group having 7-20 carbon atoms.
19. 19. A polymer P having amide and ester groups, characterized in that it is prepared by a process according to one of claims 1 to 18.
20. 20. A polymer P having amide and ester groups, characterized in that it is prepared by a process of according to claim 18 and because the ratio of a: b1: b2: c = (0.1-0.9): (0-0.06): (0.001-0.4): (0.099-0.899), and where the sum of a + b1 + b2 + c forms the value 1 and where the ratio b2 / a > 0 and < 1.
21. The use of a polymer P having amide and ester groups, according to claim 19 or 20, as a plasticizer for hydraulic setting compositions, especially concrete and mortar.
22. 22. A hydraulic setting composition comprising at least one polymer P having glucosamide and ester, according to claim 19 or 20.
23. 23. A hydraulic setting composition coated with water, comprises at least one polymer P having amide and ester groups according to claim 19 or 20.
24. 24. The use of a polymer P having amide and ester groups according to claim 19 or 20, as a dispersant.