Dispersing substance, containing copolymer mixture

FIELD: chemistry.

SUBSTANCE: invention relates to polymer composition used in composition of dispersing substance, its obtaining and application. Claimed is polymer composition for application as dispersing substance, which contains 3-95 wt % of copolymer H and 3-95 wt % of copolymer K, with each of copolymers H and K containing structural units of polyether macromonomer and structural units of acid monomer , which are present in copolymers H and K, in each case, in molar ratio 1:20-1:1, and at least 20 mol. % of all structural units of copolymer H and at least 25 mol% of all structural units of copolymer K, in each case, are present in form of structural unit of acid monomer, with structural units of polyether macromonomer of copolymers H and K containing side chains, in each case, which contain, at least, 5 atoms of ether oxygen, and quantity of atoms of ether oxygen in side chain of structural units of polyether macromonomer of copolymers H and K, in each case, varies in such a way that respective diagrams of density of distribution of probabilities, where quantity of atoms of ether oxygen, in each case, is presented on abscissa axis and respectively corresponding frequencies of occurrence of copolymers H and K, in each case, are presented on ordinate axis, contain, in each case, at least, 2 maximums, whose abscissa values, in each case, differ from each other by more than 7 atoms of ether oxygen, and diagrams of density of distribution of probability of copolymers H and K differ from each other by the fact that abscissa value of, at least, one maximum of copolymer H, in each case, differs by more than 5 atoms of ether oxygen from abscissa values of all maximums of copolymer K, and/or by the fact that mean arithmetic values of atoms of ether oxygen of structural units of macromonomer of polyether of copolymers H and K differ from each other by more than 5 atoms of ether oxygen. Method of obtaining said composition, its application and based on it dispersing preparation are also claimed.

EFFECT: dispersing preparation based on claimed composition is economical, makes it possible to obtain effective hydraulic binding substances, used as superplasticiser for concrete.

23 cl, 2 dwg, 4 ex

 

The present invention relates to a polymer composition, a dispersing agent, to the preparation of polymeric composition and dispersing substances and to the use of the polymeric composition.

It is known that additive in the form of dispersing substances are often added to aqueous suspensions of powdered inorganic or organic substances, such as clay, silica powder, chalk, carbon black, crushed stone and hydraulic binders, in order to improve their ability to resist treatment, i.e. zameshivaete, flowability, dispersibility, pumpability or mobility. This Supplement helps to prevent the formation of hard lumps dispersed particles, which were previously present, and particles, which are only formed through hydration, and, thus, improves the ability to resist treatment. This effect applies, in particular, the target method in the preparation of mixtures of building materials, which contain hydraulic binders such as cement, lime, gypsum, hemihydrate or anhydrite.

In order to make the compounds of building materials based on these matrices when ready for use, workable form, as a rule, requires considerably more water for the ena, than that required for the subsequent hydration or hardening process. Part of the voids formed in the thickness of the concrete due to excess water, which then evaporates, it leads to significantly lower strength and durability.

In order to reduce the excess ratio of the water processed in the specified consistency and/or to improve the ability to resist the processing in a specified ratio water/binder, additives used, which mainly referred to as substance reduce the water content, or dosage of the additive. In particular, in practice, as such substances are applied copolymers, which are prepared by copolymerization of monomers of acid and/or monomers derived acids with macromonomers polyethers.

WO 2005/075529 describes copolymers which, in addition to the structural units of monomers acids contain structural units vinylacetylene(ethylene glycol) as structural units of macromonomer simple polyester. Such copolymers are widely used as high-performance superplasticizers supplements as they have excellent performance.

Although described copolymers are referred to as cost-effective high-performance superplasticizers supplements, continue the W a desire to further improve the quality and profitability of the copolymers.

Therefore, an object of the present invention is the provision of economical dispersant substances for hydraulic binders, which would be suitable, in particular, as the dosage of the additive for concrete.

The achievement of this object represents a polymer composition comprising 3-95 weight % of the copolymer H and 3-95 weight % of the copolymer, each of the copolymers H and K contains structural units of macromonomer polyether structural units of monomer acids, which are present in the copolymers H and K, in each case in a molar ratio which is 1:20-1:1 and at least 20 mol % of all structural units of the copolymer H and at least 25 mol % of all structural units of the copolymer To be present, in each case in the form of structural units of the monomer acid, while the structural links of macromonomer polyether copolymers H and K have side chains containing in each case at least 5 atoms of oxygen simple ether, and the number of oxygen atoms simple ester in the side chain structural units of macromonomer polyether copolymers H and K varies in each case, so that the corresponding graph of the probability density functions, where the number of oxygen atoms is a simple ester in the side chain the structural unit macromonomer polyether, in each case, displayed on the x-axis and respectively corresponding to the frequency of occurrence for copolymers of N or, in each case, displayed on the y axis, in each case contain at least 2 maximum values of the abscissa which differ from each other, in each case, more than 7 atoms of oxygen simple ether, and the graph of the density probability distribution of the copolymers H and K are different from each other so that the value of the abscissa at least one maximum of the copolymer of N, in each case, differ by more than 5 oxygen atoms of simple ether from the values of the abscissa of all maxima of the copolymer and/or the fact that the average arithmetic value of the oxygen atoms of the simple ester structural units of macromonomer polyether copolymers H and K are different from each other by more than 5 atoms of oxygen simple ether.

The structural links of the monomer acid get through the inclusion of appropriate acid monomers as polymerized units. In this context, the acid monomer should be understood in the value of monomers which are capable of radical copolymerization, have at least one double bond between carbon atoms, containing at least one acid group and react as an acid in the aquatic environment. In addition, mono the EP acid must also be understood in the meaning of the monomers, which is capable of radical copolymerization, have at least one double bond between carbon atoms, to form at least one acid group in the reaction of hydrolysis in an aqueous environment and react as an acid in water (for example: maleic anhydride or gidrolizuacy esters of acrylic acid, such as acrylate. The structural links of macromonomer polyether get through the inclusion of relevant macromonomers simple polyester in the form of polymerized units. In this regard, macromonomer polyether in the context of the present invention are compounds which are capable of radical copolymerization and have at least one double bond between carbon atoms and which contain oxygen atoms of simple ether. For this reason, the structural links of macromonomer polyether present in the copolymer, are, in each case at least one side chain that contains oxygen atoms of simple ether.

Basically, we can say that the mechanism of action of the respective copolymers having structural units of macromonomer polyether structural units of monomer acid is determined by their structural parameters. Range of highly relevant SOPs the materials cover the full range from the limit of lowering the water content to limit preserving the mobility of the concrete mix, where structural parameters, which provide a lower water content in conflict with the structural parameters that provide good preservation of the mobility. Thus, in addition to the magnitude of the charge on the weight of the link length of the side chains is also crucial, for example, in relation to the ability of lowering the water content. The dimension of the corresponding copolymers dosage of additives usually perform as a percentage of weight of cement cementitious mixture, i.e. on the basis of weight. As a rule, not only the existing mass of the molecules, but also the number of molecules of active substances are crucial for the mechanism of action. With long side chains have a high mass, which increases the opposite of most possible number of molecules of the copolymer on the weight of the link. Through directional inclusion of short side chains in addition to the long side chains, the molar mass of the copolymers can be reduced, but without adverse effects on dispersion effect, which is possible due to the long lateral chains. Thus, it is often optimal to include in the copolymer molecule short and long side chain polyether at the same time and to perform specified in accordance with the principle of "in each case, the Maxim is the emotional amount of the longer side chains, required, but the minimum quantity possible." Thus, the copolymer dosage supplements can be optimized in respect of their effective mass. This optimization can be carried out separately for both diametrically opposite phenomena-spectrum (lowering the water content, the preservation of the mobility). In the application, where required as lowering the water content and the preservation of consistency, it may be useful to use a physical mixture of these respective weight-optimised copolymer dosage of additives compared to the use of the individual copolymer additives, superplasticizers, optimized for the application. Advantages are the most reliable in terms of quality of cement (the content of alkali and sulfate), the variation of the temperature, or the possibility of easy processing of the mixture. In conclusion, it can be noted that the polymer composition in accordance with the invention represents a particularly economical and high quality dispersing agent or additive dosage.

Basically, the polymer composition in accordance with the invention contains 10-85 weight % of the copolymer H and 10-85 weight % of the copolymer K.

Preferably, at least 50 mol % of all structural links with the polymer N and at least 50 mol % of all structural units of the copolymer To be present in each case in the form of structural units of the monomer acid.

