Emulsifying polymers and use thereof

FIELD: chemistry.

SUBSTANCE: invention relates to emulsifying polymers and use of these polymers for stable emulsification of hydrophobic additives in aqueous concrete plasticisers. Disclosed is a polymer P, obtained via copolymerisation (a) of at least one ethylenically unsaturated monomer A selected from a group consisting of unsaturated mono- and dicarboxylic acids, sulphonic acids, phosphonic acids in form of free acids or salts or partial salts or halide or anhydride, with (b) at least one ethylenically unsaturated monomer B of formula ,

or ,

where radicals and coefficients are as described in the claim and (c) with at least one ethylenically unsaturated monomer C of formula

,

where radicals and coefficients are as described in the claim and with (d) at least one ethylenically unsaturated monomer D of formula

,

where radicals and coefficients are as described in the claim and optionally (e) with at least one basic ethylenically unsaturated monomer E of formula ,

where radicals and coefficients are as described in the claim and optionally (f) with at least one other ethylenically unsaturated monomer W. Use of the polymer as a plasticiser for water-curable compositions and a water-curable composition are also disclosed.

EFFECT: polymer improves quality of mortar.

19 cl, 5 tbl

 

The technical field

The present invention relates to emulsifying polymers, in particular to the use of these polymers for the stable emulsification of hydrophobic additives to water softeners concrete.

The level of technology

Polymers of α-β-unsaturated carboxylic acids with polyalkyleneglycols side chains long been used in concrete technology as plasticizers because of their strong water absorption. These polymers have a comb-like structure and with the introduction of can make a significant amount of air in mineral construction materials, so because of air pores in the concrete voids, which leads to deterioration of mechanical properties and durability of concrete.

To reduce the content of air pores in the concrete by the use of such plasticizers, these plasticizers are mainly used together with deaerators or defoamers. Such defoamers should have a solubility in water from bad to complete insolubility, that is to be hydrophobic, so that you can effectively exhibit its inhibitory foam effect. Due to poor solubility in water, after the introduction of the defoamer in water softener concrete over time it may come to a phase separation, which prevents the end-use product. Therefore, a mixture of plasticizers based polycarboxyl the s and hydrophobic defoamers not sufficiently stable during storage. Long-term stability there. To date, this problem is bypassed, for example, the fact that the storage tanks obespechennogo product revolve.

Document WO 00/17128 describes the mixture of plasticizer on the basis of polycarboxylates and butoxycarbonyl of polyalkyleneglycol as a deaerator, which is due to the high pH of the precipitate and thus exerts its defoaming action. However, such defoamers remove the air from the concrete is less effective than hydrophobic materials, and should be used in high dosages, which is economically disadvantageous.

Sometimes to obtain stable water mixtures of polymers and hydrophobic defoamers are added surfactants. So, for example, from the document WO 2004/056445A1 known surfactants with functional amino group, which dissolves the water-insoluble defoamer. From the document US6569924B2 known surfactants based alkoxysilane, carboxylating, from sulphonated or sulfated aliphatic compounds, sorbitan, polypropylene, fatty acids, fatty alcohols and isononanol. They, as well as copolymers of maleic acid with styrene, are used to dissolve the hydrophobic foam in aqueous solutions of polymeric plasticizers in the form of micelles. Micelles with the addition of a cement collapse and release of Peng the Khabibullina. The use of Surfactants to dissolve water-insoluble materials in aqueous solutions of polymers has the disadvantage that such surfactants when used in concrete, in principle, can, depending on the type of cement or additives how to delete and enter the air. Thus, a certain damping foam is provided only at a greater cost.

Therefore, the known solution to obtain a stable mixtures of water-insoluble substances in aqueous solutions of polymers for use in Vodootvodny systems still require improvement. There is a need in the possibility of obtaining stable mixtures which are stable when stored for longer periods of time.

Summary of invention

Thus, the present invention is to provide a composition which overcome the disadvantages of the prior art and which allows you to add a hydrophobic additive in aqueous solutions of polymers, without this led to the separation of the phases. Accordingly, by using the composition according to the invention has achieved long-term stability during storage hydrophobic foam in aqueous solutions of polymers.

Unexpectedly, it was found that this can be achieved by using polymer P according to paragraph 1 of the claims. So, suddenly able to establish that the polymer P is according to the invention is able to emulsify the hydrophobic defoamers in water polycarboxylate plasticizers so, so they were stable during storage. In addition, the polymer P according to the invention result in additional water absorption and improved plasticization obtained with them Vodootvodny compositions. Thus, the use of the polymer P according to the invention allows to obtain a stable mixture of hydrophobic foam and aqueous solutions of polymers, which is stable during storage for a long time and which has the sole plasticizing properties, without the introduction of excessive amounts of air in Vodootvodny system.

In addition, the invention relates to the use of polymer P according to the invention as plasticizers for Vodootvodny compositions, as well as emulsifier for aqueous compositions. In addition, the invention relates to aqueous compositions containing the polymer P according to the invention, at least one antifoam M and at least one plasticizer V. Further advantageous form of implementation of the invention emerge from the dependent claims.

Ways of carrying out the invention

The present invention relates to a polymer P, which can be obtained by copolymerization

(a) at least one monomer A with ethylene unsaturation, which contains ionic groups, with

(b) at least one monomer B with ethylene narasiman the stew, which has a hydrophilic oxyalkylene group, and

(c) at least one monomer C with ethylene unsaturation, which contains vinylaromatic fragments, and

(d) at least one hydrophobic ethyleneamines monomer D of the formula (V); and if necessary

(e) at least one main aminoguanidinium E with ethylene unsaturation; and, if necessary, with

(f) at least one other monomer W, which is able to copolymerisate with components (a)to(d) and optionally (e).

Under the "copolymerization" refers to the reaction of polymerization, preferably radical polymerization, in which monomers are polymerized, preferably in the presence of radiculopathy connection. Radical polymerization is a standard method that is well-known specialist. As radiculopathy compounds are suitable, for example, inorganic or organic peroxides, such as benzoyl peroxide or hydroperoxides, persulfates, esters of percolate or organic azo compounds. The polymerization can be run also redox initiators.

The monomer A is selected from the group consisting of unsaturated mono - or dicarboxylic acids or analogues of unsaturated mono - or dicarboxylic acids, unsaturated, sulfo the OIC acids or analogues unsaturated sulfonic acids, and unsaturated phosphonic acids or analogues unsaturated phosphonic acids.

The monomer A is, in particular, formula (VII).

