Polymers for purification from metals

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer obtained via condensation polymerisation. The polymer is obtained from at least two monomers: acrylic monomer and alkylamine. Said polymer is modified such that it contains a dithiocarbamate salt group capable of cleaning one or more compositions containing one or more metals. The polymer has molecular weight of 500-200000.

EFFECT: obtaining polymers for various media as means of purification from metals, including waste water systems.

13 cl, 5 ex, 1 dwg

 

The technical field to which the invention relates

The invention relates to new polymers for the purification of metals.

The level of technology

Cleaning of metals for different environments, such as the treatment of water and air, is present in various industries, including heavy and light industries, such as power plants and mining. In addition, the purification of metal for industrial water is also an object of household applications.

Ongoing research to improve the technology of cleaning of metals necessary for various industries. The present invention describes various control processing of metals in industrial and domestic processes. These chemicals can potentially be used for other various applications that require cleaning from metals.

Brief description of figures

Figure 1 shows the General diagram of the wastewater system.

Summary of the invention

The present invention relates to compositions comprising a polymer derived at least two monomers: acrylic-x and an alkyl amine, where the said acrylic-x has the following formula:

where X=OR, HE and its salts, or NHR2and where R1and R2represent H or alkylen�Yu or aryl group, where R represents an alkyl or aryl group, wherein the molecular weight of the specified polymer is from 500 to 200,000, and where the specified polymer is modified so that it comprises a functional group capable of cleaning one or more compositions containing one or more metals.

The present invention also relates to a method for removing one or more metals from the environment containing these metals which comprises the following steps: (a) treatment of the said medium containing metals with a composition comprising a polymer derived at least two monomers: acrylic-x and an alkyl amine, where the said acrylic-x has the following formula:

where X=OR, HE and its salts, or NHR2and where R1and R2represent H or alkyl or aryl group, wherein the molecular weight of the specified polymer is from 500 to 200,000, and where the specified polymer is modified so that it comprises a functional group capable of cleaning one or more compositions containing one or more metals; (b) and collecting the removed metals.

Detailed description of the invention

A. Composition

The present invention relates to compositions comprising a polymer derived at least two monomers: acrylic-x and alkyl�Jn, where the said acrylic-x has the following formula:

where X=OR, HE and its salts, or NHR2and where R1and R2represent H or alkyl or aryl group, where R represents an alkyl or aryl group, wherein the molecular weight of the specified polymer is from 500 to 200,000, and where the specified polymer is modified so that it comprises a functional group capable of cleaning one or more compositions containing one or more metals.

Metals may include metals with zero valence, and monovalent and polyvalent metals. Metals can be modified with organic or inorganic compounds or may be unmodified. In addition, metals can be radioactive and non-radioactive. Examples include, but are not limited to, transition metals and heavy metals. Specific metals may include, but are not limited to: copper, Nickel, zinc, lead, mercury, cadmium, silver, iron, manganese, palladium, platinum, strontium, selenium, arsenic, cobalt and gold.

The molecular weight of the polymers may vary. For example, target species/use of polymers can be considered one factor. Another factor may be the choice of monomer. The molecular weight can be calculated in a different way�mi, known to those skilled in the art. For example, this may be a gel-chromatography, as described below in the examples.

When given the molecular weight, it denotes the molecular weight of the unmodified polymer, otherwise known as the main chain of the polymer. Functional groups that are added to the main chain, not included in the calculation. Thus, the molecular weight of the polymer with functional groups can greatly exceed the range of molecular masses.

In one embodiment, the implementation of the molecular weight of the polymer is from 1000 to 16000.

In another embodiment of the molecular weight of the specified polymer is from 1500 to 8000.

Various functional groups can be used for cleaning metal. The following phrases will be well understood by a person skilled in the art: when the specified polymer is modified so that it comprises a functional group capable of cleaning one or more compositions containing one or more metals. More specifically, the polymer is modified so that it comprises a functional group that can bind metals.

In one embodiment, the implementation of the functional group contains a sulfide group.

In another embodiment of the functional group represented�splash zones a group dithiocarbamate salt.