Basically, the number of oxygen atoms simple ester in the side chain structural units of macromonomer polyether copolymers H and K, in each case, vary in such a way that the corresponding graph of probability density functions, where the number of oxygen atoms simple ester in the side chain the structural unit macromonomer polyether, in each case, displayed on the x-axis and respectively corresponding to the frequency of occurrence for copolymers of N or, in each case, are shown on the ordinate axis, contain in each case at least 2 maximum values of the abscissa which, in each case, differ from each other by more than 10 oxygen atoms of simple ether.

Often the number of oxygen atoms simple ester in the side chain structural units of macromonomer polyether copolymers H and K vary in each case, so that the corresponding graph of the probability density functions, where the number of oxygen atoms simple ester in the side chain the structural unit macromonomer polyether, in each case, displayed on the x-axis and respectively corresponding the existing frequency of occurrence for copolymers of N or K, in each case, displayed on the y axis, in each case contain at least 2 maximum values of the abscissa which in each case differ from each other by more than 10 oxygen atoms of simple ether, and the graph of the density probability distribution of the copolymers H and K are different from each other so that the value of the abscissa at least one maximum of the copolymer of N, in each case, differs by more than 10 oxygen atoms of simple ether from the values of the abscissa of all highs copolymer K.

Typically, the structural links of the monomer acid copolymers H and K, in each case, present in accordance with one of the General formulas (Ia), (Ib), (Ic) and/or (Id)

(Ia)

where

R1are the same or different and represented by H and/or a straight or branched C1-C4alkyl group:

X are identical or different and presents NH-(CnH2n), where n=1, 2, 3 or 4 and/or O-(CnH2n), where n=1, 2, 3 or 4, and/or unrepresented link;

R2are the same or different and presents IT, SO3H, RHO3H2O-RO3H2and/or para-substituted C6H4-SO3H, provided that when X is non-link, R2IT is presented:

(Ib)

the de

R3are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;

n=0, 1, 2, 3 or 4;

R4are the same or different and presents SO3H, RHO3H2O-RO3H2and/or para-substituted C6H4-SO3H;

(Ic)

where

R5are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;

Z are identical or different and represented by O and/or NH;

(Id)

where

R6are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;

Q are the same or different and are represented by NH and/or Oh;

R7are the same or different and represented by H, (CnH2n)-SO3H, where n=0, 1, 2, 3 or 4, (CnH2n)-HE, where n=0, 1, 2, 3 or 4: (CnH2n)RHO3H2where n=0, 1, 2, 3 or 4, (CnH2n)ORO3H2where n=0, 1, 2, 3 or 4, (C6H4)-SO3H, (C6H4)RHO3H2, (C6H4)ORO3H2and/or (CmH2m)e-O-(A O)α-R9where m=0, 1, 2, 3, or 4, e=0, 1, 2, 3 or 4, A'=Cx'H2'where x'=2, 3, 4 or 5, and/or CH2C6the 5)N, α = an integer from 1 to 350 with R9that are the same or different and presents a straight or branched C1-C4alkyl group.

Depending on the pH of the structural units of monomer acids can also be present in deprotonirovannoi form as a salt, where the typical counterions are Na+To+and CA2+.

Often the structural links of the monomer acid copolymers H and To receive in each case by the inclusion of the acid monomers of methacrylic acid, acrylic acid, maleic acid, maleic anhydride and/or complex monoamino maleic acid in the form of polymerized units.

Preferably structural units of macromonomer polyether copolymers H and K, in each case, present in accordance with one of the General formulas (IIa), (IIb) and/or (IIe)

(IIa)

where

R10, R11and R12in each case are identical or different and, independently from each other presents N and/or a straight or branched C1-C4alkyl group;

E are identical or different and presents a straight or branched C1-C6alkalinous group, tsiklogeksilnogo group, CH2-C6H10, ortho-, meta - or para-substituted C6sub> 4and/or unrepresented link;

G are the same or different and represented by O, NH and/or CO-NH, provided that when E is unrepresented link, then G is also present as unrepresented link:

And are the same or different and represented by CxH2xwhere x=2, 3, 4 and/or 5 (preferably x=2), and/or CH2CH(C6H5):

n are identical or different and represented by 0, 1, 2, 3, 4 and/or 5;

and are the same or different and is an integer from 5 to 350 (preferably 10-200);

R13are the same or different and represented by H, a straight or branched C1-C4alkyl group, CO-NH2and/or the PINES3;

(IIb)

where

R14are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;

E are identical or different and presents a straight or branched C1-C6alkalinous group, tsiklogeksilnogo group, CH2-C6H10, ortho-, meta - or para-substituted C6H4and/or unrepresented link;

G are the same or different and is represented unrepresented link, Oh, NH and/or CO-NH, provided that when E is unrepresented link, then G is also present as the e unrepresented link;

And are the same or different and represented by CxH2xwhere x=2, 3, 4 and/or 5 and/or CH2CH(C6H5):

n are identical or different and represented by 0, 1, 2, 3, 4 and/or 5;

and are the same or different and is an integer from 5 to 350;

D are the same or different and is represented unrepresented link, NH and/or Oh, provided that when D is unrepresented link: b=0, 1, 2, 3 or 4 and C=0, 1, 2, 3 or 4, where b+C=3 or 4, and provided that, if D is NH and/or O: b=0, 1, 2 or 3, with=0, 1, 2 or 3, where b+C=2 or 3;

R15are the same or different and represented by H, a straight or branched C1-C4alkyl group, CO-NH2and/or PINES3;

(IIc)

where

R16, R17and R18in each case are identical or different and, independently from each other presents N and/or a straight or branched C1-C4alkyl group;

E are identical or different and presents a straight or branched C1-C6alkalinous group, tsiklogeksilnogo group, CH2-C6H10and/or ortho-, meta - or para-substituted C6H4;

And are the same or different and are represented WithxH2where x=2, 3, 4 and/or 5 and/or CH2-CH(C6H5);

n ablauts the same or different and represented by 0, 1, 2, 3, 4 and/or 5;

L are identical or different and represented by CxH2xwhere x=2, 3, 4 and/or 5 and/or CH2-CH(C6H5);

and are the same or different and is an integer from 5 to 350;

d are the same or different and is an integer from 1 to 350;

R19are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;

R20are the same or different and represented by H and/or a direct C1-C4alkyl group.

Often the structural links of macromonomer polyether copolymers H and K, in each case, get through the inclusion of macromonomers polyether alkoxysilane hydroxymethylcellulose simple ester, and/or alkoxysilanes dietilaminoetilovogo simple ester, and/or alkoxysilanes of isoprene, and/or alkoxysilanes (meth)allyl alcohol, and/or vinnilirunnu of methylpolysiloxanes, which preferably in each case have an average number of 6) is 300 oxyalkylene groups in the form of polymerized units.

CNS links macromonomer polyether usually present as ethoxyline group or as a mixture ethoxyline and propoxyphenol group (specified macromonomer PR the buffer of net polyester may be obtained by amoxilonline or ethoxycarbonyl and propoxycarbonyl corresponding monomers alcohols).

The copolymers H and K can have in each case the same or different types of structural links macromonomer polyether and/or structural parts of monomer acid.

As a rule, in each case, at least 45 mol %, preferably at least 80 mol % of all structural units of the copolymers H and K receive by incorporation of acid monomer and macromonomer simple polyester in the form of polymerized units.

The invention also relates to a dispersion liquid that contains at least 30 weight % of water and at least 10 weight % of the polymer composition described above. Dispersing agent is preferably present in the aqueous solution.

In addition, the present invention also relates to a method for preparing a polymeric composition in accordance with the invention or the method of preparation of the dispersant substances in accordance with the invention, in which each of the copolymers H and K are prepared separately from each other in aqueous solution separately prepared copolymers or separately prepared aqueous solutions are then mixed with each other.

Typically, the monomer acid and macromonomer polyether react with radical polymerization with the use of peroxide system initiator of oxidation-is vosstanovleniya in aqueous solution, thus the temperature of the aqueous solution during the polymerization is 10-45°C and the pH is 3.5-6.5.

Finally, the invention also relates to the use of polymer compositions in accordance with the invention as a dispersing substances for hydraulic binders and/or binding agents with latent hydraulic properties. Typically, the hydraulic binder is present as cement, lime, gypsum, hemihydrate or anhydrite or a mixture of these components, preferably as cement. Binder with latent hydraulic properties usually present as fly ash, volcanic tuff or blast furnace slag. Polymer composition in accordance with the invention may also be applied, for example (especially in dehydrated form), as an additive in cement production (dispersing agent and a substance that lowers the water content in finely ground Portland cement, or composite cements).

Below the invention is explained in more detail in relation to the demonstration of the examples in combination with graphic material.