While X1means CO2, SO3or PO3, R13means H, CH3, COOM or CH2COOM, in particular H, or R13together with X may form a ring with-CO-O-CO-, R14means H, alkyl with 1-5 carbon atoms, COOM or CH2COOM, in particular H, and R15means H, CH2COOM or alkyl with 1-5 carbon atoms, in particular H or CH3. R16independently of one another denote phenyl group or a linear or branched alkylenes group with 1-20 carbon atoms, which may optionally contain functional groups with heteroatoms, and p is 0 or 1. R16may also, if R is 0, not present or mean, for example, CH2or to have as the functional groups, amide, amino, ester group, a group of simple ether or ketone group.

M stands for H, alkali metal, alkaline earth metal, ammonium, ammonium cation, or a mixture thereof. In particular, M can be a cation, in particular N+, PA+, CA++MD++, NH4+or organic ammonium. Specialist it is clear that in the case of multivalent ions must be another counterion, which mo is et to be among others, the carboxylate or another polymer molecule R. Ammonium compounds are, in particular, tetraalkylammonium or HR3N+and R means an alkyl group, in particular C1-C6alkyl group, preferably ethyl or butyl. Ammonium ions receive, in particular, the neutralization of the carboxyl groups of the standard commercially available tertiary amines.

Examples of suitable monomers are acrylic acid, methacrylic acid, musicanova acid, Tarakanova acid, glucagonoma acid, fumaric acid, maleic acid, melaminovaya acid, taconova acid, vinylbenzoic acid, crotonic acid, vinylsulfonic acid, arylsulfonate acid, Metallistov acid, 2-acrylamide-2-methylpropanesulfonic acid or vinylphosphonic acid or their derivatives or analogs, such as, for example, Polyamid maleic acid from maleic acid and sulfanilic acid, in particular amide N-(4-sulfophenyl)maleic acid. Particularly preferred monocarboxylic acid. Particularly suitable acrylic acid or methacrylic acid or their analogues.

Analogue unsaturated mono - or dicarboxylic acid is, for example, the salt of the acid, acid halide or acid anhydride. Analogue unsaturated Sul the background acid or phosphonic acid is for example, the salt of the acid.

Used according to the invention unsaturated mono - or dicarboxylic acid, sulfonic acid or phosphonic acid may be present as free acid or as a salt or partial salt, the term "salt" hereinafter covers in addition to the classical salts, which are obtained by neutralization of the base, and also complex chemical compounds of metal ions and the carboxylate or carboxyl groups as ligands.

Monomer B contains hydrophilic oxyalkylene group and has, in particular, the formula (I), (II) or (III):

Thus R1independently from each other mean a mono - or dicarboxylic acid, a specific monomer A, in particular the output from the formula (VII), after removal of the n groups of carboxylic acid, and n independently of one another denote 1 in the case of monocarboxylic acid or 1 or 2 in the case of a dicarboxylic acid.

R2independently from one another mean H, alkyl with 1-20 carbon atoms or alkylaryl with 7-20 carbon atoms. Particularly preferably, R2means H. Also suitable monomers B, ending with the end group on the one hand, and R2means alkyl with 1-20 carbon atoms, in particular methyl, or alkylaryl with 7-20 atom and carbon.

R3independently from each other mean a structural group which is obtained from a specific monomer A dicarboxylic acid after removal of the two carboxylic acid groups, in particularor.

R4independently of one another denote an alkyl group with 1-20 carbon atoms, alcylaryl group with 7-20 carbon atoms or H, preferably R4= H.

Y independently of one another mean,or

and x, y, z each independently from each other has a value of from 0 to 250, and x+y+z=3 or more. Preferably the sum of x+y+z is at least 20, particularly preferably from 20 to 100.

R independently of one another have the value 0 or 1.

Q means the residue of a polyhydric alcohol of the formula Q(OH)q+1after removing all the OH groups, and q means 2-5, in particular 2 or 3.

Examples of monomer B of formula (I) are simple monovinyl esters of polyoxyalkylene, in particular monomineralic ether of polyethylene glycol, monoallelic ether polyoxyalkylene, ester of polyoxyalkylene and butenova acid, ester of polyoxyalkylene and acrylic acid, ester of polyoxyalkylene and methacrylic acid, polyoxyalkylene, polyoxyalkylene the Ministry of foreign Affairs, polyoxyalkylene or the amide polyoxyalkylene-N-(2-hydroxyethyl)maleic acid.

Particularly preferred monomers B of the formula (I)in which Y represents-O - or-CH2-O-, the so-called simple alkenilovyh ether polyoxyalkylene, in particular allyl ether polyoxyalkylene, metalloy ether polyoxyalkylene, isopropanolamine ether polyoxyalkylene or vinyl ether polyoxyalkylene.

Thus R1means, in particular,orand R2means H or methyl, n is 1, x is a number from 0 to 100, y is a number from 0 to 100, z is 0, and x+y is greater than 3, preferably equal to at least 20, and oxyalkylene group (C2H4O) and (C3H6O) can go in any order, for example, random, statistical, alternating or block. Particularly preferably y=0 and x=20-60. Thus, the monomer B is preferably monovinyl or monoallyl ether of polyethylene glycol. Especially preferred monoallelic ether of polyethylene glycol.

Examples of monomer B of formula (II) are vinyl ether or allyl ether alkoxysilane, in particular ethoxylated alcohols. As alcohols are suitable, for example, alkalemia alcohols, such as propanol, propandiol, butanol, butanediol or glycerol, diglycerin, poly icarin, trimethylated, trimethylolpropane, 1,3,5-penthetria, aritra, pentaerythritol, dipentaerythritol, sorbitol, sorbitan or isosorbide. Preferred monomers B of the formula (II) are, for example, ethoxylated hydroxybutylidene ester or 3-allyloxy-1,2-propandiol.

The monomer B of formula (III) are the reaction products of dicarboxylic acids, in particular maleic acid, fumaric acid, tarakanovas acid or glucagonomas acid, polyoxyalkylene with the formation of imides of dicarboxylic acids. As polyoxyalkylene suitable, in particular, the monoamines, which are sold, for example, the firm Huntsman under the name Jeffamine® m-series

Monomer C is vinylaromatic connection and has, in particular, formula (IV):

At the same time balances R5independently from each other mean a linear or branched alkyl residue with 1-30 carbon atoms, alkoxy of formula-OR6polyoxyalkylene formula-O-[(C2H4O)x-(C3H6O)y-(C4H8O)Z]-R2, Cl or methyl chloride, F or methylphenid, Br or methyl, or NO2where m is a number from 0 to 5, preferably 0, R6independently of one another denote alkyl with 1-30 carbon atoms, and x, y, z each independently from each other has a value of from 0 to 250, and x+y+z=3 or larger is, and R2independently from one another mean H, alkyl with 1-20 carbon atoms or alkylaryl with 7-20 carbon atoms.

