Method of producing polyguanidine

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing polyguanidine, having improved biocidal properties. Described is a method of producing polyguanidine via polycondensation of a guanidine salt with a diamine in the presence of an organic acid or a mixture of organic acids and in the presence of an inorganic salt of a transition metal or aluminium, or a mixture thereof with step-by-step heating as follows: gradually raising temperature to 120…130°C and maintaining said temperature for a hour, raising temperature to 150…160°C and maintaining said temperature for 3.5…4 hours and raising temperature to 170…180°C and maintaining said temperature for 1…1.5 hours.

EFFECT: obtained polyguanidines are characterised by low content of monomer residue and high biological activity, owing to which they can be used to purify drinking and waste water and to produce low-toxic, environmentally safe disinfecting, antiseptic and cosmetic agents.

17 cl, 2 tbl, 20 ex

 

The invention relates to polymeric organic chemistry, namely to method of obtaining polyguanidine, and can be used in the preparation of biocidal agents used in medicine, veterinary medicine, for the treatment of drinking and waste waters, in the home, in food industry and in other industries using disinfectants and antiseptics.

Antiseptic and disinfectants on the basis of guanidino compounds are more active, less toxic, more stable and less aggressive than traditional chlorine or aldehydebase drugs. Chlorine means are toxic, cause corrosion of metal objects, destroyed by time, which poses a risk to human health and the environment. Aldehydebase disinfectants, as a rule, highly toxic, affecting the skin and mucosa of man, often cause allergic reactions.

Much attention is paid to the development and improvement of obtaining polyguanidine as an environmentally safe and low-toxic funds with high disinfectant properties.

A method of producing polyguanidine by polycondensation of hexamethylenediamine and melt guanidinopropionic when heated in which to improve the disinfecting properties of the target product�the KTA hexamethylendiamine pre-melt (SU, copyright certificate №1616898, C07C 279/00, A61L 2/16 [1]). The process is conducted at a molar ratio of melts hexamethylendiamine and guanidinopropionic 1:(0,85...to 0.95), respectively, and uniform addition of the obtained melt hexamethylendiamine to melt guanidinopropionic at 180°C for 2.5 hours. Then, the resulting mixture was heated to 240°C and maintained at this temperature for 5 hours.

This method is quite energy intensive, and polyguanidine obtained by this method contains a significant amount of starting monomers, making it toxic and unsuitable for use in some areas, e.g. in drinking water treatment, pharmaceuticals, cosmetics.

A method of producing polyguanidine, including the polycondensation guanidine salts with amines, taken in equimolar ratios, with subsequent purification of the obtained polyguanidine from a mixture of unreacted starting materials. Cleaning is carried out by precipitation or anion exchange using operations bundle (RU, patent No. 2172748, CL C08G 73/00, A61L 2/16, publ. 27.08.2001 [2]). Then the drying and cooling of the resulting product. In the polycondensation as amines using diamines or a mixture thereof with diaminoethane or tertiary amines. The process of polycondensation is carried out at step lifting tempo�atmospheric temperature regime: heating to 120°C and holding at this temperature for 3 hours, temperatures up to 150°C and holding at this temperature for 5 h, then heating to a temperature of 180°C and holding at this temperature for 1 h. In the purification of the obtained crude polycondensate add water until complete dissolution of polycondensate, add salt (sodium chloride or ammonium phosphate) with stratification of the reaction mixture and the formation of a solution of polyguanidine and a saturated solution of salt. Next, a saturated salt solution is removed and polyguanidine, stripped of monomers and lower oligomers, cool.

A method of producing polyguanidine is not enough technological, as it includes the stage of cleaning of polyguanidine, which produces significant amounts of wastewater. This biocidal activity of the obtained polyguanidine not high enough.

The closest is a method of obtaining polyguanidine by polycondensation of guanidine salt with a diamine by heating in the presence of organic acid or mixture of organic acids, which is carried out stepwise heating mode: gradual increase to a temperature of 120...130°C and holding at this temperature for one hour, raising the temperature and holding at the temperature of 150...160°C for 3.5...4 hours, raising the temperature and holding at the temperature of 170...180°C for about 1...1.5 h (UA, patent of�Britanie No. 79720, CL C08G 73/00, C07C 279/00, [3]).

However, the known method does not allow polyguanidine with high reproducibility of their properties. Polyguanidine obtained by a known method, characterized by considerable range of variation as the concentration of residual monomer, and biological activity. It is not possible to vary freely the components to obtain a product with high properties.

In addition, in areas such as potable water, limited to the use of polyguanidine with the concentration of residual monomer is greater than 0.23 wt.% since at high doses of polyguanidine source diamine goes to purify water and is not removed on the following stages of treatment.

The object of the invention is the improvement of the method of obtaining polyguanidine in which due to the conditions of the polycondensation get polyguanidine with consistently high reproducibility of their properties. With the resulting polyguanidine are characterized by high biological activity and low residual monomer content.

The problem is solved by the proposed method of obtaining polyguanidine, in which the polycondensation guanidine salt with the diamine is carried out by stepwise heating in the presence of organic acid or mixture of organic acids, as well as in Pris�accordance inorganic salt of a transition metal or aluminum, or mixtures thereof. Stepwise heating was carried out by the regime: a gradual increase to a temperature of 120...130°C and holding at this temperature for one hour, a further increase in temperature and exposure at a temperature of 150...160°C for 3.5...4 hours, then raising the temperature and holding at the temperature of 170...180°C for about 1...1.5 hours.