In another embodiment of the functional group represents at least one of the following groups:

alkylenediamine group, alkalescence acids and their salts, oxime group, a group amidoxime, dithiocarbamate acid and salts thereof, hydroxamic acids, and oxides of nitrogen.

The molar amount of functional groups in relation to total amines contained in an unmodified polymer can also vary. For example, the reaction of 3.0 molar equivalents of carbon disulfide with 1,0:1,0 molar ratio of acrylic acid/copolymer TERA, which contains 4 molar equivalent of the amine on the repeat unit after polymerization, produces a polymer that has been modified so that it comprises 75 mol. % group dithiocarbamate salt. In other words, 75% of the total content of amines in an unmodified polymer is transformed into a group dithiocarbamate salt.

In one embodiment of the polymer contains from 5 to 100 mol.% group dithiocarbamate salt. In yet another embodiment of the polymer contains from 25 to 90 mol.% group dithiocarbamate salt. In yet another embodiment of the polymer contains from 55 to 80 mol.% group dithiocarbamate salt.

The choice of monomer will depend on the target polymer, which is a specialist in the art wants sex�cation.

The alkyl amines can vary by type.

In one embodiment, the implementation of alkyl amine constitutes at least one of the following alkyl amines: the ethyleneamine, polyethylene polyamine, Ethylenediamine (EDA), Diethylenetriamine (DETA), Triethylenetetramine (TETA) and Tetraethylenepentamine (TERA) and pentamethylenebis (REN).

The Monomeric acrylic group-x can also vary.

In another embodiment of the acrylic-x represents at least one of the following groups: methyl acrylate, methyl methacrylate, acrylate and methacrylate, propylacetate and papermaterial.

In another embodiment of the acrylic-x represents at least one of the following groups: acrylic acid and its salts, methacrylic acid and salts thereof, acrylamide and methacrylamide.

The molar ratio between the monomers that constitute the polymer, especially an acrylic-x and an alkyl amine, can vary and depends on the resulting final polymer product. Used in a molar ratio defined as the number of moles of the acrylic-x, divided by the number of moles of alkylamine.

In one embodiment, the implementation of the molar ratio between acrylic-x and an alkyl amine is from 0.85 to 1.5.

In another embodiment, the implementation of the molar ratio between acrylic-x and an alkyl amine ranges from 1.0 to 1.2.

Various combinations and�RIL-x and alkyl amines included in the scope of this invention, as well as related molecular weight polymers.

In one embodiment of the acrylic-x is an acrylic esters, and alkyl amine is a WREN, or TERA, or DETA or TETA or EDA. In yet another embodiment of the molar ratio between acrylic-x and an alkyl amine is from 0.85 to 1.5. In yet another embodiment of the molecular weight may range from 500 to 200,000, from 1000 to 16000, or from 1500 to 8000. In yet another embodiment of the acrylic ester may be at least one of the following esters: methyl acrylate, methyl methacrylate, acrylate and methacrylate, propylacetate and propylbetaine, which is combined with at least one of alkyl amines, which includes RENA, or TERA, or DETA or TETA or EDA. In yet another variant implementation, the polymer is modified so that it contains the following ranges of groups dithiocarbamate salts: 5 to 100 mol.%, from 25 to 90 mol.%, from 55 to 80 mol.%.

In another embodiment of the acrylic-x is an acrylamide, and alkyl amine is a TERA or DETA or TETA or EDA. In another embodiment, the implementation of the molar ratio between acrylic-x and alkylamine is from 0.85 to 1.5. In another embodiment of the molecular weight may range from 500 to 200,000, from 1000 to 16000, or from 1500 to 8000. In other�ohms embodiment of the acrylamide may constitute at least one compound or a combination of acrylamide and methacrylamide, which are combined with at least one of alkyl amines, which include RENA or TERA or DETA or TETA or EDA. In yet another variant implementation, the polymer is modified so that it contains the following ranges of groups dithiocarbamate salts: 5 to 100 mol.%, from 25 to 90 mol.%, or from 55 to 80 mol.%.