As monomer C are suitable, for example, styrene or alkylthio, for example methyl - or atillery, or oxyalkylation, vinyltoluene, vinylcolor or vinylbenzoic. Especially preferred as monomer C styrene.

The monomer D is hydrophobic, that is not soluble in water, and preferably contains at least one structural group with affinity for non-polar substances. The monomer D is, in particular, formula (V):

Thus R7means H or methyl, and R8linear or branched alkyl residue with 2 to 30 carbon atoms, cycloalkyl, alkenyl, alkylaryl or aralkyl with 7-20 carbon atoms, substituted or unsubstituted aryl residue or a divalent residue with 2-30 carbon atoms, and R8if X isorforms, if necessary together with R9or R10and N, the ring, in particular 5-8-tier ring which optionally contains an aromatic structure, and optionally contains heteroatoms in or on the ring.

X means

or

R9means alkyl with 1-20 carbon atoms, alkylaryl with 7-20 carbon atoms or H, preferably R9=H, and R9if necessary, together with N and R8forms a ring, in particular 5-8-tier ring, and optionally contains heteroatoms in or on the ring.

R10means alkyl with 1-20 carbon atoms, alkylaryl with 7-20 carbon atoms or alkenyl with 1-20 carbon atoms, and R10if necessary together with N and R8forms a ring, in particular 5-8-tier ring, and optionally contains heteroatoms in or on the ring.

Preferably R7means H, X -orand R8- a branched or linear alkyl residue with 3-20 carbon atoms.

Especially suitable are simple vinyl or allyl ether, such as, for example, butylvinyl ether, isobutylphenyl ether, arylpropionic ether, allylboronic ether or allergenicity ether.

In highly preferred complex vinyl or allyl ester of fatty acids, such as WikiProject, vinylboronate, arylpropionate, allylboronic or vinyl ester of lauric acid. Particularly suitable is a complex one vinyl ester of fatty acids, in particular acid Versatic®-9, which is sold, for example, under the name VeoVa 9™ Shell. Under Tamimi fatty acids, which aeriferous are, for example, carboxylic acids with 3 to 30 carbon atoms, in particular propionic acid, butyric acid, valeric acid, lauric acid, palmitic acid or stearic acid.

Other examples of monomers D are esters of acrylic acid, as, for example, butyl ester of acrylic acid, isobutyl ester of acrylic acid, 2-ethylhexyloxy ester of acrylic acid or laurelcrest. Also suitable esters butenova acid, such as tert-butyl ether 3-butenova acid.

As monomer D are also suitable, for example, vinylbilt, vinyl(2)-ethylhexanoate, vinylistic, vinylbenzoate, N-allylmethylamine, phenylacrylate or alkylenediamine.

Especially preferred as monomer D are selected such monomers introduced into the polymer structure is hydrophobic, or water-insoluble groups. Therefore preferred, in particular, the monomers D, which as R8have a branched or linear alkyl residue with at least 3 and preferably at least 4 carbon atoms. As "hydrophobic monomer" is preferably suitable such monomers, the homopolymers are insoluble in water.

It was unexpectedly found that the monomer D, in particular, contributes to the replacement of the sustained fashion emulsifying action of the polymer P. If the polymer is produced without monomer D, the polymer foams when getting much more than if to obtain a polymer P was additionally used monomer D.

If necessary, the polymer P further comprises at least one basic ethanobotany monomer E of the formula (VI)

Thus R11means H or methyl, Y1-orand R12means the residue with at least one primary, secondary or tertiary amino group, if Y1and the rest with at least one secondary or tertiary amino groups, if Y1means.

Preferably Y1means-CH2-. R12means, for example, an amino group or a branched or linear alkylamines, which optionally contains heteroatoms, such as politermogroup. For example, the monomer E can be allylamine or N-methylacrylamide.

The following examples of possible monomers E are products of the interaction of simple allylglycidylether ester with ammonia or with at least one amine. The amine may be selected, for example, from the group consisting of ethanolamine, diethanolamine, alkylamine, aniline, Jeffamin® (which is sold, for example, encourage company the Huntsman GmbH, Hamburg, under the name Jeffamine® M series), amino acids or alkylamine, such as butylamine. Especially preferred products of the interaction of simple allylglycidyl ether ethanolamine or sulfanilic acid.

The amino group may be present in protonated or deprotonated form.

One particularly preferred example of the monomer E is allylamine.

Additional monomer W can be any monomer with ethylene unsaturation, which may polymerization with the monomers A, B, C, D and E. for Example, the monomer W may be different amide or ester monomer. For example, the monomer W can be a complex ether, which is obtained, for example, by the reaction of mono - or dicarboxylic acid with alkilany alcohol, in particular C6-C20alkilany alcohol.

To obtain the polymer P can be used a combination of different monomers A, B, C and D and optionally E and/or W in various quantities. For example, you can use several monomers in A mixture, for example, a mixture of monomers of maleic acid with monomers of acrylic acid. Or you can use together several monomers B, for example allyl ether polyoxyalkylene with complex air polyoxyalkylene and (meth)acrylic acid. Can also be applied to various substituted styrene or different monomers, D.

the Polymer P preferably receive radical polymerization in the usual ways. The polymerization may be conducted in bulk or solvent, for example toluene, benzene, water or their mixtures, preferably in water. The conversion of monomer in the polymer P is preferably at a temperature up to 100°C. Over or through the reaction mixture can be allowed to flow the gas flow. As the gas stream may be used an inert gas or nitrogen.

Polymerization proceeds preferably under such conditions that the resulting polymers were formed from 10-500, preferably 20-200, in particular 25-60, of monomer units. The polymer P preferably has a molecular weight of Mwfrom 2000 to 200000 g/mol, preferably from 5000 to 100,000 g/mol, preferably from 8000 to 80000 g/mol, particularly preferably from 10,000 to 50,000 g/mol.

By "molecular weight" or "molar weight" in the context of the invention refers to the average molecular weight of Mw.

To regulate the molecular weights can be used by the controller as, for example, inorganic or organic sulfur compounds, aldehydes, formic acid or inorganic compounds of phosphorus.

Upon receipt of the polymer P preferably the amount used of the monomers is A monomer 5-90 mol.%, preferably 30-70 mol.%, particularly preferably 55-65 mol.%, for monomer B of 8 to 40 mol.%, preferably 0-20 mol.%, particularly preferably 12 to 18 mol.%, for the monomial is and C is 0.1-30 mol.%, preferably 10-20 mol.%, particularly preferably 12 to 18 mol.%, monomer D of 0.1-30 mol.%, preferably 6-10 mol.%, particularly preferably 7 to 9 mol.%, for monomer E 0-10 mol.%, preferably 0-7 mol.%, particularly preferably 0.1 to 2 mol.%, and for monomer W 0-5 mol.%, preferably 0-1 mol.%, particularly preferably 0-0,1 mol.%, each time calculated on the full amount of the monomers A, B, C, D, E and W.