Inorganic salt of the transition metal, in the presence of which the polymerization was conducted according to the invention may be selected from the group of salts containing as cations zinc, copper, Nickel, cobalt, chromium or titanium and containing as anion chloride, bromide, iodide, sulfate or nitrate.

The amount of inorganic salt of the transition metal, or aluminum, or mixtures thereof, in the presence of conducting the polycondensation, is 0.01...16, preferably 0,05...1,0 wt%.% by weight of the reaction mixture. While inorganic salt of the transition metal is introduced into the reaction mixture before or at the first stage of step heating.

To obtain polyguanidine use a diamine of the General formula (I):

Where R1- (CH2)n, (CH2)p-O-(CH2)q-O-(CH2)r, (CH2)p-O-(CH2)q-O-(CH2)r-O-(CH2)s, where n=2...6, p=2...6, q=2...6, r=2...6 and s=2...6,

or a mixture thereof.

As deeminnomegus to be used hexamethylendiamine, octamethylene, dioxadodecane-1,12-diamine, trioxatridecane-1,13-diamine, 3,6-diamino-1,8-diaminooctane.

As a guanidine salt using salt with organic or inorganic acids.

When carrying out the polycondensation, the ratio of the guanidine salt and a diamine is(0,8...1,2):(1,2...0,8) respectively.

Mainly, as the organic salt use guanidine guanidine acetate, guanidine citrate or dehydroacetate guanidine, and salts of inorganic acid is used guanidine chloride, guanidine sulfate, guanidine carbonate and guanidine nitrate.

Obtaining polyguanidine by polycondensation of guanidine salt with the diamine is carried out in the presence of organic acid which is selected from the group:

monocarboxylic acid of the General formula (II)

where R2- C9N19...C18N37-alkyl, C9N17...C18N35-alkenyl, C6H5, C5H4N C5H4CH3, C5H4NH2, C5H4OH, C5H4OCOCH3;

dicarboxylic acid of the General formula (III)

where R3- (CH2)n, CmH2m-1NH2, (CHOH)m, CkH2k-2With6N5, where n=0...8, m=1...4, k=2...6;

tricarboxylic acid of the General formula (IV)

where R4- CnH2n-1-m(OH), where n=3...5, m=0...1.

As specified organic acid as the monocarboxylic acid is preferably used dekanovu, metandienone, itondekanya, preponderanoa, butandione, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecane, degenova, metandienone, atendimento, propantelinom, balancenew, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonindigenous, benzoic, ortho-, meta-, para-Truelove, ortho-, meta-, para-aminobenzoic, ortho-, meta-, para-oxybenzoyl, ortho-, meta-, para-acetyloxybenzoic, pyridylcarbonyl acid or mixtures thereof.

As specified organic acid as dicarboxylic acid is preferably used in identicality, propandiol, butanedioate, intangibility, hexadecanoate, heptanedionato, octadecanoate, noninducibility, decodecolor, α-aminopropanol, α-aminosalicylate, α-aminophenylacetate, α-aminohexanoate, α,β-dioxymethylene, α,β,γ,ω-tetraoxygenated, butandikislota, intangibility, lexingtonlaw, heptanedionato, attendability, 1,2-compounds are benzene dicarboxylic, 1,3-compounds are benzene dicarboxylic, 1,4-compounds are benzene dicarboxylic acid, or mixtures thereof.

As specified tricarboxylic'or�anceschi acid is used, for example, 2-hydroxy-1,2,3-propanetricarboxylate acid, or 3-hydroxy-1,3,5-pentatriacontane acid, or a mixture thereof.

The amount of organic acid or mixture of organic acids, in the presence of which carry out the polycondensation, is 0.01...16, preferably 0,05...1,0% by weight of the reaction mixture. Thus in the reaction mixture an organic acid or a mixture of organic acids is administered before or at the first stage of step heating.

The method is as follows.

The guanidine salt and a diamine in a molar ratio of(0,8...1,2):(1,2...0,8) respectively transferred into a container containing a stirrer, thermometer and return to the refrigerator.

Suitable components of the reaction mixture are diamines such as, for example: hexamethylendiamine, octamethylene, dioxadodecane-1,12-diamine, trioxatridecane-1,13-diamine, 3,3'-ethylendiaminetetraacetic, such salts of inorganic acids, guanidine, guanidine chloride, guanidine sulfate, guanidine carbonate and guanidine nitrate, or salts of organic acids, guanidine, guanidine acetate, guanidine citrate or dehydroacetate guanidine.

The polycondensation reaction of the reaction mixture: guanidine salt and a diamine is carried out in the presence of catalysts: organic acids, or mixtures thereof, and in the presence of an inorganic salt of the transition meth�lia, or inorganic salt of aluminum, or mixtures thereof. To do this, in the obtained reaction mixture was added to these catalysts: organic acid (or a mixture of organic acids) and inorganic salt of a transition metal or an inorganic salt of aluminum (or mixtures thereof). In this organic acid or organic acid is added in an amount of from 0.01 to 16%, preferably from 0.05 to 1.0% by weight of the reaction mixture, and an inorganic salt of a transition metal, or an inorganic salt of aluminum, or mixtures thereof are added in an amount of from 0.01 to 16%, preferably 0,05...1,0% by weight of the reaction mixture.

These catalysts are introduced into the mixture of guanidine salt and a diamine prior to heating. Next up is carried out stepwise heating with stirring for mode: gradual increase to a temperature of 120...130°C and holding at this temperature for one hour, raising the temperature and holding at the temperature of 150...160°C for 3.5...4 hours, raising the temperature and holding at the temperature of 170...180°C.