Graphic material shows:

The Figure 1 shows a diagram which schematically shows the frequency of occurrence of the number of oxygen atoms of simple ether side chains and which is tositsa to polymeric compositions in accordance with the invention according to the application example

Figure 2 depicts a diagram that shows a draft of the cone as a function of time and where the polymer composition in accordance with the invention according to example of application compared with other polymer compositions.

Example of Synthesis 1 - Copolymer of N polymer compositions in accordance with the invention

227 g of deionized water and 250 g of vinyloxycarbonyloxy-1100 (product fitting 22 mol of ethylene oxide with hydroxyethylmonium simple ether) and 113,6 g vinyloxycarbonyloxy-500 (product of accession of 9 mol of ethylene oxide with hydroxyethylmonium simple ether) were initially placed in a glass laboratory reactor, equipped with stirrer, electrode for measuring pH values and number of feeders, and were cooled to the temperature of the beginning of polymerization, which was 12°C (source taken mixture).

In a separate vessel supply to 39.3 g of acrylic acid and 29,58 g hydroxypropylmethacrylate homogeneous mixed with 206,65 g of deionized water. Using 23,27 g 40%aqueous concentrated solution of potassium hydroxide and cooling, the solution was brought to a temperature of 20°C, and the pH value was brought to 4.0. Was then added 2,88 g 3-mercaptopropionic acid as a regulator of the molecular weight (solution A).

At the same time was prepared with the second solution, Ostoji from 2,07 g of a mixture of disodium salt of 2-hydroxy-2-sulfametoxazol acid, disodium salt of 2-hydroxy-2-sulfametoxazol acid and sodium sulfite (Brüggolit® FF6 from Brüggemann GmbH) and 66,93 g of water (solution B).

Then 89,6 g of the solution a and then 5.9 g of a 20%concentration aqueous solution of sodium hydroxide and 1.55 g of 3-mercaptopropionic acid as a regulator of the molecular weight were added to the original mixture taken, accompanied by stirring and cooling.

of 0.085 g of iron sulfate heptahydrate(II) and with 5.22 g of hydrogen peroxide (30% in water) were then added to the original mixture taken. At the same time started adding solution a and solution to the mixed initial mixture taken.

The rate of addition of the remaining solution As shown by the following scheme added. The speed of addition of the solution is 33.5 g/h for 45 minutes, then increased to 205 g/h, and the addition is continued until the entire solution is in the reactor. During the reaction gradually add 18 g of 20%concentration aqueous solution of sodium hydroxide.

t (min)01.5369121518 2124273033363945
A solution (g/h)14328750260055850243034327221217012710372630

After complete addition of solutions a and b peroxide in the chemical reactor is no longer there.

The resulting polymer solution was then brought to pH, which was 6.5, with approximately 42 g of 20%concentration of sodium hydroxide solution.

The obtained copolymer was present in slightly yellowish solution, which contained 44.3% solids. The average molecular weight of the copolymer MV was 24000 g/mol; the transformation in accordance with GPC: 95%.

Example of Synthesis 2 - Copolymer of the polymer composition in accordance with the invention

423,4 g of deionized water and 16,65 g vinyloxycarbonyloxy-1100 (product fitting 22 mol of ethylene oxide with hydroxyethylmonium simple ether) and 351,25 g vinyloxycarbonyloxy-5800 (product fitting 129 mol of ethylene oxide with hydroxyethylmonium simple ether) were initially placed in a glass laboratory reactor, equipped with stirrer, electrode for measuring pH values and number of feeders, and were cooled to the temperature of the beginning of polymerization of 15°C (source taken mixture).

In a separate vessel supply 19,64 g of acrylic acid and 15,76 g hydroxypropylmethacrylate homogeneous mixed with 106,20 g of deionized water. Using 5,44 g 40%concentrated potassium hydroxide solution and cooling the solution was brought to a temperature of 20°C, and the pH was brought to 3.5. Was then added 2,52 g 3-mercaptopropionic acid as a regulator of the molecular weight (solution A).

At the same time was prepared with a second solution consisting of 1.68 g of a mixture of disodium salt of 2-hydroxy-2-sulfametoxazol acid, disodium salt 2-hydroxy-2-sulfametoxazol acid and sodium sulfite (Brüggolit® FF6 from Brüggemann GmbH) and 26,32 g of water (solution B).

Then were added of 73.5 g of the solution, then taken to the original mixture were added to 11.0 g of a 20%concentration aqueous solution of sodium hydroxide and 0.28 g of 3-mercaptopropionic acid as a molecular weight regulator, accompanied by stirring and cooling.

Then taken to the original mixture were added in turn 0,1488 g of iron sulfate heptahydrate(II) 2,53 and g p is rekishi hydrogen (30% in water). At the same time started adding solution a and solution to the mixed initial mixture taken.

The rate of addition of the remaining solution As shown by the following scheme added. The speed of addition of the solution is 36.9 g/h for 30 minutes, then increased to 89 g/h, and the addition continues until the entire solution is in the reactor. During the time of the reaction gradually add 1.6 g of a 20%concentration aqueous solution of sodium hydroxide.

t (min)024681012141618222630
A solution (g/h)2222472572572472221821491199256.9 350

After complete addition of solutions a and b peroxide in the chemical reactor is no longer there.

Then the resulting polymer solution was brought to pH 6.5 with approximately 30 g of a 20%concentration of sodium hydroxide solution.

The obtained copolymer was present in slightly yellowish solution, which contained 40.6% of the solid particles. The average molecular weight of the copolymer MV was 73000 g/mol; the transformation in accordance with GPC: 87%.

Example of Synthesis of 3 - (for comparison - not relevant to polymer compositions in accordance with the invention)

"Chemical mixture" corresponds to 0.7 parts of copolymer To and 0.3 parts of a copolymer of N, 59,64 g of deionized water and 15.95 g vinyloxycarbonyloxy-1100 (product fitting 22 mol of ethylene oxide with hydroxyethylmonium simple ether and 162,40 g vinyloxycarbonyloxy-5800 (product fitting 129 mol of ethylene oxide with hydroxyethylmonium simple ether) and 3.75 g of vinyloxycarbonyloxy-500 (product of accession 10 mol of ethylene oxide with hydroxyethylmonium simple ether) was initially placed in a glass laboratory reactor, equipped with stirrer, electrode for measuring pH and a number of drawers, and was cooled to the temperature of the beginning of polymerise the AI 15°C (source taken mixture).

In a separate vessel supply was homogeneous mixed 10,38 g of acrylic acid and compared to 8.26 g hydroxypropylmethacrylate with 67.2 per g of deionized water. With the help of 3.05 g of 40%aqueous concentrated potassium hydroxide solution and cooling the solution was brought to a temperature of 20°C, and the pH was brought to 3.5 (solution A).

At the same time was prepared with a second solution consisting of 3 g of a mixture of disodium salt of 2-hydroxy-2-sulfametoxazol acid, disodium salt 2-hydroxy-2-sulfametoxazol acid and sodium sulfite (Brüggolit® FF6 from Brüggemann GmbH) and 47 g of water (solution B).

To the original taken mixture was added 44,75 g of the solution a and then 2.6 g of a 20%concentration aqueous solution of sodium hydroxide and 0.16 g of 3-mercaptopropionic acid as a molecular weight regulator, accompanied by stirring and cooling. To the remaining solution a was added 1.44 g of 3-mercaptopropionic acid.

Once taken in the original mixture, the pH value was increased to 5.3, taken to the original mixture was in turn added 0,0875 g of iron sulfate heptahydrate(II) and (1,49 g hydrogen peroxide (30% in water). At the same time to the mixed source is taken of the mixture was started by the addition of solution a and solution C.

The rate of addition of the remaining solution As shown by the following scheme added. The speed of adding rastvorov is to 20.8 g/h for 30 minutes, then increased to 100 g/h, and the addition is continued until the entire solution is in the reactor. During the time of the reaction gradually add to 3.9 g of 20%concentration aqueous solution of sodium hydroxide.

t(min)024681012141618222630
A solution (g/h)14015516216215514011494755836220

After complete addition of solutions a and b peroxide in the chemical reactor is no longer there.

The resulting polymer solution was then brought to pH value, which amounted to 6.5, with approximately 15 g of 20-Noy concentration of the sodium hydroxide solution.

The obtained copolymer was present in slightly yellowish solution, which contained 41.5 percent solids. The average molecular weight of the copolymer MV was 57000 g/mol; the transformation in accordance with GPC: 89%.