The molar ratio of the monomers A:B is preferably ≤10:1, preferably ≤8:1, in particular ≤3:1.

Particularly preferred polymer P can be obtained by the reaction of copolymerization of acrylic acid or methacrylic acid and optionally maleic acid as A monomer with a simple vinyl ether of polyethylene glycol or simple allyl ether of polyethylene glycol as a monomer B, styrene as monomer C, vinyl ester of C4-C20fatty acids, in particular VeoVa 9™, as monomer D and, if necessary, allylamine as monomer E.

The preferred polymer P has the formula (VIII).

The substituents R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13-R15, Q, X, X1Y, Y1and the indices n, q, r, x, y and z each independently from each other matter which has already been described for the monomers a, b, C, D and E.

The indices f, g, g', g", g'"g"" h, i, k means the number, and the sum f+g+g'+g"+g'"+g"+h+i+k is from 10 to 500, and f>0, (g+g'+g"+g'+g")>0, h>0, i>0 and k≥0.

The letters a, b, b', b", b'", b'", c, d and e indicate the structural links, and the structural unit a is formed by polymerization of A monomer, and a structural unit (b, b', b", b'or b"" - polymerization of monomer B, a structural unit c is in the polymerization of monomer C, a structural unit d in the polymerization of monomer D, a structural unit e - as a result of polymerization of a monomer E with the corresponding other monomers.

The sequence of structural units a, b, b', b", b'", b'", c, d and optionally e can be alternating, statistical, block or random.

The polymer P preferably contains 5 to 90 mol.% structural units a, 8 to 40 mol.% structural units (b+b'+b"+b'"+b"", 0.1 to 30 mol.% structural links of c, 0.1 to 30 mol.% structural sections d and 0-10 mol.% structural sections of e, each time calculated on the full amount of the structural units a, (b+b'+b"+b'"+b""), c, d and e of the polymer P. the Molar ratio a:(b+b'+b"+b'"+b"") preferably ≤10:1.

The polymer P may have a combination of different structural units of the respective structural units a, b, c, d and optionally e. For example, the polymer P can be several heterogeneous structural units a, for example, a mixture of parts of maleic acid with parts of acrylic acid. Or W is in the polymer P can be several heterogeneous structural units b, b', b", b'", b'", or different structural units of the respective units b, b', b", b'", b ' " in the mix. In the polymer P can also have a number of styrene units c, which, for example, styrene substituted in different ways.

Similarly, the polymer P can be present together various hydrophobic structural units d, for example, a simple vinyl ether complex with a vinyl ester of a fatty acid.

Different structural units may be present in the polymer P in any sequence, for example, a random, alternating or block.

Depending on the amount and type of monomers used, we can obtain different properties of the final product. Therefore, another advantage of the polymer P according to the invention is the fact that you can simply and economically by using different monomers and / or different amounts of monomers to obtain several different derived by order of the polymer P. It has great advantages both from the point of view of logistics and economy.

The polymer P finds application in various fields, in particular in the technology of concrete and cement.

The polymer P according to the invention because of their structure, which includes both hydrophilic and hydrophobic structural units, is particularly well suited for use as an emulsifier for aqueous compositions, in particular for emulsions "is aslo in the water". Therefore, the present invention relates to the use of the polymer P according to the invention as emulsifier for aqueous compositions, in particular additive in Vodootvodny system. For example, the polymer P according to the invention is exceptionally well suited to emulsify water softener plaster or concrete and hydrophobic defoamer.

In addition, the present invention relates to the composition Z contains at least one polymer P according to the invention and at least one antifoam M. as antifoam M is suitable, in particular, esters of phosphoric acid, such as tributyl phosphate or triisobutylene (TIBP), polyalkylene glycols, such as, for example, polypropyleneoxide, block copolymers containing ethylene-, propylene - or builtoutside, mineral or vegetable oils, fatty acid, ester of fatty acids, fatty alcohols, alkoxysilane fatty acids or fatty alcohols, silicones, esters of silicone or hydrophobic organic compounds.

The share of the polymer P in the composition Z contains at least one polymer P and at least one antifoam M typically ranges from 20 to 80 wt.%, in particular from 30 to 49 wt.%, while the share of antifoam M is preferably from 0.1 to 20 wt.%, in particular from 0.5 to 10 wt.%, based on the weight of the composition Z. the ratio of the polymer P to PE is easialy M in water of the composition Z is preferably from 2:3 to 49:1, in particular from 3:2 to 10:1. Preferably the composition Z additionally contains water.

The following form of the present invention relates to aqueous compositions of Z containing water, at least one polymer P according to the invention, at least one antifoam M and at least one plasticizer V for Vodootvodny compositions. As the plasticizer preferably V fit polycarboxylate plasticizers which are known, for example, in the chemistry of concrete as a highly effective plasticizers. Such polycarboxylate plasticizers described, for example, in documents EP 0056627B1, EP 0840712B1, EP 1136508A1, EP 1138697B1 or EP 1348729A1. Particularly preferred plasticizers that have been received polymeranalogous transformation, such as described in EP 1138697B1 or EP 1348729A1. Equally as plasticizers V can be used lignosulfonates, from sulphonated condensation products of melamine or naphthalene with formaldehyde, vinyl copolymers or mixtures thereof. Generally speaking, you can use any composition that is capable of diluting Vodootvodny composition. However, particularly suitable are aqueous polymer mixture polycarboxylate plasticizers.

To obtain a composition Z, in particular aqueous composition Z containing the polymer P according to the invention, this on minicamera one polymer P according to the invention is mixed with antifoam M, and optionally with a plasticizer V. Preferably first pre-mixed polymer P is preferably in the form of an aqueous emulsion, antifoam M and then if necessary add an aqueous solution of plasticizer V. as a result of mixing of the polymer P according to the invention with antifoam M and plasticizer V in water is obtained a stable aqueous polymer mixture Z without phase separation, which is stable during storage for several months.

If desired, the aqueous composition Z can before applying to transfer in powder form, for example, by spray drying, using protective colloids or other auxiliary drying means. An aqueous mixture of Z can be stored in powder form or added to a dry mix containing at least one Vodootvodny material. The dry mixture is suitable for storage for a long time and typically Packed in bags or stored in the bunker.

The polymer P and, if necessary, antifoam M can also first be obtained in bulk and then added to the plasticizer V, which is in the form of a polymer melt. If the polymer melt with the plasticizer V, added to the polymer P and antifoam M cool, get the composition in solid form, in particular in the form of flakes, flakes, granules or plates. This solid polymer composition can be sent to storage and before use what begins to dissolve in water, the resulting aqueous composition Z according to the invention.