According to another embodiment of the invention, these catalysts are added to the reaction mixture in the first stage of step heating. In this case the reaction mixture of guanidine salt and a diamine is gradually heated to a temperature of 120...130°C, maintained at this temperature and in the process raise the temperature of or extracts from the�tion is added to the organic acid or the mixture of organic acid and inorganic salt of the transition metal, or aluminium or a mixture thereof in the amounts indicated.

Inorganic salt, in the presence of conducting the polycondensation reaction mixture, the cation may contain zinc, copper, Nickel, cobalt, chromium or titanium, and as an anion may contain chloride, bromide, iodide, sulfate or nitrate. Suitable inorganic salts as catalysts are, for example: aluminum chloride (AlCl3,), titanium sulfate (Ti(SO4)2), zinc bromide (ZnBr2), copper sulfate (CuSO4), Nickel nitrate (Ni(NO3)2), chromium iodide (Crl3) and etc.

Organic acid, in the presence of conducting the polycondensation may be monocarboxylic, dicarboxylic or tricarboxylic.

Suitable monocarboxylic acids are, for example: dukanova, metandienone, amandikova, preponderancy, botanbekova, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecane, degenova, metandienone, amandikova, preponderanoa, botanbekova, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonaddictive, benzoic, ortho-, meta-, para-tolarova, ortho-, meta-, para-aminobenzoic, ortho-, meta-, para-oxybenzone, ortho-, meta-, para-acetyloxybenzoic, piridinkarbonovaya.

Suitable dicarboxylic acids are, for example: this�dikelola, perpendiculat, butanedioate, intangibility, hexadecanoate, heptanedionato, octadecanoate, nonantibiotic, decodecolor, α-aminopropanol, α-aminosalicylate, α-aminophenylacetate, α-aminohexanoate, α,β-dioxymethylene, α,β,γ,ω-tetraoxygenated, butandikislota, intangibility, hexadecanoate, heptanedionato, octadecanoate, 1,2-compounds are benzene dicarboxylic, 1,3-compounds are benzene dicarboxylic, 1,4-compounds are benzene dicarboxylic acid.

Suitable tricarboxylic acids are, for example: 2-hydroxy-1,2,3-propanetricarboxylate acid or 3-hydroxy-1,3,5-pentatriacontane acid.

Below are examples showing a possible implementation of the invention, but not limiting it.

Example 1.

Guanidinopropionic and hexamethylenediamine in a molar ratio of 1:1 is transferred to a container containing a stirrer, thermometer and return to the fridge, and mix. To the resulting reaction mixture was added 0.01% of its weight of citric acid and 0.01 wt%. aluminum chloride (table 1, example 1). The heating of the reaction mixture is carried out in a water bath, with stirring, for mode: gradual increase to a temperature of 120...130°C and holding at this temperature for one hour, raising the temperature and holding at the temperature of 150...160°C for 3.5 hours, the temperature rise and exposure at a temperature of 180°C � for 1.5 hours.

The result is a polymer product, polyguanidine, in the form of a transparent glassy mass, light yellow-green color. Received polyguanidine characterized by the following properties (table 2, example 1):

the viscosity of 0.14 DL/g,

the concentration of the monomer residue of hexamethylendiamine is 0.07 wt.%,

biological activity:

The test-cultureMICK, mg/l×10-2(minimum inhibitory concentration)MBC, mg/l×10-2(minimum bactericidal concentration)
Staf Aureus0,0950,095
Candida Alb.0,050,05
E. Coli0,030,03

Similarly were obtained by other polyguanidine claimed method. Information about the source components and the conditions of the polycondensation is presented in Table 1.

Properties of the obtained polyguanidine presented in Table 2. Polyguanidine was obtained as a glassy transparent or light yellow-green mass. The viscosity of the obtained polyguanidine is within 0,11 0,17..., concentration �of STATCOM monomer hexamethylendiamine - 0,03 0,11...wt%. The resulting polyguanidine characterized by a low content of residual monomers and high biological activity. Thanks to that obtained polyguanidine with high efficiency are used for wastewater treatment, obtaining disinfectants, obtain antiseptic and receipt of cosmetics.

Known
Table 1
No. exampleThe reaction mixtureOrganic acidInorganic saltThe heating in the polycondensation
salt guanidinethe diaminerationamenumber % wt. from the reaction mixtureformulanumber % wt. from the reaction mixturefirst degreesecond degreethe third degree
temperature, °Cexposure, htemperature, °Cexposure, htemperature, °Cexposure, h
Proposed
1guanidinopropionichexamethylendiamine1:1lemon0,01AlCl30,01120-1301150-1603,51801,5
2guanidinopropionichexamethylendiamine1:1lemon0,05AlCl30,05120-1301150-1603,51801,5
3guanidinopropionic hexamethylendiamine1:1lemon0,23AlCl30,23120-1301150-1603,51801,5
4guanidinopropionichexamethylendiamine1:1lemon1AlCl311251150-1603,5170-1801,5
5guanidinopropionichexamethylendiamine1:1lemon5AlCl351251150-1603,5170-1801,5
6guanidinopropionichexamethylendiamine1:1lemon10AlCl3101251150-1603,5170-1801,5
7guanidinopropionichexamethylendiamine1:1lemon16AlCl3161251150-1603,5170-1801,5
8guanidinopropionichexamethylendiamine1:1salicylic0,01Ti(SO4)20,01120-1301150-160 41800,5
9guanidinopropionichexamethylendiamine1:1salicylic0,1Ti(SO4)20,1120-1301150-16041800,5
10guanidinopropionichexamethylendiamine1:1salicylic1Ti(SO4)21120-1301150-1604170-1800,5
11guanidinopropionichexamethylendiamine1:1oxalic0,01ZnBr20,01 120-1301150-1603,51801
12guanidinopropionichexamethylendiamine1:1oxalic0,5ZnBr20,5120-1301150-1603,51801
13guanidinopropionichexamethylendiamine1:1oxalic1ZnBr21120-1301150-1603,5170-1801
14guanidinoacetatehexamethylendiamine, octamethylene1:075:0,25palmitic 0,27CuSO40,27120-1301150-16041801,5
15guanidinoacetatedioxadodecane-1-12-diamnd1:1maleic0,9CoSO40,9120-1301150-1603,51801,5
16guanidinopropionichexamethylendiamine0,8:1,2isophthalic0,7Ni(NO3)20,7120-1301150-1603,51801,5
17guanidinopropionicGE�sameyandej 1:1isophthalic0,7Ni(NO3)20,7120-1301150-1603,51801,5
18guanidinopropionichexamethylendiamine1,2:0,8isophthalic0,7Ni(NO3)20,7120-1301150-1603,51801,5
19guanidinopropionichexamethylendiamine1:1citric, oxalic0,5CrI30,5120-1301150-1603,51801
guanidinopropionichexamethylendiamine1:1lemon0,0512511553,5170-1801,5