In another embodiment of the acrylic-x is acrylic acid and its salts and alkyl amine is a WREN or TERA or DETA or TETA or EDA. In another embodiment, the implementation of the molar ratio between acrylic-x and alkylamine is from 0.85 to 1.5. In another embodiment of the molecular weight may range from 500 to 200,000, from 1000 to 16000, or from 1500 to 8000. In another embodiment of the acrylic acid may be at least one compound or a combination of acrylic acid or its salts and methacrylic acid or its salts, which are combined with at least one of alkyl amines, which include TERA or DETA or TETA or EDA. In yet another variant implementation, the polymer is modified so that it contains the following ranges of groups dithiocarbamate salts: 5 to 100 mol.%, from 25 to 90 mol.%, or from 55 to 80 mol.%.

Additional monomers can be integrated into the main chain of the polymer composed of monomers of the acrylic-x and alkylamine. Scheme re�functions of the condensation polymer can be used to obtain the main polymer chain. Various other methods of synthesis can be used for functionalization of the polymer, for example, dithiocarbamate and/or other functional groups for removal of non-metals.

Specialist in the art can functionalitywith polymer without conducting additional experiments.

Furthermore, the composition of the present invention can be obtained with other polymers, for example, described in patent US 5164095 given here as a reference, in particular, water-soluble dichlorocinnamic polymer with a molecular weight of from 500 to 100,000 which contains from 5 to 50 mol.% groups dithiocarbamate salt. In one embodiment, the implementation of the molecular weight of the polymer is from 1500 to 2000 and contains from 15 to 50 mol.% groups dithiocarbamate salt. In yet another embodiment of the molecular weight of the polymer is from 1500 to 2000 and contains from 25 to 40 mol.% groups dithiocarbamate salt.

Furthermore, the composition of the present invention can be obtained with other low-molecular sulfide precipitants, such as sodium sulfide, sodium hydrosulfide, TMT-15 ® (sodium or calcium salt tetrameric-3-triazine; Evonik Industries Corporation 17211 Camberwell Green Lane Houston, TX 77070, USA), dimethyldithiocarbamate and diethyldithiocarbamate.

V. Dosage

The dosage of the polymers described for use�FL may vary. The calculation of the batching quantity can be carried out without carrying out additional experiments.

The quality of the environment for the method and the degree of purification of the environment for the method are some of the factors that may be considered skilled in the art the dosage. Test analysis of the vessel is a typical example that is used as the basis for determining the amount of dosage required to achieve effective removal of metals in the context of the processing of the aquatic environment, for example, sewage.

In one embodiment, the implementation of the amount of the modified polymer according to the invention is able to efficiently remove metals from contaminated water, preferably is in the range from 0.2 to 2 moles of dithiocarbamate per mole of metal. More preferably, the dosage ranges from 1 to 2 moles of dithiocarbamate per mole of the metal contained in the water. In accordance with one variant of the invention, the dosage of polymer for removal of metal required for the chelation and precipitation with 100 ml of 18 parts per million of dissolved copper to about 1 part per million or less is 0,011 g (11.0 mg) of the polymer. The obtained metal-polymer complexes semilocally and settle quickly. These flocculants are easily separated from the treated water.

In the context of applying the polymer to the gas�howling system such as flue gases, the polymer can be dosed gradually, and the capture rate for a particular metal, such as mercury, can be calculated known in this field techniques.

C. Methods of use

The present invention also relates to a method for removing one or more metals from the environment containing these metals which comprises the following steps: (a) treatment of the said medium containing metals with a composition comprising a polymer derived at least two monomers: acrylic-x and an alkyl amine, where the said acrylic-x has the following formula:

where X=OR, HE and its salts, or NHR2and where R1and R2represent H or alkyl or aryl group, where R represents an alkyl or aryl group, wherein the molecular weight of the specified polymer is from 500 to 200,000, and where the specified polymer is modified so that it comprises a functional group capable of cleaning one or more compositions containing one or more metals, and (b) collecting the removed metals.

As described above the compositions included in this section and can be used in the claimed methods included in the scope of the invention.