The share of the polymer P in the composition containing water, at least one polymer P, at least one antifoam M and at least one plasticizer V, typically ranges from 0.04 to 10 wt.%, in particular from 0.05 to 5 wt.%, based on the weight of aqueous composition Z.

The ratio of polymer P to the antifoam M in water of the composition Z is preferably from 2:3 to 10:1, in particular from 3:2 to 3:1. If the water composition Z contains at least one plasticizer V, the proportion of plasticizer V is preferably from 3 to 50 wt.%, in particular from 20 to 40 wt.%, based on the weight of aqueous composition Z.

The water composition Z can contain additional components. Examples are solvents or additives which are commonly used in construction chemicals, in particular surface-active substances, heat and light stabilizers, dyes, accelerators, retarders, foaming agents.

The hydrophilic effect of the polymer P obtains, in particular, through the use of polyoxyalkylene groups of monomer B upon receipt of the polymer P.

The hydrophobic effect is achieved by applying a hydrophobic monomers C and D. it is Therefore particularly advantageous to along with a hydrophobic monomer C were chosen such monomers D, which contribute Hydra is fonye, or poorly soluble in water, or hydrophobic groups in the polymer structure. The addition of the monomer D is achieved emulsifying action according to the invention.

As the polymer P and itself determines the plasticizing action, he, in addition, can also be used as a plasticizer for Vodootvodny compositions. Therefore, in the following aspect of the invention relates to the use of the polymer P according to the invention as a plasticizer for Vodootvodny compositions, in particular for concrete and mortar.

As the polymer P can simultaneously act as an emulsifier, as well as an additional plasticizer, it can actually exacerbate the effects of plasticizers plaster or concrete plaster or concrete and can lead to exceptionally good mechanical property of plaster or concrete.

The polymer P is preferably used in the content of the polymer or solids 0.005 to 5 wt.%, based on the weight of hydraulic binder. To achieve the desired effect you can also apply multiple polymers P in the mixture.

As Vodootvodny systems or compositions, in principle, can be used all Vodootvodny materials known to the specialists in concrete. In particular, we are talking about hydraulic binders such as cement, such as Portland cement or aluminous PL is established with representation from the cement, and, accordingly, their mixtures with fly ash, silica fume, slag, granulated blast furnace slag and limestone fillers. The following vodootvedenie materials in the context of the present invention are gypsum, anhydrous form, in the form of a hemihydrate or dihydrate or burnt lime. As vodootvedenie compositions preferred cement. Further possible additives, such as sand, gravel, stones, quartz powder, chalk as well as conventional as additive components, such as other concrete plasticizers, such as lignosulfonates, from sulphonated condensation products of naphthalene with formaldehyde, from sulphonated condensation products of melamine with formaldehyde or a simple polycarboxylate esters, accelerators, corrosion inhibitors, retarders, shrinkage reducers, defoamers or pore.

The polymer P according to the invention can be a component of the aqueous composition, which is stable during storage for a long time, or it can be a component vodootvedenie composition. As a component vodootvedenie composition, the polymer P can be added to the normal vodootvedenie composition together with the addition of water or shortly before or after that. It is particularly appropriate was the addition of the polymer P in the form of aqueous solution or the var the var, in particular, as the mixing water or as part of the mixing water.

The polymer P has the property plasticizer for Vodootvodny compositions, in particular for cement compositions, which means that if customary in the technology of cement and concrete water / cement (W/Z), the resulting mixture has a much greater fluidity compared to the composition without plasticizer. Turnover is typically measured by the effective flowing property. On the other hand, you can get a mix that with equal fluidity require significantly less water, so that the mechanical properties utverzhdenii vodootvedenie composition is greatly improved. A particular application is a concurrent use of a polymer P as emulsifier in obtaining a polymer mixture, which contains the actual plasticizer V, and use as an additional plasticizer, which enhances the effect of the actual plasticizer V.

Examples

1.1 abbreviations

Table 1
Used abbreviations. Mw = average molecular weight
ReductionValueMwP is osmotical
allyl-PEGallyl ether of polyethylene glycol1100 g/molClariant
allyl-PEGallyl ether of polyethylene glycol2000 g/molClariant
vinyl-PEGthe vinyl ether of polyethylene glycol1000 g/molClariant
VEOVA®9complex vinyl ether acid Versatic®-9Christ Chemie AG

1.2. Instructions to obtain A polymer P8-P10

In the reaction vessel with anchor stirrer (stirrer IKA®), temperature probe, reflux condenser and two separate inlet pipes were placed in approximately equal quantities of water and allyl-PEG (production Clariant, Basel, Switzerland), and styrene (Fluka, Switzerland) and VEOVA®9 (manufacture of Christ Chemie AG, Switzerland) as specified in table 2 the number and brought to 85°C. as soon As it was reached 85°C, was added 0.1 g of hypophosphite sodium (from Fluka, Switzerland). Then for 2 hours at a time through the first supply was added acrylic acid and, if necessary the spine of maleic acid (both from Fluka, Switzerland) and through the second inlet 20 g of 10% solution of sodium persulfate (Fluka, Switzerland). While the temperature was kept in the range of 85-95°C. After everything was added, additional polymerizable another hour at 90°C. then diluted with the appropriate amount of water to the desired solids content of the polymer 40 wt.%, calculated on the total weight of the polymer solution.

1.3. Instruction B for polymers P1-P7

In the reaction vessel with anchor stirrer (stirrer IKA®), temperature probe, reflux condenser and two separate inlet pipes were placed in approximately equal quantities of water and allyl-PEG-or vinyl-PEG (produced by Clariant, Basel, Switzerland), and if necessary, allylamine (from Fluka, Switzerland) as specified in table 2 the number and cooled to 22°C. Then was added styrene (Fluka, Switzerland), VEOVA®9 (manufacture of Christ Chemie AG, Switzerland) and maleic acid or taconova acid. If instead of allyl-PEG was used a simple vinyl ether, the pH was raised with sodium hydroxide solution to pH 5.5). Adding a little bit of Fe(II)SO4(0.1 g) and then acrylic acid or salt of acrylic acid were transferred into the collection.

Then under stirring collection through the first supply dropwise introduced a 15%solution of 10 g of rongalite™C (manufactured by BASF, Germany) in water and through the second inlet 35% solution 21 is hydrogen peroxide (Fluka, Switzerland) in water, and the temperature was raised from 22°C to 55°C. the Solution regalite™S dripping through the first supply within 25 minutes, and the hydrogen peroxide solution through the second supply within 35 minutes. After the emulsion was diluted with water to the desired content of the polymer 40 wt.%, calculated on the total weight of the polymer solution.