For the preparation of polymeric compositions in accordance with the invention (for the following example of the application of "physical mixture" in accordance with the invention) 129,21 g polymer copolymer solution To (synthesis example 2) was mixed with 50 g of the polymer solution of the copolymer of N (synthesis example 1), which is based on the respective polymer particles of the copolymers H and K, corresponding to the ratio of components in the mixture as 70:30. Schematic diagram in accordance with Figure 1 shows on the abscissa axis (X) the number of oxygen atoms simple ester in the side chain structural units of macromonomer polyether (all of the copolymers H and K) polymer compositions in accordance with the invention, which was prepared by this method? and on the ordinate axis (Y) shows the respective associated frequency of occurrence. The highest incidence occurs in the average number of oxygen atoms of simple ether, which is 23, because of the frequency of occurrence of the copolymers H and K here, that correspond to the source material vinylacetylene jingleball-1100 (product fitting 22 mol of ethylene oxide with hydroxyethylmonium simple ether), which is used in both examples of the synthesis of 1 and 2 are cumulative. The average number 23 receive, taking into account the additional oxygen atom of a simple ester of a vinyl end group" elementary level macromonomer. The same applies to the other two vinyloxycarbonyloxy that apply. Figure 1 also shows the distances between the corresponding maxima of the distribution of physical mixtures of the copolymers H and K. Reproduced the distribution of the oxygen atoms of the simple ester, corresponding to a "bell schedule"is just schematic (actual width of the distribution may differ).

All polymer mixtures investigated in the application examples below, mixed with a small amount of conventional defoaming means in order to control the volume of air in the pores.

Examples of the application

Slump cone according to DIN EN 12350-5 (German industrial standard), in the study of freshly prepared concrete, 400 kg SEM 1 52.5 R Mergelstetten,/C=0,36, the addition of 0.21% each

The results of the application examples shown in the diagram of Figure 2, where the time is displayed in minutes on the x-axis (N) and sediment cone in cm is displayed on the y-axis (M), circles represent the standard dosage Supplement (without added Boko what's chains), the diamonds represent the copolymer of N as an optimized dosage of the additive, the triangles represent the physical mixture of the copolymers H and K in accordance with the invention, and the squares represent the mixture in accordance with synthesis example 3.

Copolymer of N (diamonds) as an optimized version of the standard dosage of the additive (Glenium ACE 30 from BASF, which contains no added side chains, circles) shows a particularly good ability to resist treatment with the appropriate addition of 0.21% (dry substance dosage of the additive based on the weight of the cement mixture) during the initial 40 minutes For comparison, the physical mixture of the copolymer H and copolymer in accordance with the invention when the ratio of components in a mixture of 0.7:0.3, and based on the content of the polymer in solution, shows a much higher performance (triangles), even to 60 minutes the Mixture in accordance with synthesis example 3 (squares) is worse than the mixture in accordance with the invention (triangles), because, first, it leads to much additional plasticization (increased precipitation cone from 56 to 63.5 cm during the initial 10 minutes) and, secondly, does not provide the ability to resist the treatment over time compare is ina good way (sediment cone is 55 cm even after 40 minutes, while the mixture according to the invention still has a settling cone 61 cm after 60 minutes).

1. Polymer composition for use as a dispersant compounds containing 3-95 weight % of the copolymer H and 3-95 weight % of the copolymer, each of the copolymers H and K contains structural units of macromonomer polyether structural units of monomer acids, which are present in the copolymers H and K, in each case in a molar ratio of 1:20-1:1, and at least 20 mol % of all structural units of the copolymer H and at least 25 mol % of all structural units of the copolymer K, in each case, present in the form of structural parts of monomer acid, while the structural links of macromonomer polyether copolymers H and K have side chains containing in each case at least 5 atoms of oxygen simple ether, and the number of oxygen atoms simple ester in the side chain structural units of macromonomer polyether copolymers H and K, in each case varies, so that the corresponding graph of probability density functions, where the number of oxygen atoms simple ester in the side chain the structural unit macromonomer polyether, in each case, displayed on the x-axis and, accordingly, appropriate to eastwoodiae frequency of occurrence copolymers of N or K, in each case, are shown on the ordinate axis, contain in each case at least 2 maximum values of the abscissa which in each case differ from each other more than 7 atoms of oxygen simple ether, and the graph of the density probability distribution of the copolymers H and K are different from each other so that the value of the abscissa at least one maximum of the copolymer of N, in each case, differ by more than 5 atoms of oxygen simple ether from the values of the abscissa of all maxima of the copolymer, and/or the fact that average arithmetic oxygen atoms of simple ether structural units of macromonomer polyether copolymers H and K are different from each other by more than 5 atoms of oxygen simple ether.

2. Polymer composition in accordance with claim 1, containing 10-85 weight % of the copolymer H and 10-85 weight % of the copolymer K.

3. Polymer composition in accordance with claim 1 or 2, characterized in that at least 50 mol % of all structural units of the copolymer H and at least 50 mol % of all structural units of the copolymer K, in each case, is in the form of structural units of the monomer acid.

4. Polymer composition in accordance with claim 1, characterized in that the oxygen atoms of the simple ester in the side chain structural units of macromonomer simple floor the ether copolymers H and K, in each case, vary in such a way that the corresponding diagram of the density of the probability distribution, where the number of oxygen atoms simple ester in the side chain the structural unit macromonomer polyether, in each case, displayed on the x-axis and respectively corresponding to the frequency of occurrence of copolymers of N, or, in each case, are shown on the ordinate axis, contain at least 2 maximum values of the abscissa which in each case differ from each other by more than 10 oxygen atoms of simple ether.

5. Polymer composition in accordance with claim 2, characterized in that the oxygen atoms of the simple ester in the side chain structural units of macromonomer polyether copolymers H and K, in each case, vary in such a way that the corresponding diagram of the density of the probability distribution, where the number of oxygen atoms simple ester in the side chain the structural unit macromonomer polyether, in each case, displayed on the x-axis and respectively corresponding to the frequency of occurrence of copolymers of N, or, in each case, are shown on the ordinate axis, contain at least 2 maximum values of the abscissa which, in each case differ from each other by more than 10 oxygen atoms of simple ether.

p> 6. Polymer composition in accordance with claim 3, characterized in that the oxygen atoms of the simple ester in the side chain structural units of macromonomer polyether copolymers H and K, in each case, vary in such a way that the corresponding diagram of the density of the probability distribution, where the number of oxygen atoms simple ester in the side chain the structural unit macromonomer polyether, in each case, displayed on the x-axis and, respectively, the corresponding frequencies of occurrence of copolymers of N, or, in each case, are shown on the ordinate axis, contain at least 2 maximum values of the abscissa which, in each case, differ from each other by more than 10 oxygen atoms of simple ether.

7. Polymer composition in accordance with claim 1 or 2, characterized in that the oxygen atoms of the simple ester in the side chain structural units of macromonomer polyether copolymers H and K are different from each other so that the corresponding graph of the density probability distribution, where the number of oxygen atoms simple ester in the side chain the structural unit macromonomer polyether is displayed relative to each other on the x-axis and respectively corresponding to the frequency of occurrence of copolymers of N is To be displayed relative to each other on the axis of ordinates, contain with respect to each other, at least 2 maximum values of the abscissa which differ from each other by more than 10 oxygen atoms of simple ether, and the graph of the density probability distribution of the copolymers H and K are different from each other so that the value of the abscissa at least one maximum of the copolymer of N, in each case, different from the values of the abscissa of all maxima of the copolymer To more than 10 oxygen atoms of simple ether.

8. Polymer composition in accordance with claim 3, characterized in that the oxygen atoms of the simple ester in the side chain structural units of macromonomer polyether copolymers H and K are different from each other so that the corresponding graph of the density probability distribution, where the number of oxygen atoms simple ester in the side chain the structural unit macromonomer polyether is displayed relative to each other on the x-axis and respectively corresponding to the frequency of occurrence of copolymers of N, or To appear relative to each other on the axis of ordinates, contain in relation to each other, at least 2 maximum values of the abscissa which differ from each other more than 10 oxygen atoms of simple ether, and the graph of the density probability distribution of the copolymers H and Otlichautsya from each other, what is the value of the abscissa at least one maximum of the copolymer of N, in each case, different from the values of the abscissa of all maxima of the copolymer To more than 10 oxygen atoms of simple ether.

9. Polymer composition in accordance with claim 4, characterized in that the oxygen atoms of the simple ester in the side chain structural units of macromonomer polyether copolymers H and K are different from each other so that the corresponding graph of the density probability distribution, where the number of oxygen atoms simple ester in the side chain the structural unit macromonomer polyether is displayed relative to each other on the x-axis and respectively corresponding to the frequency of occurrence of copolymers of N, or To appear relative to each other on the axis of ordinates, contain in relation to each other, at least 2 maximum values of the abscissa which differ from each other more than 10 oxygen atoms of simple ether, and the graph of the density probability distribution of the copolymers H and K are different from each other so that the value of the abscissa at least one maximum of the copolymer of N, in each case, different from the values of the abscissa of all maxima of the copolymer To more than 10 oxygen atoms of simple ether.