Table 2
No. exampleThe total time of synthesis, hThe concentration of monomer residue, % wt.Viscosity, DL/gThe biological activity, the test-culture
Staf AiireusCandida AlbicansE. Coli
MICK*, mg/l×102MBK**, mg/l×102MICK, mg/l×102MBC, mg/l×102MICK, mg/l×102MBC, mg/l×102
Example 160,070,140,0950,0950,050,050,030,03
Example 260,030,170,0050,0950,030,050,010,02
Example 360,090,130,0950,190,050,050,020,03
Example 460,080,120,190,190,050,050,050,05
Example 560,08/td> 0,120,190,190,050,080,040,05
Example 660,090,130,190,190,050,080,080,08
Example 760,100,120,190,190,050,080,080,08
Example 85,50,080,130,0480,0950,050,070,030,06
Example 95,50,060,150,030,095 0,030,080,030,03
Example 105,50,090,120,190,190,080,080,040,08
Example 115,50,060,150,190,190,080,080,040,04
Example 125,50,050,160,0950,0950,030,080,030,05
Example 135,50,070,120,0480,190,0950,0950,04 0,04
Example 146,50,100,120,190,190,0950,0950,030,04
Example 1560,090,130,190,190,0950,0950,030,04
Example 1660,100,120,0950,190,050,0950,020,04
Example 1760,050,160,0480,0950,050,050,020,04
Example 1860,120,0950,190,050,0950,020,06
Example 195,50,100,130,190,190,080,080,030,06
Known60,110,110,380,380,0950,095
* Minimum inhibitory concentration.
** The minimum bactericidal concentration.

1. Method of obtaining polyguanidine by polycondensation of guanidine salt with a diamine by heating in the presence of organic acid or mixture of organic acids, and is carried out stepwise heating mode: gradual increase to a temperature of 120...130°C and holding at this temperature � for one hour, increasing the temperature and holding at the temperature of 150...160°C for 3.5...4 hours, raising the temperature and holding at the temperature of 170...180°C for about 1...1.5 h, characterized in that the polycondensation is carried out in the presence of an inorganic salt of a transition metal or aluminum, or mixtures thereof.

2. A method according to claim 1, characterized in that the inorganic salt of the transition metal, in the presence of conducting the polycondensation, selected from the group, the cation of which is zinc, copper(II), Nickel, cobalt, chromium(III) or titanium(IV).

3. A method according to claim 1, characterized in that the inorganic salt of the transition metal, in the presence of conducting the polycondensation, selected from the group, the anion is chloride, bromide, iodide, sulfate, nitrate.

4. A method according to claim 1, characterized in that the amount of inorganic salt of the transition metal, or aluminum, or mixtures thereof, in the presence of conducting the polycondensation, is 0.01...16% by weight of the reaction mixture, preferably 0,05...1,0 wt%.

5. A method according to claim 1, characterized in that the inorganic salt of the transition metal, or aluminum, or mixtures thereof is introduced into the reaction mixture before or at the first stage of step heating.

6. A method according to claim 1, characterized in that a diamine of the General formula (I)
NH2-R1-NH2(I)
where R1-(CH2)n(CH 2)p-O-(CH2)q-O-(CH2)r, (CH2)p-O-(CH2)q-O-(CH2)r-O-(CH2)s, where n=2...6, p=2...6, q=2...6, r=2...6 and s=2...6,
or a mixture thereof.

7. A method according to claim 6, characterized in that the diamine used hexamethylendiamine, octamethylene, dioxadodecane-1,12-diamine, trioxatridecane-1,13-diamine, 3,3'-ethylendiaminetetraacetic.

8. A method according to claim 1, characterized in that the guanidine salt is used as salt of an organic or inorganic acid.

9. A method according to claim 8, characterized in that as the organic salt use guanidine guanidine acetate, guanidine citrate or dehydroacetate guanidine.

10. A method according to claim 1, characterized in that as inorganic salts use guanidine chloride, guanidine, guanidine sulfate, guanidine carbonate and guanidine nitrate.