Table 2
The polymers P (P-1 - P-10) according to the invention. The number specified in moles
No.Monomer AMonomer BMono-Mer CMono-Mer DMono-Mer EThe way to obtain
Acrylic acidMaleic acidTaconova acidAllyl-PEG-1100Allyl-PEG-2000Vinyl-PEG-1000StyreneVEOVA
®9
Allyl-amine
P-11,20,3 0,40,4150,215B
P-21,20,3880,40,3920,215B
P-31,20,4910,40,4150,199B
P-41,2 salt Na0,3880,40,4150,215B
P-51,360,2 0,40,4150,21511,4B
P-620,50,490,268B
P-71,20,20,40,4150,215B
P-820,50,490,268A
P-91,20,3 0,2940,16A
P-101,20,1420,30,3090,16A

2. Receiving water compositions Z

To obtain water of a composition Z according to the invention is first received 40% aqueous emulsion of the polymer P according to the invention. For this 40 wt.% polymer P from table 2 was mixed with 60 wt.% water. A 40% aqueous emulsion polymer was mix up the antifoam M and depending on the experience of this mixture with stirring or shaking) was added a 30% aqueous solution of plasticizer V, as shown in table 3 the number. 30% aqueous solution of plasticizer V was obtained by mixing 30 wt.% plasticizer V with 70 wt.% water.

As a plasticizer V was applied polymer which was obtained polymeranalogous transformation and which is described in table 2 of WO 2005/123621A1 as the polymer A4. As antifoam M-1 used Pronal® 735 S (manufactured in the sale of Toho Chemical Industry Co., Ltd), as M-2 used polypropylenglycol with what they molecular weight M w1200 g/mol (Fluka, Switzerland), as M is 3 - triisobutylene (from Fluka, Switzerland) and in the M-4 Pluronic® PE 3100 (manufactured in the sale of BASF, Germany).

In the case of the composition Z-21 instead of the emulsifying polymer P were used for comparison of conventional surfactants Texapon NSO manufactured by Cognis GmbH, Monheim, Germany). In addition, used a 1.75 wt.% purchase Texapon NSO, not 40% emulsion.

Table 3
Stability of aqueous compositions Z-1 - Z-23; number of plasticizer V is listed as a 30%aqueous solution of the polymer P as a 40% aqueous emulsion of antifoam M as 100% liquid. The percentage data in table 3 are weight percent, calculated on the total weight of the aqueous composition Z. Exception is Texapon NSO in Z-21, which was used in the amount of 1.75 wt.% the purchase of the product, and 40% aqueous emulsion
Composition ZThe plasticizer V (as 30% solution)The polymer P (40% emulsion)Antifoam MStability (after 30 days of storage at 20°C)
Z-1its 98.45%1,25% P-10,3% M1 stable
Z-2its 98.45%1,25% P-2a 0.3% M-1stable
Z-3its 98.45%1,25% P-3a 0.3% M-1stable
Z-4its 98.45%1,25% P-4a 0.3% M-1stable
Z-5its 98.45%1,25% P-5a 0.3% M-1stable
Z-6its 98.45%1,25% P-6a 0.3% M-1stable
Z-7its 98.45%1,25% P-7a 0.3% M-1stable
Z-8its 98.45%1,25% P-8a 0.3% M-1stable
Z-9its 98.45%1,25% P-9stable
Z-10its 98.45%1,25% P-10a 0.3% M-1stable
Z-11its 98.45%1,25% P-60,2% M-1
0,1% M-4
stable
Z-1298,35%1,25% P-60,2% M-1
0,2% M-4
stable
Z-1398,25%1,25% P-60,2% M-1
a 0.3% M-4
stable
Z-1497,9%a 1.5% P-60,2% M-1
a 0.4% M-4
stable
Z-1598,5%1,25% P-10,25% M-3stable
Z-1696,95%a 2.5% P-10.15% of M-1
a 0.4% M-2
stable
Z-17 3,75% P-1a 0.3% M-1
0,6% M-2
stable
Z-1897,02%2.5% of P-30,38% M-1
0,1% M-3
stable
Z-1994,12%5% P-40,88% M-1stable
Z-20100,00%stable
Z-2197,95%1,75% Texapon NSOa 0.3% M-1division
Z-22No80,0% P-420,0% M-1stable
Z-2399,7no0,3division

Table 3 shows that the polymer P has exceptional properties as an emulsifier and leads to a stable aqueous emulsion of a mixture of plasticizer and defoamer. In contrast, the mixture is of plastificator and antifoam without emulsifier according to the invention is not stable (see composition Z-23). As usual surfactants (for example, Texapon NSO from Cognis GmbH) unable to emulsify the mixture of plasticizer and defoamer, and there is a separation of phases (see composition Z-21).

3. Determination of air content in freshly prepared mortar

The effectiveness of water compositions Z according to the invention was tested in freshly prepared construction solutions.

The composition of the mortar (MM): (maximum grain size of 8 mm)Number
Cement (Swiss CEM I 42.5)750 g
Lime filler141 g
Sand 0-8 mm3150 g
Water440 g
The water composition Z according to table 35.3g

Sand, filler and cement was mixed for 1 minute in a Hobart mixer in a dry condition. Within 30 seconds was added mixing water in which was dissolved in water composition Z, and stirred for another 2.5 minutes. Full wet mix is 2.5 minutes. Water composition Z was kept in bottles of 30 days at room temperaturebased this pipette from the bottom of the bottles were selected by the used quantity of the sample (5.3g).

The air content in the mortar was determined by analyzer air content according to the standard EN 1015-7. If the air content was measured after 30 minutes, the mortar mixture before measuring stirred for 10 seconds in a Hobart mixer.

Table 4
The content of air pores in a freshly prepared solution in %, measured after 3 minutes or 30 minutes
The mortar mixture MMComposition Z according to table 3The air content in mortar in % after 3 minutesThe air content in mortar in % after 30 minutes with a 10 second mixing
MM-1Z-12,83,0
MM-2Z-22,63,1
MM-3Z-32,62,8
MM-4Z-42,73,3
MM-5Z-52,93,5
MM-6Z-63,03,1
MM-7Z-72,52,6
MM-8Z-82,73,2
MM-9Z-92,42,6
MM-10Z-102,52,9
MM-11Z-111,82,2
MM-12Z-121,62,0
MM-13Z-131,61,9
MM-14Z-141,52,1
MM-15Z-153,3 3,5
MM-16Z-162,53,0
MM-17Z-172,42,6
MM-18Z-183,22,6
MM-19Z-191,61,5
MM-20Z-208,87,8
MM-21Z-2113,213,8
MM-22Z-221,81,8
MM-23Z-234,0the 4.7

Table 4 shows that the aqueous composition containing the polymer P according to the invention, the plasticizer V and antifoam M, leading to improved quality of mortar, and air content as in the beginning, and after a long time can be kept low. If you do not add any polymer P (motri mortar mix MM-20) or if instead of the polymer P add conventional surfactants (see mortar mix MM-21), the air content is significantly increased, and the quality of the mortar is deteriorating.