10. Polymer composition in accordance with the tvii with claim 1 or 2, characterized in that the structural units of monomer acid copolymers H and K, in each case, present in accordance with one of the General formulas (Ia), (Ib), (Ic) and/or (Id)
(Ia)

where
R1are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
X are identical or different and presents NH-(CnH2n), where n=1, 2, 3 or 4 and/or O-(CnH2n), where n=1, 2, 3 or 4 and/or unrepresented link;
R2are the same or different and presents IT, SO3H, RHO3H2O-RO3H2and/or para-substituted C6H4-SO3H, provided that when X is non-link, R2IT is presented;
(Ib)

where
R3are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
n=0, 1, 2, 3 or 4;
R4are the same or different and presents SO3H, RHO3H2O-RO3H2and/or para-substituted C6H4-SO3H;
(Ic)

where
R5are the same or different and represented by H and/or a straight or branched C1-C4alkyl group:
Z are the same or different and performance is aulani Oh and/or NH;
(Id)

where
R6are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
Q are the same or different and are represented by NH and/or Oh;
R7are the same or different and represented by H, (CnH2n)-SO3H, where n=0, 1, 2, 3 or 4, (CnH2n)-HE, where n=0, 1, 2, 3 or 4; (CnH2n)RHO3H2where n=0, 1, 2, 3 or 4, (CnH2n)ORO3H2where n=0, 1, 2, 3 or 4, (C6H4)-SO3H, (C6H4)RHO3H2, (C6H4)ORO3H2and/or (CmH2m)e-O-(A O)α-R9where m=0, 1, 2, 3, or 4, e=0, 1, 2, 3 or 4, A'=Cx'H2'where x'=2, 3, 4, or 5 and/or CH2C6H5)N, α = an integer from 1 to 350 with R9that are the same or different and presents a straight or branched C1-C4alkyl group.

11. Polymer composition in accordance with claim 3, characterized in that the structural units of monomer acid copolymers H and K, in each case, present in accordance with one of the General formulas (Ia), (Ib), (Ic) and/or (Id)
(Ia)

where
R1are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
X are dinasovymi or different and presents NH-(C nH2n), where n=1, 2, 3 or 4 and/or O-(CnH2n), where n=1, 2, 3 or 4, and/or unrepresented link:
R2are the same or different and presents IT, SO3H, RHO3H2About RHO3H2; and/or para-substituted C6H4-SO3H, provided that when X is non-link, R2IT is presented:
(Ib)

where
R3are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
n=0, 1, 2, 3 or 4;
R4are the same or different and presents SO3H, RHO3H2About RHO3H2and/or para-substituted C6H4-SO3H;
(Ic)

where
R5are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
Z are identical or different and represented by O and/or NH;
(Id)

where
R6are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
Q are the same or different and are represented by NH and/or Oh;
R7are the same or different and represented by H, (CnH2n)-SO3H, where n=0, 1, 2, 3 or 4, (CnH2n)-HE, where n=0, 1, 2, ili 4; (CnH2n)RHO3H2where n=0, 1, 2, 3 or 4, (CnH2n)ORO3H2where n=0, 1, 2, 3 or 4, (C6H4)-SO3H, (C6H4)RHO3H2, (C6H4)ORO3H2and/or (CmH2m)e-O-(A O)α-R9where m=0, 1, 2, 3, or 4, e=0, 1, 2, 3 or 4, A'=Cx'H2'where x'=2, 3, 4 or 5, and/or CH2C6H5)N, α = an integer from 1 to 350 with R9that are the same or different and presents a straight or branched C1-C4alkyl group.

12. Polymer composition in accordance with claim 4, characterized in that the structural units of monomer acid copolymers H and K, in each case, present in accordance with one of the General formulas (Ia), (Ib), (Ic) and/or (Id)
(Ia)

where
R1are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
X are identical or different and presents NH-(CnH2n), where n=1, 2, 3 or 4 and/or O-(CnH2n), where n=1, 2, 3 or 4, and/or unrepresented link;
R2are the same or different and presents IT, SO3H, RHO3H2O-RO3H2and/or para-substituted C6H4-SO3H, provided that when X is non-link, R2 IT is presented;
(Ib)

where
R3are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
n=0, 1, 2, 3 or 4;
R4are the same or different and presents SO3H, RHO3H2O-RO3H2and/or para-substituted C6H4-SO3H;
(Ic)

where
R5are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
Z are identical or different and represented by O and/or NH;
(Id)

where
R6are the same or different and represented by H and/or a straight or branched C1-C4alkyl group:
Q are the same or different and are represented by NH and/or Oh;
R7are the same or different and represented by H, (CnH2n)-SO3H, where n=0, 1, 2, 3 or 4, (CnH2n)-HE, where n=0, 1, 2, 3 or 4: (CnH2n)RHO3H2where n=0, 1, 2, 3 or 4, (CnH2n)ORO3H2where n=0, 1, 2, 3 or 4, (C6H4)-SO3H, (C6H4)RHO3H2, (C6H4)ORO3H2and/or (CmH2m)e-O-(A O)α-R9where m=0, 1, 2, 3, or 4, e=0, 1, 2, 3 or 4, A'=Cx'H2'where x'=2, 3, 4 or 5, and/Ilin 2C6H5)N, α = an integer from 1 to 350 with R9that are the same or different and presents a straight or branched C1-C4alkyl group.

13. Polymer composition in accordance with claim 5, characterized in that the structural units of monomer acid copolymers H and K, in each case, present in accordance with one of the General formulas (Ia), (Ib), (Ic) and/or (Id)
(Ia)

where
R1are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
X are identical or different and presents NH-(CnH2n), where n=1, 2, 3 or 4, and/or O-(CnH2n), where n=1, 2, 3 or 4, and/or unrepresented link;
R2are the same or different and presents IT, SO3H, RHO3H2About RHO3H2and/or para-substituted C6H4-SO3H, provided that when X is non-link, R2IT is presented;
(Ib)

where
R3are the same or different and represented by H and/or a straight or branched C1-C4alkyl group:
n=0, 1, 2, 3 or 4;
R4are the same or different and presents SO3H, RHO3H2O-RO3H2and/or para-substituted C6H -SO3H;
(Ic)

where
R5are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
Z are identical or different and represented by O and/or NH;
(Id)

where
R6are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
Q are the same or different and are represented by NH and/or Oh;
R7are the same or different and represented by H, (CnH2n)-SO3H, where n=0, 1, 2, 3 or 4, (CnH2n)-HE, where n=0, 1, 2, 3 or 4: (CnH2n)RHO3H2where n=0, 1, 2, 3 or 4, (CnH2n)ORO3H2where n=0, 1, 2, 3 or 4, (C6H4)-SO3H, (C6H4)RHO3H2, (C6H4)ORO3H2and/or (CmH2m)e-O-(A O)α-R9where m=0, 1, 2, 3, or 4, e=0, 1, 2, 3 or 4, A'=Cx'H2'where x'=2, 3, 4 or 5, and/or CH2C6H5)N, α = an integer from 1 to 350 with R9that are the same or different and presents a straight or branched C1-C4alkyl group.

14. Polymer composition in accordance with claim 1 or 4, characterized in that the structural units of monomer acid copolymers H and K, in each case, ucaut by the inclusion of acid monomers, methacrylic acid, acrylic acid, maleic acid, maleic anhydride and/or complex monoamino maleic acid in the form of polymerized units.