11. A method according to claim 1, characterized in that the organic acid, in the presence of which the reaction of the polycondensation, selected from the group:
monocarboxylic acid of the General formula (II)
R2-COOH (II)
where R2-C9N19...C18N37-alkyl, C9N17...C18N35-alkenyl, C6H5, C5H4N, S5N4CH3, C5H4NH2, C5H4OH, S5N4OSON3;
dicarboxylic acid about�her formula (III)
HOOC-R3-COOH (III)
where R3-(CH2)n, CmH2m-1NH2, (CHOH)m, CkH2k-2, C6H5, where n=0...8, m=1...4, k=2...6;
tricarboxylic acid of the General formula (IV)
R4(COOH)3(IV)
where R4-CnH2n-1-m(OH), where n=3...5, m=0...1.

12. A method according to claim 11, characterized in that the monocarboxylic acid is selected from the group: dukanova, metandienone, amandikova, preponderancy, botanbekova, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecane, degenova, metandienone, amandikova, preponderanoa, botanbekova, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonaddictive, benzoic, ortho-, meta-, para-tolarova, ortho-, meta-, para-aminobenzoic, ortho-, meta-, para-oxybenzone, ortho-, meta-, para-acetyloxybenzoic, piridinkarbonovaya, or a mixture thereof.

13. A method according to claim 11, characterized in that the dicarboxylic acid is selected from the group: ethicality, perpendiculat, butanedioate, intangibility, hexadecanoate, heptanedionato, octadecanoate, nonantibiotic, decodecolor, α-aminopropanol, α-aminosalicylate, α-aminophenylacetate, α-aminohexanoate, α,β-dioxymethylene, α,β,γ,ω-tetraoxygenated, butandikislota, penangites�OTA, hexadecanoate, heptanedionato, octadecanoate, 1,2-compounds are benzene dicarboxylic, 1,3-compounds are benzene dicarboxylic, 1,4-compounds are benzene dicarboxylic acid, or a mixture thereof.

14. A method according to claim 11, characterized in that 2-hydroxy-1,2,3-propanetricarboxylate acid, or 3-hydroxy-1,3,5-pentatriacontane acid, or a mixture thereof.

15. A method according to claim 1, characterized in that the amount of organic acid or mixture of organic acids, in the presence of which carry out the polycondensation, is 0.01...16% by weight of the reaction mixture, preferably 0,05...1,0 wt%.

16. A method according to claim 1, characterized in that the organic acid or a mixture thereof is introduced into the reaction mixture before or at the first stage of step heating.

17. A method according to claim 1, characterized in that the polycondensation is carried out at a ratio of guanidine salt and a diamine, equal(0,8...1,2):(1,2...0,8) respectively.



 

Same patents:

FIELD: metallurgy.

SUBSTANCE: invention refers to composition for electrolytic metal deposition, application of polyalkanolamine or its derivatives, and method of metal layer deposition. Composition for electrolytic metal deposition includes metal ion source and at least one leveller. Copper ions are used as metal ions. Leveller is polyalkanolamine or its derivatives obtained by alkoxylation, substitution, or alkoxylation and substitution of polyalkanolamine. Polyalkanolamine is obtained by condensation of at least one trialkanolamine of a general formula N(R1-OH)3 (la) and/or at least one dialkanolamine of a general formula R2-N(R1-OH)2 (lb), where R1 radical is selected separately out of bivalent linear or bifurcated aliphatic hydrocarbon radical with 2 to 6 carbon atoms, R2 radical is selected out of hydrogen, linear or bifurcated aliphatic, cycloaliphatic and aromatic hydrocarbon radicals with 1 to 30 carbon atoms. Polyalkanolamine or its derivatives are used in solution for electrolytic metal deposition. Method of metal layer deposition on a substrate involves application of solution for electrolytic metal deposition, containing the composition described above, on a substrate in advance. Then current of definite density is connected to the substrate for time period sufficient for metal layer deposition.

EFFECT: obtainment of leveller with good levelling properties, obtainment of flat metal layer with level surface by flaw-free filling with nano-sized and micro-sized elements.

15 cl, 6 dwg, 1 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: group of inventions relates to adhesive composition and method of its obtaining, to polyamidoamine-epihalogenhydrin resin (PAE), as well as to method of obtaining composite material based on wood, laminate, plywood, chipboard, fibreboard. Method on obtaining adhesive composition includes combination of PAE with protein source. Adhesive composition possesses content of solid substances exceeding 45 wt % counted per the total glue weight. The total content of solid substances in PAE resin and protein source constitutes not less than 45% of the total content of solid substances in glue. PAE resin possesses content of solid substances, exceeding 40% and is characterised by Brookfield viscosity, measured by means of Brookfield LV viscometer, equal less than 200 cP, content of azetidine groups equal more than 0.75 meq./g, RSV value, equal lower than 0.3 dl/g, stability in ageing, exceeding one week at 32°C. Method of composite material obtaining includes addition of adhesive composition to suitable substrate.

EFFECT: invention makes it possible to considerably increase content of solid substances in glue and characteristics of composite material.

28 cl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to drilling mud emulsifiers. Disclosed is a polyamide compound of formula (A), where a is an integer from 1 to 5, b and c are each independently selected from integers from 0 to 10, under the condition that b and c are not equal to 0 at the same time, d is an integer from 0 to 10, e is an integer from 1 to 5, Y is selected from H, X, -C(O)R1 or -C(O)R2 and Z is selected from -C(O)R1 or X, where R1 and R2 are linear or branched, saturated or unsaturated hydrocarbyl groups having 7 to 30 carbon atoms, and X is a carbonyl group obtained from a carboxylic acid. The invention also discloses a method of producing said compound, use thereof as an emulsifier in drilling mud and the respective drilling mud composition.

EFFECT: disclosed compound is an effective emulsifier at high temperature and pressure, which reduces the required amount of the emulsifier and the cost of the system; Y{O(CH2)e}a{NX(CH2)e}b{N[C(O)R2](CH2)e}c{NH(CH2)e}d NHZ (A).