4. The fluidity of the polymer P

To study the validity of the polymer P to the fluidity of the slurry was determined fluidity (ABM).

For comparative experiments without polymer P and without the usual PAVA or conventional plasticizer 100 grams of Portland cement type CEM I 42.5 stirred for one minute with 33 grams of water (the value of W/Z 0.33) and then the mixture was filled in minicons (inner diameter at the top of 18.5 mm, at the bottom of 37.5 mm, height 57,2 mm). Immediately after filling the cone gently raised. Then with calipers after 90 seconds measured amount of cement cakes.

For the experiment with polymers P-1 To P-10 according to the invention the portion of water was reduced by 5%, which means that 100 grams of Portland cement type CEM I 42.5 stirred for one minute with 31.5 grams of water (the value of W/Z is 0,315) and 0.5 grams of 40% aqueous emulsion of the polymer P according to the invention (which corresponds to 0.2 gram of solid polymer substance) and then the mixture was filled minicons.

For comparison instead of the polymer P according to the invention was added to conventional surfactants (Texapon NSO from Cognis GmbH) or a conventional plasticizer (Flube OS 39 produced by Giovanni Bozzetto S.P.A, Italy).

Table 5
The flowability (ABM) in mm after 90 seconds
The polymer P, or surfactant or plasticizerThe flowability (ABM) in mm after 90 seconds
P-1101
P-2122
P-389
P-4106
P-5143
P-660
P-7113
P-8130
P-9105
P-1090
Flube OS 39110
Texapon NSO40
without all40

Table 5 shows that the polymer P according to the invention without additional plasticizer detects the plasticizing action and leads to effective flowing property, which is comparable with conventional plasticizers. In contrast, traditional surfactants do not exhibit any of plastopil the respective steps.

Of course, the invention is not limited to the illustrated and described embodiments. It is understood that the abovementioned features of the invention can be applied not only in the specified combination, but also in other modifications, combinations and modifications or individually, without leaving the scope of the invention.

1. The polymer P obtained by copolymerization of
a) at least one monomer And ethylene unsaturation selected from the group consisting of unsaturated mono - or dicarboxylic acids as free acids or as salts or in the form of incomplete salts, or in the form of a halide or anhydride, unsaturated sulfonic acids in the form of free acids or as salts or in the form of incomplete salts, or in the form of a halide or anhydride and an unsaturated phosphonic acids as free acids or as salts or in the form of incomplete salts or in the form of a halide or anhydride, with
b) at least one ethyleneamines monomer In formula (I), (II) or (III)



where R1independently from each other means specified in (a) mono - or dicarboxylic acid after removal of the n groups of carboxylic acid,
R2independently from one another mean H, alkyl with 1-20 carbon atoms which kind or alkylaryl with 7-20 carbon atoms,
R3means specified in (a) dicarboxylic acid after removal of both groups of carboxylic acid,
Y independently of one another mean
,,,,or
where R4independently of one another denote alkyl with 1-20 carbon atoms, alkylaryl with 7-20 carbon atoms or H, preferably R4=H
n independently of one another denote 1 or 2,
where r independently of one another are 0 or 1,
x, y, z each independently from each other has a value of from 0 to 250 and
x+y+z=3 or more;
where Q denotes the residue of a polyhydric alcohol of the formula Q(OH)q+1after removing all Oh-groups,
q has a value from 2 to 5, in particular 2 or 3, and
C) at least one ethyleneamines a monomer With formula (IV)

where R5independently of one another denote alkyl with 1-30 carbon atoms, alkoxy of formula-OR6polyoxyalkylene formula-O-[(C2H4O)x-(C3H6O)y-(C4H8O)z]-R2, Cl, F, Br or NO2,
where m is a number from 0 to 5, preferably 0,
R6independently of one another denote alkyl with 1-30 carbon atoms,
x, y, z each independently from each other has a signature is a group of from 0 to 250 and
x+y+z=3 or more;
R2independently from one another mean H, alkyl with 1-20 carbon atoms or alkylaryl with 7-20 carbon atoms,
and
d) at least one ethyleneamines monomer D of the formula (V)

where R7means H or methyl,
R8means a linear or branched alkyl residue with 2 to 30 carbon atoms, cycloalkyl or alkenyl with 2-30 carbon atoms, alkylaryl or aralkyl with 7-20 carbon atoms, substituted or unsubstituted aryl residue or a divalent residue with 2-30 carbon atoms, and where R8optionally, if X means
or
together with R9or R10and with N form a ring, in particular 5-8-tier ring which optionally contains an aromatic structure, and optionally contains heteroatoms in or on the ring,
X means
,,,,
,,,,,
or
where R9means alkyl with 1-20 carbon atoms, alkylaryl with 7-20 carbon atoms, and a and N, preferably R9=H, and if necessary, R9together with N and R8forms a ring, in particular 5-8-tier ring, and optionally contains heteroatoms in or on the ring,
R10means alkyl with 1-20 carbon atoms, alkylaryl with 7-20 carbon atoms or alkenyl with 1-20 carbon atoms and optionally R10together with N and R8forms a ring, in particular 5-8-tier ring, and optionally contains heteroatoms in or on the ring;
and, if necessary
e) at least one main ethyleneamines the monomer of formula (VI)

where R11means H or methyl,
Y1meansor
R12means the residue with at least one primary, secondary or tertiary amino group, if Y1meansand the rest with at least one secondary or tertiary amino group, if Y1is; and, if necessary
f) with at least one other ethyleneamines monomer W.

2. The polymer P according to claim 1, characterized in that the monomer a has the formula (VII)

where X1means CO2, SO3or PO3,
M stands for H, alkali metal, alkaline earth metal, ammonium or Katya is n ammonium,
R13means H, CH3The SOOMA or CH2COOM, in particular H, or R13together with X forms a ring with-CO-O-CO-;
R14means H, alkyl with 1-5 carbon atoms, SOOMA or CH2The SOOMA, in particular N;
R15means H, CH2The SOOMA or alkyl with 1-5 carbon atoms, in particular H or CH3,
R16independently of one another denote phenyl group or a linear or branched alkylenes group with 1-20 carbon atoms, which optionally contains functional groups with heteroatoms;
p is 0 or 1.

3. The polymer P according to claim 1 or 2, characterized in that the monomer a is a (meth)acrylic acid, metaconule acid, tarakanovas acid, glucagonomas acid, fumaric acid, maleic acid, taconova acid, vinylbenzoic acid, cretonne easy acid, vinylsulfonic acid, arylsulfonate acid, Metallistov acid, 2-acrylamide-2-methylpropanesulfonic acid or vinylphosphonic acid, preferably acrylic acid or methacrylic acid.