15. Polymer composition in accordance with claim 1 or 4, characterized in that the structural units of macromonomer polyether copolymers H and K, in each case, present in accordance with one of the General formulas (IIa), (IIb) and/or (IIc)
(IIa)

where
R10, R11and R12in each case are identical or different and, independently from each other, represented by H and/or a straight or branched C1-C4alkyl group;
E are identical or different and presents a straight or branched C1-C6alkalinous group, tsiklogeksilnogo group, CH2-With6H10, ortho-, meta - or para-substituted C6H4and/or unrepresented link;
G are the same or different and represented by O, NH and/or CO-NH, provided that when E is unrepresented link, then G is also present as unrepresented management;
And are the same or different and are represented WithxH2where x=2, 3, 4 and/or 5 (preferably x=2), and/or CH2CH(C6H5);
n are identical or different and represented by 0, 1, 2, 3, 4 and/or 5;
and are the same or different and, not only is t an integer from 5 to 350 (preferably 10-200);
R13are the same or different and represented by H, a straight or branched C1-C4alkyl group, CO-NH2and/or the PINES3;
(IIb)

where
R14are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
E are identical or different and presents a straight or branched C1-C6alkalinous group, tsiklogeksilnogo group, CH2-C6H10, ortho-, meta - or para-substituted C6H4and/or unrepresented link;
G are the same or different and is represented unrepresented link, Oh, NH and/or CO-NH, provided that when E is unrepresented link, then G is also present as unrepresented management;
And are the same or different and are represented WithxH2where x=2, 3, 4 and/or 5 and/or CH2CH(C6H5);
n are identical or different and represented by 0, 1, 2, 3, 4 and/or 5;
and are the same or different and is an integer from 5 to 350;
D are the same or different and is represented unrepresented link, NH and/or Oh, provided that when D is unrepresented link: b=0, 1, 2, 3 or 4 and C=0, 1, 2, 3 or 4, where b+C=3 or 4, and provided that, if D is NH and/or O: b=0, 1, 2 or 3, with=0, 1, 2 is 3, where b+C=2 or 3;
R15are the same or different and represented by H, a straight or branched C1-C4alkyl group, CO-NH2and/or PINES3;
(IIc)

where
R16, R17and R18in each case are identical or different and, independently from each other, represented by H and/or a straight or branched C1-C4alkyl group;
E are identical or different and presents a straight or branched C1-C6alkalinous group, tsiklogeksilnogo group, CH2-C6H10and/or ortho-, meta - or para-substituted C6H4;
And are the same or different and represented by CxH2xwhere x=2, 3, 4 and/or 5 and/or CH2CH(C6H5);
n are identical or different and represented by 0, 1, 2, 3, 4 and/or 5;
L are identical or different and represented by CxH2xwhere x=2, 3, 4 and/or 5 and/or CH2-CH(C6H5);
and are the same or different and is an integer from 5 to 350;
d are the same or different and is an integer from 1 to 350;
R19are the same or different and represented by H and/or a straight or branched C1-C4alkyl group;
R20are the same or different and represented by H and/or a direct C 1-C4alkyl group.

16. Polymer composition in accordance with claim 1 or 4, characterized in that the structural units of macromonomer polyether copolymers H and K, in each case, get through the inclusion of polyester macromonomers alkoxysilanes hydroxymethylcellulose simple ester, and/or alkoxysilanes of isoprene, and/or alkoxysilanes (meth)allyl alcohol, and/or vinnilirunnu of methylpolysiloxanes that, in each case, it is preferable to have the arithmetic mean 6) is 300 oxyalkylene groups in the form of polymerized units.

17. Polymer composition in accordance with claim 1 or 4, characterized in that the copolymers H and K, in each case, have the same or different types of structural links macromonomer polyether and/or structural parts of monomer acid.

18. Polymer composition in accordance with claim 1 or 4, characterized in that, in each case, at least 45 mol %, preferably at least 80 mol % of all structural units of the copolymers H and To get through the incorporation of acid monomer and macromonomer simple polyester in the form of polymerized units.

19. Dispersing agent containing at least 30 weight % of water and at least 10 weight % of the polymer composition in accordance with any of the item is.1-18.

20. Dispersing agent according to claim 19, which is present in aqueous solution.

21. The method of preparation of the polymer composition according to any one of claims 1 to 18, characterized in that each of the copolymers H and K are prepared separately from each other in an aqueous solution and then separately prepared copolymers or separately prepared aqueous solutions are mixed with each other.

22. Method according to item 21, wherein the acid monomer and macromonomer polyether react by radical polymerization with the use of peroxide system initiator of oxidation-reduction in aqueous solution, while the temperature of the aqueous solution during the polymerization is 10-45°C and the pH is 3.5 to 6.5.

23. Applying a polymeric composition according to any one of claims 1 to 18 as a dispersing substances for hydraulic binders and/or binding agents with latent hydraulic properties.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer composition and a method for preparation thereof, a dispersant and a method for preparation thereof, as well as to use of the polymer composition. The polymer composition contains 3-90 wt % copolymer H and 3-90 wt % copolymer K. Each of the copolymers H and K contains structural links of a polyether macromonomer and structural links of an acid monomer in molar ratio of 1:20-1:1. At least 20 mol % of all structural links of copolymer H and at least 25 mol % of all structural links of copolymer K, in each case, are present in form of structural links of the acid monomer. At least 60 mol % structural links of the polyether macromonomer of copolymer H are represented by a structural link of an α derivative of isoprenol polyether of general formula (Ia) , where A are identical or different and denote an alkylene group in accordance with CxH2x, where x=2, 3, 4 or 5, and a are identical or different and denote an integer from 4 to 300. At least 60 mol % of structural links of the polyether macromonomer of copolymer K are represented by a structural link of a β derivative of a vinyloxy polyether of general formula (Ib) , where RA are identical or different and denote a hydrogen atom, a linear or branched C1-C12alkyl group, C5-C8cycloalkyl group, phenyl group or C7-C12arylalkyl group, A are identical or different and denote an alkylene group in accordance with CxH2x, where x=2, 3, 4 or 5, b are identical or different and denote an integer from 6 to 450. The arithmetic average of alkylene groups A of structural links belonging to the structural link of the β derivative of vinyloxy polyether is at least 1.5 times greater than the arithmetic average of alkylene groups A of structural links belonging to the structural link of the α derivative of isoprenol polyether. The dispersant contains at least 30 wt % water and at least 10 wt % said polymer composition. The method of preparing the polymer composition and the dispersant involves preparing each of the copolymers H and K separately from each other in an aqueous solution and then mixing the separately prepared copolymers or separately prepared aqueous solutions. The polymer composition is used as a dispersant for hydraulic binding agents and/or for binding agents with latent hydraulic properties.

EFFECT: invention enables to produce a highly effective super-plasticising additive.

54 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a curable sealing resin composition. The curable composition contains at least one anhydride-functionalised polymer in amount of 30-60 wt %, a polyol in amount of 10-25 wt %, an epoxide-functionalised polymer, oligomer or monomer in amount of 15-40 wt %, a urethane polyol-functionalised compound selected from a group consisting of urethane diol, polyurethane diol and combination thereof in amount of 5-15 wt % and a catalyst with respect to total weight of the resin. The resin composition can be cured at room temperature. Components used to prepare and cure the resin composition can be provided in form of two or more parts.

EFFECT: hydrolytic stability, high hardness, flexibility and low cost of production of the sealing resin which can be used to restore insulation and/or for environmental protection of cable joints, sealed articles etc.

13 cl, 4 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer composition and a method for preparation thereof, a dispersant and a method for preparation thereof, as well as to use of the polymer composition. The polymer composition contains 3-90 wt % copolymer H and 3-90 wt % copolymer K. Each of the copolymers H and K contains structural links of a polyether macromonomer and structural links of an acid monomer in molar ratio of 1:20-1:1. At least 20 mol % of all structural links of copolymer H and at least 25 mol % of all structural links of copolymer K, in each case, are present in form of structural links of the acid monomer. At least 60 mol % structural links of the polyether macromonomer of copolymer H are represented by a structural link of an α derivative of isoprenol polyether of general formula (Ia) , where A are identical or different and denote an alkylene group in accordance with CxH2x, where x=2, 3, 4 or 5, and a are identical or different and denote an integer from 4 to 300. At least 60 mol % of structural links of the polyether macromonomer of copolymer K are represented by a structural link of a β derivative of a vinyloxy polyether of general formula (Ib) , where RA are identical or different and denote a hydrogen atom, a linear or branched C1-C12alkyl group, C5-C8cycloalkyl group, phenyl group or C7-C12arylalkyl group, A are identical or different and denote an alkylene group in accordance with CxH2x, where x=2, 3, 4 or 5, b are identical or different and denote an integer from 6 to 450. The arithmetic average of alkylene groups A of structural links belonging to the structural link of the β derivative of vinyloxy polyether is at least 1.5 times greater than the arithmetic average of alkylene groups A of structural links belonging to the structural link of the α derivative of isoprenol polyether. The dispersant contains at least 30 wt % water and at least 10 wt % said polymer composition. The method of preparing the polymer composition and the dispersant involves preparing each of the copolymers H and K separately from each other in an aqueous solution and then mixing the separately prepared copolymers or separately prepared aqueous solutions. The polymer composition is used as a dispersant for hydraulic binding agents and/or for binding agents with latent hydraulic properties.

EFFECT: invention enables to produce a highly effective super-plasticising additive.