15 cl, 2 dwg, 6 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: described are compositions for hair care, containing a β-aminoether compound in a cosmetically acceptable carrier, such as a spray or cream. Described is a compound of formula

:

in which n represents an integer number from 1 to 100; Z and Z′ together with atoms, which they are bound to, represent acrylate, methacrylate or amino-terminal groups; R2 represents C1-C20alkyl, possibly substituted with: hydroxyl, siloxyl, C1-C20alkoxygroup, substituted with hydroxyl, amino-C1-C20alkyl, substituted with from one to two hydroxyl groups, C6-C10aryl, substituted with C1-C20alkoxygroup, or C5-C10heteroaryl, containing one nitrogen heteroatom; and A contains a rubber fragment, which has a molecular weight in the range from approximately 1000 g/mol to approximately 10000 g/mol, selected from the group, consisting of butadiene and isoprene units. Also described is a cosmetic composition for hair, containing the said compound and cosmetically acceptable carrier. The application of the said cosmetic composition for scalp care is described.

EFFECT: obtaining the cosmetic composition for hair, increasing adhesion of hairs to each other, adding volume, texture and shape to the hair.

10 cl, 4 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an electrochemical method for synthesis of metal-doped polyaniline, which involves preparation of a solution with the following concentration of components: sulphuric acid 0.5-1.5 mol/dm3, aniline 0.1-0.4 mol/dm3, transition metal salts 0.1-1.0 mol/dm3; conducting electrolysis at temperature of 10-30°C using a working electrode and an auxiliary electrode, wherein the solution preparation step involves further addition of 0.1-0.5 mol/dm3 aminoacetic acid or 0.1-0.5 mol/dm3 disodium salt of ethylenediaminetetraacetic acid; the transition metal salts used are transition metal sulphates; the working electrode and auxiliary electrode used are stainless steel electrodes; electrolysis is carried out with constant current density of 1-10 mA/cm2, and after the electrolysis step, the obtained metal-doped polyaniline is treated with an alkaline solution at pH 8-10.

EFFECT: electrochemical method for synthesis of metal-doped polyaniline is cheap owing to use of stainless steel electrodes, and the obtained metal-doped polyaniline has high passivating capacity.

1 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: method of producing polyphenyl polyamines comprises steps of producing an aqueous stream containing polyphenyl polyamines and removing the polyphenyl polyamines from the aqueous stream. The method of removing polyphenyl polyamines involves preparing pertraction equipment, having a membrane which has a first side and a second side opposite the first side. The membrane is then soaked with a liquid characterised by surface tension of less than 40 mN/m. Further, the aqueous stream containing polyphenyl polyamines linked by bridge methylene groups is brought into contact with the first side fo the membrane and the second side of the membrane is brought into contact with an organic stream. During this process, there is transfer of polyphenyl polyamines from the aqueous stream through the membrane into the organic stream.

EFFECT: invention reduces the number of steps of the method, makes the extraction step more robust when operating in varying process conditions.

14 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to use of alkoxylated polyalkanolamines to demulsify oil-in-water emulsions, primarily oil emulsions. Alkoxylated polyalkanolamines are obtained (A) by condensing at least one trialkanolamine to a polyalkanolamine, the obtained polyalkanolamine having number-average molecular weight from 1000 to 20000 g/mol, and (B) alkoxylating the obtained polyalkanolamine with ethylene oxide and propylene oxide. The formed polyoxyalkylene groups have a block structure of general formula: -(CH2CH2O)x(CH2CH(CH3)O)yH, in which x and y denote a number from 3 to 100, respectively, and the ratio y/x is greater than 1.

EFFECT: disclosed demulsifiers are suitable for faster and complete phase separation of oil-in-water emulsions, primarily oil emulsions.

11 cl, 2 tbl, 8 ex

FIELD: oil and gas industry.

SUBSTANCE: method for extraction of oil from carbonate formations involves dilution in water or salt solution (in quantity of 0.01-20%) of quarternary polyamines of the specified formula, where n≥1; R1 represents H, CH3, CH2CH3, CnH2n+1; R2 represents H2CHOHCH2, CH2, CH2CH=CH2, R3 represents CH3, CH2CH3, CnH2n+1; R4 represents CH2, CH2CH=CH3; and if R2 and R4 represent allyl groups, then altogether they can form aliphatic cyclic structures; ratio between atoms of carbon and nitrogen (C/N) is at the interval of 2 to 30, and further introduction to the well.

EFFECT: increasing oil extraction degree.

15 cl, 30 ex, 4 tbl, 5 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to polyamines and methods of using said polyamines for scale treatment in different industrial process streams. Disclosed are hydrophobically modified silicon-containing polyamines, containing repeating structural links of two types, a composition based thereon and a method of reducing or eliminating scales in an industrial process, involving addition of the disclosed polymer or composition into a process stream.

EFFECT: disclosed hydrophobically modified silicon-containing polyamines are suitable for aluminosilicate scale treatment in hard-to-clean industrial process streams, such as process streams in a Bayer method of extracting alumina from bauxite, streams of radioactive wastes and effluent streams formed during production of kraft paper.

30 cl, 9 tbl, 156 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to biodegradable polymers suitable for delivery of biological agents to cells. Proposed is a polymer containing a link with formula (I) where PEI is a link of polyethylenimine with molecular weight less than 600 Daltons; R is a pair of electrons; L is selected from among C2-C50 carboxialkenyl and residues of fatty acid from C12 to C18; m is an integer from 1 to 30. Additionally proposed is a polymer complex with an oligonucleotide and a method for eukaryote cells transfection using such complex.