4. The polymer P according to claim 1 or 2, characterized in that the copolymerization takes place in the presence of radiculopathy connection.

5. The polymer P according to claim 1 or 2, characterized in that the monomer In a complex air polyoxyalkylene and (meth)acrylic acid, or simply blame the new air polyoxyalkylene, or simple allyl ether of polyoxyalkylene.

6. The polymer P according to claim 1 or 2, characterized in that the monomer is styrene.

7. The polymer P according to claim 1 or 2, characterized in that the monomer D is a complex with a vinyl ester of a fatty acid with 3 to 30 carbon atoms.

8. The polymer P according to claim 1 or 2, characterized in that the monomer E is allylamine.

9. The polymer P according to claim 1 or 2, characterized in that the monomer E is obtained by reaction of simple allylglycidylether ester with ammonia or at least one amine.

10. The polymer P according to claim 1 or 2, characterized in that the amount used of the monomer ranges for 5-90 mole%, In 8-40% mol, for From 0.1 to 30 mole%, for D 0.1 to 30 mole%, for E 0-10 mole% and for W 0-5 mole%, each time calculated on the full amount of the monomers a, b, C, D, E, and W used in the preparation of the polymer P, and the molar ratio of monomers:≤10:1.

11. The polymer P according to claim 10, characterized in that the amount used of the monomer is a 30-70 mole%, 10-20 mole%, 10 To 20 mole%, for D 6-10 mole%, for E 0-7% mol and W 0-1 mole%, each time calculated on the full amount of the monomers a, b, C, D, E, and W used in the preparation of the polymer P.

12. The polymer P according to claim 11, characterized in that the amount used of the monomer is And 55-65% mol, for 12-18% mol, With 12-18% mol, D 7-9% mol, for E 0.1 to 2 mole% and 0-0 W,1% mol, every time in the calculation of p is lnoe the number of monomers A, B, C, D, E, and W used in the preparation of the polymer P.

13. The polymer P according to claims 1, 2, 11 or 12, characterized in that the ratio A:In is ≤8:1, preferably ≤3:1.

14. The use of the polymer P according to one of claims 1 to 13 as a plasticizer for Vodootvodny compositions, in particular of concrete and mortar.

15. Vodootvodny composition Z contains at least one polymer P according to one of claims 1 to 13, at least one antifoam M, water and at least one plasticizer V for Vodootvodny compositions.

16. Composition Z according to item 15, wherein the ratio of polymer P to the antifoam M is from 2:3 to 49:1, in particular from 3:2 to 4:1.

17. Composition Z according to item 15 or 16, characterized in that the antifoam M represents an ester of phosphoric acid, polyalkyleneglycol, fatty acid, ester of fatty acid or silicone.

18. Composition Z according to item 15, wherein the plasticizer V is polycarboxylates.

19. Composition Z according to § 15, characterized in that the composition Z contains from 0.04 to 10 wt%, in particular from 0.05 to 5 wt%, polymer P, from 0.01 to 10 wt%, in particular from 0.05 to 5% by weight. antifoam M and from 3 to 50 wt%, in particular from 20 to 40 wt%. plasticizer V, based on the weight of aqueous composition Z.



 

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3 cl, 1 tbl, 8 ex

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FIELD: chemistry.

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4 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: method is described for preparing aqueous solutions of copolymers, involving a fundamental step for copolymerisation of partially neutralised acrylic and maleic acid in the presence of hydrogen peroxide in amount of 2 to 4% of total mass of monomers at temperature ranging from 85 to 105°C in an aqueous medium, which is realised through gradual addition of an aqueous solution of hydrogen peroxide for 3 to 6 hours into an aqueous solution of partially neutralised maleic acid and simultaneous gradual addition of an aqueous solution of partially neutralised acrylic acid, or an aqueous solution of free acrylic acid, or aqueous solutions of free acrylic acid and a base, and subsequent addition of hydrogen peroxide for 30 to 60 minutes after completion of simultaneous addition of hydrogen peroxide and acrylic acid, and a step for pre-polymerisation by keeping the reaction mixture at polymerisation temperature, distinguished by that, the pre-polymerisation step is realised by keeping the reaction mixture at polymerisation temperature for 35 to 60 minutes, subsequent simultaneous addition of aluminium or potassium persulphate in amount ranging from 0.10 to 0.15% of total mass of monomers and subsequent keeping at polymerisation temperature for 45 to 90 minutes.

EFFECT: increased dispersion capacity of copolymers.

1 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: method is carried out via radical continuous emulsion polymerisation of monomers and optionally subsequent drying of the resultant polymer dispersion, wherein emulsion polymerisation is carried out in a state consisting of a) at least one precursor heat-exchanger, b) at least two series-arranged reactors with mixers operating under pressure and c) at least one subsequent reactor operating under pressure, such that the degree of conversion at the output of the heat-exchanger is at least 10% of the entire degree of conversion during polymerisation, wherein a pressure gradient which falls from the first to the last of the series-arranged apparatus is created and at the end of polymerisation in the reactors operating under pressure, further polymerisation is carried out in a reactor which operates without pressure. The invention also includes an apparatus for realising said method.

EFFECT: linear macromolecules with high molecular weight are obtained and lower content of cross-linked molecules.

14 cl, 1 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: method is carried out via radical continuous emulsion polymerisation of monomers and optionally subsequent drying of the resultant polymer dispersion, wherein emulsion polymerisation is carried out in a state consisting of a) at least one precursor heat-exchanger, b) at least two series-arranged reactors with mixers operating under pressure and c) at least one subsequent reactor operating under pressure, such that the degree of conversion at the output of the heat-exchanger is at least 10% of the entire degree of conversion during polymerisation, wherein a pressure gradient which falls from the first to the last of the series-arranged apparatus is created and at the end of polymerisation in the reactors operating under pressure, further polymerisation is carried out in a reactor which operates without pressure. The invention also includes an apparatus for realising said method.

EFFECT: linear macromolecules with high molecular weight are obtained and lower content of cross-linked molecules.

14 cl, 1 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer powdered composition re-dispersed in water. The powdered polymer composition re-dispersed in water contains one or more anhydrides of fatty acids in amount of 0.1-70 wt % per total weight of the powdered polymer composition. The method of preparing said powdered composition involves drying an aqueous polymer dispersion and a fatty acid anhydride or only the said anhydride in the presence of a protective colloid if necessary. Use of the said powdered composition combined with hydraulically setting binding materials in different areas of the construction industry. The invention is developed in subclaims.

EFFECT: enhancement of hydrophobic properties.

10 cl, 6 ex, 1 tbl

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