54 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to a method of obtaining heterogeneous mixture used in the paper industry. Described is the method of manufacturing heterogeneous mixture of polymers, including: (a) introduction into a solution of the first portion of a polymerisation initiator and one or several anionic or cationic monomers, with monomers carrying the same charge; (b) introduction into the solution of the second portion of the polymerisation initiator and one or several non-ionic monomers; (c) introduction of the third portion of the polymerisation initiator and one or several ionic monomers, whose charge is opposite to the charge of monomers from (a); (d) gradual introduction of the fourth portion of polymerisation initiator for a reaction of any remaining monomer with formation of a heterogeneous mixture of polymers; and (e) in case of necessity neutralisation of the obtained heterogeneous mixture of polymers, with anionic monomers being selected from the group, consisting of: (1) acrylic acid, (2) methacrylic acid, (3) styrene sulfonic acid, (4) vinyl sulfonic acid, (5) acrylamido methylpropane sulfonic acid and (6) their mixtures; cationic monomers are selected from the group, which includes: (1) diallyldimethylammonium chloride, (2) acryloylethyl trimethylammonium chloride, (3) methacryloylethyltrimethylammonium chloride, (4) acryloylethyltrimethylammonium sulfate, (5) methacryloyl ethyltrimethylammonium sulfate, (6) acrylamidopropyltrimethylammonium chloride, (7) methacrylamidopropyl trimethylammonium chloride, (8) non-quaternised forms (2)-(7), (9) vinylformamide (further hydrolised into vinylamine) and (10) their mixtures, and non-ionic monomers are selected from the group, consisting of: (1) acrylamide, (2) methacrylamide, (3) N-alkylacrylamide, (4) vinylformamide and (5) their mixtures. Also described is the heterogeneous mixture of polymers, intended for increasing the content of a filling agent in paper or carton, obtained by the method described above. Methods of increasing the content of the filling agent in a paper or carton sheet with application of the said heterogeneous mixture of polymers are described.

EFFECT: increase of the content of an inorganic filling agent in paper with simultaneous preservation of weight, strength and suitability of the final product for processing.

17 cl, 9 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a vulcanising polymer composition, a polymer vulcanisate obtained from the polymer composition and a method for production thereof. The vulcanising polymer composition contains (i) a hydrogenated polymer having a polymer backbone chain formed from (ia) 25-89.5 wt %, preferably 30-80 wt % and more preferably 45-75 wt % with respect to the polymer of a first monomer, which includes at least one secondary carbon atom and a tertiary carbon atom into the polymer backbone chain, such as at least one diene monomer, and (ib) 10-74.9 wt %, preferably 10-60 wt %, more preferably 15-55 wt %, even more preferably 20-50 wt % with respect to the polymer of a second monomer, such as an α,β-ethylenically unsaturated nitrile monomer; (ic) 0.1-20 wt %, preferably 0.5-20 wt %, more preferably 1-15 wt %, even more preferably 1.5-10 wt % with respect to the polymer of at least one monomer of a monoester of α,β-ethylenically unsaturated dicarboxylic acid, a monomer of α,β-ethylenically unsaturated dicarboxylic acid, a monomer of an anhydride of α,β-ethylenically unsaturated dicarboxylic acid or a diester of α,β-ethylenically unsaturated dicarboxylic acid as a third monomer, where the total content of all monomer links given in (ia), (ib) and (ic), is equal to 100 wt %; (ii) at least one cross-linking agent - polyamine, and (iii) at least one bi- or polycyclic amine-base which is selected from a group comprising 1,5-diazabicyclo[4,3,0]-5-nonene (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO) 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBC), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) and derivatives thereof. The invention also relates to a polymer vulcanisate and a method for production thereof.

EFFECT: obtained vulcanisates demonstrate high cross-link density and have improved properties.

16 cl, 17 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: composition contains at least one latex polymer, at least one pigment, water and at least one auxiliary additive. The auxiliary additive is ethoxylated tristyrenephenol and is present in an amount higher than about 1.3 wt % with respect to the weight of the polymer.

EFFECT: improved freeze-thaw stability, as well as other properties such as film setting time, colour stability, low film-formation temperature, film-forming resistance, blocking resistance, adhesion and sensitivity to water.

12 cl, 1 dwg, 24 tbl, 10 ex

FIELD: nanotechnologies.

SUBSTANCE: invention relates to the method to produce aqueous dispersions containing a metal salt nanogel. The method includes mixing an aqueous dispersion containing a metal salt nanogel (D-I) with an aqueous dispersion (D-II) of a polymerisation, polycondensation or addition polymerisation product to produce a stable aqueous dispersion (D-III). The metal salt nanogel (D-I) represents an aqueous dispersion of polymer particles with a diametre of balls equal in volume making the maximum of 500 nm. Polymer particles of the aqueous dispersion (D-I) are produced in three stages. At the stage (i) an aqueous dispersion is produced of an ester of acrylic or methacrylic acid of meshed structure, at the stage (ii) groups of esters of acrylic or methacrylic acid are exposed to alkaline hydrolysis at least partially by addition of an alkaline metal or ammonia hydroxide, and at the stage (iii) the ions of the alkaline metal introduced at the stage (ii) or ammonia ions are at least partially substituted with plurivalent ions.

EFFECT: production of a stable aqueous dispersion (D-III) suitable for making water-resistant optically transparent products with antimicrobial activity Also a solid intermediate product is described, as well as water-resistant products, such as a film, a fibre, a plate or a thread.

16 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: disclosed is a stabilising composition containing (A) a polymer of formula , where R1 is hydrogen or C1-12-alkyl, R2-COOM or -CH2COOM; M is hydrogen, an alkali or alkali-earth metal ion, or an ammonium ion or mixture thereof; n, m and k are molar ratios of monomers, where n ranges from 0 to 0.95, m ranges from 0.05 to 0.9 and k ranges from 0 to 0.8, and (n+m+k)=1, and the weight-average molecular weight ranges from 500 to 20 000 000 g/mol; (B) a chelating agent; (C) poly-alpha-hydroxyacrylic acid or alkaline salt thereof, or corresponding polylactone thereof, and (D) possibly a polycarboxylic acid polymer or alkaline salt thereof. The invention also discloses a method of treating fibrous material with said stabilising composition.

EFFECT: disclosed composition has a synergetic stabilising effect compared to existing stabilisers.

28 cl, 5 tbl, 8 ex

FIELD: textile, paper.

SUBSTANCE: method of paper preparation includes application of aqueous dispersion onto paper. Aqueous dispersion comprises one or more copolymers of ethylene with acrylic acid and one or more N,N-dialkylalkanolamines in amount suitable for efficient dispersion of water dispersion including dispersed solid substances with average particle size of less than approximately 100 nm. Specified aqueous dispersion does not contain hydroxides of alkaline metals. Paper is also described for use in electrophotographic or digital offset printing technologies.

EFFECT: paper has improved adhesion of toner.

22 cl, 2 tbl, 6 ex

FIELD: electricity.

SUBSTANCE: electrolyte is described, which contains eutectic mixture made of the following components: (a) compound having amide group; and (b) ionised salt that does not contain lithium. Also electrochemical device is described, which contains electrolyte. In addition, since eutectic mixture is characterised by superb thermal and chemical resistance, there is a possibility to solve problems of evaporation, exhaustion and inflammability of electrolytes, minimising side reactions between structural elements of device and electrolyte and improvement of electrochemical device safety.

EFFECT: electrolyte improved quality of electrochemical device due to superb specific conductivity by cation of metal contained in eutectic mixture, wide electrochemical window and low viscosity.

21 cl, 9 ex, 1 tbl, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention concerns colourant substances creating scale effect on plastic. Invention claims composition for plastic dyeing, where one or more colourants creating scale effect is mixed with at least partially polarised carrier material. Also invention claims method of obtaining colourant composition and its application in plastic colouring and in obtaining concentrated colourant.

EFFECT: prevented dust collection, easy flowing, increased material amount in extrusion process by double-rotor extruders and higher output of concentrated colourants in single-rotor extruders.

10 cl, 4 ex

FIELD: medicine.

SUBSTANCE: invention refers to polymers producing hydrogel and absorbing aqueous liquids, based on acid group carrying polymers produced by polymerisation of monoethylenoid-nonsaturated carboxylic acids with 3-25 carbon atoms, containing α-tocopherol as stabilising additive. Purpose of present invention is production of superabsorber with application as stabilising additive of native monomers of health-hazardless substance, as well as reduced duration of induction and production of superabsorber which does not have undesired colouring. Purpose in view is provided by the fact that as stabilising additive monoethylenoid-nonsaturated carboxylic acids with 3-25 carbon atoms, α-tocopherol is used; therefore duration of an induction of polymerisation is reduced, provided production of polymer which acts as superabsorber, having required colouring.

EFFECT: present invention concerns method of production of such polymers, their application for aqueous liquids absorption, specifically in hygienic products.