EFFECT: proposed polymer is applicable for safe and effective delivery of a small interfering RNA or oligonucleotides to the cell.

16 cl, 2 dwg, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to a method of obtaining polyketoximes. Described is the method of obtaining polyketoximes by the interaction of aliphatic polyketone of an alternating structure, obtained by the catalytic copolymerisation of carbon oxide and olefin or a mixture of olefins in the suspension mode with a reagent - a source of hydroxylamine, characterised by the fact that as the solvent used is a highly polar aprotic organic solvent or its mixture with water, with the process being carried out with polyketone, which has a molecular weight from 1000 to 700000 g/mol, the polyketone is introduced into the reaction basing on the weight ratio polyketone:solvent in the interval 1:1-10, the time of the reaction is 1-2 hours, with hydroxylamine hydrochloride, processed with sodium hydroxide, being used as a source of hydroxylamine.

EFFECT: increased range of molecular weights of applied polyketones, reduction of the weight ratio of the polyketone to the solvent, reduction of the synthesis duration.

2 cl, 1 dwg, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to a method of obtaining polycyanurate by polycyclotrimerisation of a dicyanate monomer or oligomer in the presence of a polyhedral oligomer silsesquioxane (POSS), in the presence of a catalyst by mixing at a higher temperature, placement of the obtained suspension into a metal mould, processed with an antiadhesion composition, first, with its cooling to 35°C and further heating from 35 to 320°C for 5 hours, with a cyanate monomer (oligomer) being mixed with 0.025-0.100 wt % of polyhedral oligomer silsesquioxane, containing cycloaliphatic epoxy-groups, and intensive mixing of the obtained suspension at a temperature of 170°C for 2 hours to realise chemical grafting between the components with further cooling and heating.

EFFECT: provision of more effective POSS dispersion in the polymer and an increased value of the elasticity modulus, vitrification temperature, creep onset temperature and temperature of the obtained material destruction.

1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to grafted polymer, imitating adhesive protein of mussel, to method of obtaining grafted polymer, to nanoparticles dispersed in water medium, colloid solution and contrast agent. Grafted polymer represents polyethyleneimine, grafted with polyethyleneglycol and polydihydroxyphenylalanine (PEI-graft-(PEG; PDOPA)). Polydihydroxyphenylalanine represents condensation polymer of 3,4-dihydroxyphenylalanine (DOPA). Method of obtaining grafted polymer includes several stages. At the first stage grafted copolymerisation of polyethyeleneglycol with polyethyleneamine is carried out. At the second stage after protection of hydroxyl groups of 3,4-dihydroxyphenylalanine synthesis of N-carboxyanhydride of 3,4-dihydroxyphenylalanine is performed in presence of triphosgene as catalyst. After that, reaction of polymer, obtained at the first stage, and N-carboxyanhydride of 3,4-dihydroxyphenylalanine in organic solvent is carried out. Colloid solution contains nanoparticles dispersed in water medium, with said grafted polymer being used as dispersion stabiliser. Contrast agent for magnetic-resonance tomography (MRT) includes said colloid solution.

EFFECT: invention makes it possible to obtain biocompatible stabiliser, providing stable dispersion of nanoparticles in water medium, as well as to obtain highly effective nanoparticles as contrast agent for MRT.

25 cl, 8 dwg, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: described is a method of obtaining polyphenylene ether ketone oxymate, consisting in the interaction of dioxymate anions of 4,4'-diacetyldiphenyloxide with 4,4'-dihalogenbenzophenone at higher temperatures in the aprotonic dipolar solvent dimethylsulphoxide, characterised by the fact that the synthesis of polyphenylene ether ketone oxymate is carried out in two stages: at the first stage with the reaction of potassium dioxymate of 4,4'-diacetyldiphenyloxide with 4,4'-dichlorobenzophenone with a molar ratio of 1:0.5 and the concentration of a solution C=1 mol/l in terms of dioxymate for 1 hour at a temperature of 165°C in the presence of a solid powder-like KOH obtained is a dioxymate anion of the following structure -O-N=C(CH3)-C6H4-O-C6H4-C(CH3)=N-O-C6H4-CO-C6H4-O-N=C(CH3)-C6H4-O-C6H4-C(CH3)=N-O-, at the second terminating stage of the process a mixture of 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone and crushed and annealed K2CO3 in molar ratios of 0.5:0.005:0.15, counted per 1 mol of the initial diketoxime of 4,4'-diacetyldiphenyloxide, in a water-free DMSO, with an additional volume of the water-free DMSO being taken in such an amount that the concentration of the solution by each of the monomers at the second oligopolymer stage of the synthesis becomes equal to 0.5 mol/l, the total time of carrying out the reaction is 6 hours at a temperature of 165°C.

EFFECT: intensification, optimisation and cheapening of the process of obtaining polyphenylene ether ketone oxymate.

3 ex

FIELD: chemistry.

SUBSTANCE: group of inventions relates to cyanate ester-based polymer compositions which are modified with polysulphones, reinforced with fibrous filler and are used for producing structural polymer composite materials with operating temperature of up to 200°C and articles from said materials, which can be used in aviation, aerospace, motorcar, ship-building and other industries. Disclosed is a cyanate ester-based polymer composition for polymer composite materials, which comprises a thermoplastic modifier and a curing agent, wherein the modifier used is a thermoplastic selected from polysulphone, polyestersulphone, polyarylsulphone or mixtures thereof, and the curing agent used is an amine catalyst. The invention also discloses a prepreg which includes said polymer composition and fibrous filler, and an article made from said prepreg by moulding.

EFFECT: producing a thermoplastic-modified cyanate ester-based polymer composition which is characterised by homogeneity of the composition, which enables prepreg processing thereof and enables to obtain moisture-proof articles from polymer composite materials made therefrom, with improved thermomechanical properties, a coefficient of variation of physical and mechanical properties and good retention of strength properties at high temperatures.

7 cl, 12 dwg, 3 tbl

FIELD: chemistry.

SUBSTANCE: described are compositions for hair care, containing a β-aminoether compound in a cosmetically acceptable carrier, such as a spray or cream. Described is a compound of formula

:

in which n represents an integer number from 1 to 100; Z and Z′ together with atoms, which they are bound to, represent acrylate, methacrylate or amino-terminal groups; R2 represents C1-C20alkyl, possibly substituted with: hydroxyl, siloxyl, C1-C20alkoxygroup, substituted with hydroxyl, amino-C1-C20alkyl, substituted with from one to two hydroxyl groups, C6-C10aryl, substituted with C1-C20alkoxygroup, or C5-C10heteroaryl, containing one nitrogen heteroatom; and A contains a rubber fragment, which has a molecular weight in the range from approximately 1000 g/mol to approximately 10000 g/mol, selected from the group, consisting of butadiene and isoprene units. Also described is a cosmetic composition for hair, containing the said compound and cosmetically acceptable carrier. The application of the said cosmetic composition for scalp care is described.

EFFECT: obtaining the cosmetic composition for hair, increasing adhesion of hairs to each other, adding volume, texture and shape to the hair.

10 cl, 4 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: invention relates to compositions, containing an active substance. Described is a composition for the active substance delivery, which contains: a) at least, one block-copolymer, containing, at least, one poly(2-oxazoline) block A, consisting of repeating units of formula where RA stands for a hydrocarbon group, which can be optionally substituted with -OH, -SH, -COOH, -NR'2, -COOR', -CONR', -CHO, where R' stands for H or C1-3 alkyl, and RA is selected in such a way that a repeating link of formula (I) is hydrophilic; and at least one poly(2-oxazoline) block B, consisting of repeating units of formula (II), where RB stands for a hydrocarbon group, which can be optionally substituted with halogen, -OH, -SH, -COOH, -NR''2, -COOR'', -CONR'', -CHO, where R'' stands for H, alkyl or alkenyl, and RB is selected in such a way that a repeating link of formula is more hydrophobic than the repeating link of formula (I); and (b) one or more active substances. Also described is application of a copolymer for solubilisation of the active substance in water or a water solution.

EFFECT: described copolymers serve as a universal medication delivery system with high loading.

12 cl, 6 dwg

FIELD: chemistry.

SUBSTANCE: described is a method of producing a highly purified disinfectant which contains polyhexamethylene guanidine hydrochloride, characterised by that flush water from production of polyhexamethylene guanidine hydrochloride in solid form is used. The flush water is mixed with 25% NaCl solution in ratio of 1:1 (polyhexamethylene guanidine hydrochloride solution with impurities: NaCl solution) while stirring constantly for 1 hour at temperature in the range of 50-60°C. Stirring is stopped and the mixture is cooled to 5°C, thereby dividing the mixture into two parts; the bottom part is drained, neutralised and sent for recycling and the top part containing up to 60-70% polyhexamethylene guanidine hydrochloride is further diluted to 50% with an aqueous solution of quaternary ammonium salts (QAS) to QAS concentration of not higher than 5%.

EFFECT: extracting highly purified, concentrated high-molecular weight polyhexamethylene guanidine hydrochloride from flush water, reducing the amount and toxicity of waste water, improving disinfecting properties and increasing output of the commercial-grade product when producing polyhexamethylene guanidine hydrochloride in solid form, reducing cost.

1 cl, 1 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: method of producing a disinfectant involves first carrying out polycondensation of hexamethylenediamine and guanidine hydrochloride. Polycondensation starts with preparation of a reaction mass in form of a suspension of crystalline guanidine hydrochloride in molten hexamethylenediamine, taken in ratio of 1:(1-1.5). The suspension is obtained by gradually adding crystalline guanidine hydrochloride, preheated to temperature of 90-120°C, to molten hexamethylenediamine and then stirring. The reaction mass is then heated in steps: holding for 4 hours at 120°C, then for 8 hours at 160°C and then for 3 hours at 180°C. Temperature is then gradually raised to 210°C at a rate of 3-4°C/h. The reaction mass is then subjected to vacuum treatment and cooled.

EFFECT: method enables to reduce toxicity of the end product and obtain a polymer with the required molecular weight and sufficient purity without washing steps.

2 tbl

FIELD: chemistry.

SUBSTANCE: described is a method of producing polyguanidines by polycondensation of a guanidine salt with a diamine while heating, characterised by that polycondensation is carried out in the presence of an organic acid or a mixture of organic acids and heating is carried out in steps as follows: at the first step at 120-130°C for 0.5-1 hour; at the second step at 150-160°C for 3.5-4 hours; at the third step at 170-180°C for 0.5-1.5 hours.

EFFECT: improved method.

11 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: described is a method of producing polyguanidines by polycondensation of a guanidine salt with a diamine while heating, characterised by that polycondensation is carried out in the presence of an organic acid or a mixture of organic acids and heating is carried out in steps as follows: at the first step at 120-130°C for 0.5-1 hour; at the second step at 150-160°C for 3.5-4 hours; at the third step at 170-180°C for 0.5-1.5 hours.

EFFECT: improved method.

11 cl, 2 tbl, 4 ex

Up!