10 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer composition and a method for preparation thereof, a dispersant and a method for preparation thereof, as well as to use of the polymer composition. The polymer composition contains 3-90 wt % copolymer H and 3-90 wt % copolymer K. Each of the copolymers H and K contains structural links of a polyether macromonomer and structural links of an acid monomer in molar ratio of 1:20-1:1. At least 20 mol % of all structural links of copolymer H and at least 25 mol % of all structural links of copolymer K, in each case, are present in form of structural links of the acid monomer. At least 60 mol % structural links of the polyether macromonomer of copolymer H are represented by a structural link of an α derivative of isoprenol polyether of general formula (Ia) , where A are identical or different and denote an alkylene group in accordance with CxH2x, where x=2, 3, 4 or 5, and a are identical or different and denote an integer from 4 to 300. At least 60 mol % of structural links of the polyether macromonomer of copolymer K are represented by a structural link of a β derivative of a vinyloxy polyether of general formula (Ib) , where RA are identical or different and denote a hydrogen atom, a linear or branched C1-C12alkyl group, C5-C8cycloalkyl group, phenyl group or C7-C12arylalkyl group, A are identical or different and denote an alkylene group in accordance with CxH2x, where x=2, 3, 4 or 5, b are identical or different and denote an integer from 6 to 450. The arithmetic average of alkylene groups A of structural links belonging to the structural link of the β derivative of vinyloxy polyether is at least 1.5 times greater than the arithmetic average of alkylene groups A of structural links belonging to the structural link of the α derivative of isoprenol polyether. The dispersant contains at least 30 wt % water and at least 10 wt % said polymer composition. The method of preparing the polymer composition and the dispersant involves preparing each of the copolymers H and K separately from each other in an aqueous solution and then mixing the separately prepared copolymers or separately prepared aqueous solutions. The polymer composition is used as a dispersant for hydraulic binding agents and/or for binding agents with latent hydraulic properties.

EFFECT: invention enables to produce a highly effective super-plasticising additive.

54 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to processing plastics, specifically to a polyester composition for protective coating metal surfaces. A polyester composition is described, containing the following in wt %: polyethyleneterephthalate - 10.0-92.5, dimethylphthalate and/or diethylphthalate - 4.5-87.0, copolymer of ethylene with vinyl acetate - 1.5-12.0, hydroquinone - 0.1-0.8, heat stabiliser - 0.2-2.5 and talc or basalt as filler - 0.5-12.5.

EFFECT: proposed polyester composition provides 1,5 times increase in strength and 1,5-2 times increase in adhesion strength to steel at 20°C.

2 cl, 14 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to the field of construction materials, in particular to compositions of additives, used in the production of precast reinforced concrete and commercial concrete. A complex additive for concretes and mortars, includes a plasticiser and an amine organic base, with the following ratio (wt %): plasticiser - 70÷90; amine organic base - 10÷30, as the plasticiser it contains polymethylene-naphthalenesulphonate, and as the amine organic base it contains tetra-aza-adamantane or its mixture with hydroxylamine or alkanolamines. The complex additive for the concretes and construction materials can additionally contain auxiliary components of air-entraining, stabilising, and hydrophobising action, regulators of structure-formation kinetics, foam extinguishers, additives of air-removing action or mixtures of the said compounds.

EFFECT: improvement of deformation characteristics of concretes, ie reduction of creep and shrinkage with unchanged preservability and mobility of concrete mixtures, ensuring the stable strength growth.

2 cl, 2 tbl

Concrete mixture // 2525565

FIELD: chemistry.

SUBSTANCE: concrete mixture includes Portland cement, crushed granite, quartz sand, a microfiller, a superplasticiser based on polycarboxylates and water. Additionally into the mixture introduced is TTP fly ash, as the microfiller used is ground limestone MP-1, and as the superplasticiser, based on polycarboxylates MC-RowerFlow 2695, with the following component ratio, wt %: Portland cement 8-10, ground limestone MP-16-8, TPP fly ash 3-6, quartz sand with the coarseness module Mc 1.9 30-40, crushed granite of fraction 3-10 mm 15-18, crushed granite of fraction 5-20 mm 14-16, the superplasticiser based on polycarboxylates MC-RowerFlow 2695 0.0015-0.003, water - the remaining part.

EFFECT: increase of concrete quality due to increased fluidity of the concrete mixture and its self-compaction.

1 tbl

FIELD: construction.

SUBSTANCE: dry building mixture for monolithic-type building construction, which includes Portland cement, alumina cement, hydrated lime, gypsum, quartz sand, filler, re-dispersed polymer, cellulose ester, antifoaming additive, superplasticising agent, hardening agent, retarding agent, contains bauxite cement as alumina cement, hemihydrate plaster as gypsum, quartz sand with fineness modulus of up to 1.2, filler with specific surface area S sp 2.5-2.8 cm2/g, which contains 5-7 wt % of nanoparticles, polycarboxylate superplasticising agent and in addition high-molecular chitosan at the following component ratio, wt %: Portland cement - 12-33, bauxite cement - 12-19, hydrated lime - 0.3-0.5, hemihydrate plaster - 2.5-6, quartz sand with fineness modulus of not more than 1.2 - 30-50, the above filler - 5-18, re-dispersed polymer - 4-6, cellulose ester - 0.1-0.17, antifoaming additive - 0.1-0.3, polycarboxylate superplasticising agent - 0.2-0.3, hardening agent - 0-0.5, retarding agent - 0-3.5, high-molecular chitosan (200-250 kDa) - 1-2 wt % of Portland cement weight.

EFFECT: increasing sedimentation stability of water-based building mixture; improving impact strength and reducing abrasion of hardened mixture.

4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of preparing a hardening accelerator composition by reacting a water-soluble calcium compound with a water-soluble silicate compound and a method of preparing a hardening accelerator composition by reacting a calcium compound with a silicon dioxide-containing component in an alkaline medium, in both cases the reaction of the water-soluble calcium compound with the water-soluble silicate compound being carried out in the presence of an aqueous solution which contains a water-soluble comb polymer suitable as a plasticiser for hydraulic binders. The invention also relates to a composition of calcium silicate hydrate and comb polymer, use thereof as a hardening accelerator and for reducing permeability of hardened mixtures.

EFFECT: obtaining a hardening accelerator having plasticiser properties, which is capable of increasing strength and wear resistance.

41 cl, 12 tbl, 3 dwg

FIELD: chemistry.

SUBSTANCE: claimed invention relates to application as additive, which improves processability of water formulation with hydraulic binging agent base of: a) at least, one (meth)acryl crest-branched copolymer, which has, at least, one side chain, which carries, at least, one alkoxy- or hydroxypolyalkylenglycol hydrophilic group, b) at least, one ASE (alkaline-soluble emulsion) acryl copolymer. Invention also relates to water formulation with hydraulic binding agent base, which contains as additive, which improving its processability: a) at least, one (meth)acryl crest-branched copolymer, which has, at least, one side chain, carrying, at least, one alkoxy- or hydroxypolyalkylenglycol hydrophilic group, b) at least, one ASE - alkaline-soluble emulsion acryl copolymer. Invention is advanced in dependent i.i. of invention formula.

EFFECT: improvement of processability of claimed formulation without manifestation of segregation effect.

22 cl, 10 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to production of construction materials, particularly a fine-grained concrete mixture and a preparation method thereof, and can be used to make concrete structures, both monolithic and assembled, that used in the industry of construction materials and construction. In the method of preparing a fine-grained concrete mixture, which involves pre-modification of the surface of an aggregate, followed by mixing said aggregate with cement and water, the modifier used is alkyldimethylbenzylammonium chloride in amount of 0.1% of the mass of cement, and the aggregate used in ratio of 1:1 is a mixture of quartz sand with fineness modulus of 1.9 and screenings from grinding rocks from the Argun deposit with grain size of 5-10 mm, with the following ratio of components, wt %: cement - 19-25, aggregate - 68-75, water 6-7. The disclosed fine-grained concrete mixture is prepared using said method.

EFFECT: obtaining a fine-grained concrete mixture with improved physical-mechanical and operational properties based on an aggregate made from local material.

1 tbl, 2 cl

FIELD: chemistry.

SUBSTANCE: mixture for gluing tiles is intended for gluing ceramic tiles and plates from natural stone and contains, wt %: Portland cement - 30-34.5, quartz sand - 55-59.5, limestone - 5-7, cellulose ether - 0.20-0.25, copolymer of vinylacetate and vinylversatate - 1.0-1.5, copolymer of melamine sulphoacid and formaldehyde - 0.3-0.5, calcium formate - 1.0-1.2.

EFFECT: improvement of mixture wetting capacity and increase of strength of its cohesion with glued surface on the first day of solidification.

2 tbl

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