Target metals depend on the processed system/environment.

Metals can include� metals with zero valency, monovalent and polyvalent metals. Metals can be modified with organic or inorganic compounds or may be unmodified. In addition, metals can be radioactive and non-radioactive. Examples include, but are not limited to, transition metals and heavy metals. Specific metals may include, but are not limited to, at least one of the following metals, Nickel, zinc, lead, mercury, cadmium, silver, iron, manganese, palladium, platinum, strontium, selenium, arsenic, cobalt and gold.

In one embodiment of the metal at least one metal or a combination of the following metals: copper, Nickel, zinc, lead, mercury, cadmium, silver, iron, manganese, palladium, platinum, strontium, selenium, arsenic, cobalt and gold.

In another embodiment of the metals are transition metals.

In another embodiment of the metals are heavy metals.

Environment containing metals, may vary and include at least one of the following environments: streams of sewage, liquid hydrocarbon streams, streams of flue gas, fly ash>and other solid particles. Various stages of processing may be associated with the removal of metal, including, but not limited to, stages of filtration and/or devices to control the quality�TWA air for example, bag dust collectors and electrostatic precipitators, and other devices to monitor air quality.

Environment environment containing a liquid phase medium containing a liquid phase, are one target of the claimed invention.

In one embodiment, the implementation environment is a treated stream containing water, e.g., waste water or sewage plants or industrial use (power plant, mining, burning of waste and/or process operation).

In another embodiment, the implementation environment is a stream of liquid hydrocarbons from refinery processes or petrochemical processes. Examples include flows of these processes that contain petroleum hydrocarbons, such as petroleum hydrocarbon, including crude oil and its fractions, such as naphtha, gasoline, kerosene, diesel fuel, jet fuel, mazut, gasoil vacuum residue, etc., or olefinic or naphthenic process streams, process streams of obtaining ethylene glycol, aromatic hydrocarbons and their derivatives.

In another embodiment, the implementation of additional chemicals, flocculants and/or coagulants can be used in combination with chemical substances in the present invention. Chemicals used for the environment containing metals can vary, including the addition of at least one of the following compounds: cationic polymers, anionic polymers, amphoteric polymers and zwitterionic polymers.

In another embodiment of the method of the present invention also includes further processing the process stream complexing amount of water-soluble dichlorocinnamic polymer with a molecular weight of from 500 to 100,000 which contains from 5 to 50 mol.% groups dithiocarbamate salt with obtaining a complex of these metals, for example, heavy metals. In another embodiment of the molecular weight of the polymer is from 1500 to 2000, and the polymer contains from 15 to 50 mol. % groups dithiocarbamate salt. In yet another embodiment of the molecular weight of the polymer is from 1500 to 2000, and the polymer contains from 25 to 40 mol.% groups dithiocarbamate salt.

In another embodiment of the cleaning polymer and additional cleaning agent is added in a 1:1 ratio.

Environment containing a gas phase environment/environment containing a gas phase, are another target of the claimed invention. In addition, processes containing liquid and/or gas medium, also included in the scope of the present invention.

In another embodiment, the implementation environment is part of a system that generates warm�, for example, the flue gas stream.

In another embodiment of the heat generating system represents at least one of the following systems: combustion system, the combustion system in power plant system coal combustion, incineration system, furnace, furnaces for mining and cement processes and system for the processing of ore.

In another embodiment of the method of the present invention also includes the use of an oxidant to the system, which generates heat. In another embodiment of the oxidant is applied to the processing of the specified polymer.

In another embodiment of the method of multiphase cleaning process includes cleaning of gas and liquid, for example, one or more metals in a gas, such as mercury, and one or more metals in the liquid. They can include polymeric cleaning and additional cleaning as described above.

In yet another embodiment of the oxidizer represents at least one of the following substances: a thermolabile molecular halogen, calcium bromide, or a halogen-containing compound.

In another embodiment of the present invention further includes the use of oxidizing agent to the flue gas, not necessarily where the specified oxidizing agent oxidizes the target species at a temperature of 500°C or higher, or when those�ture, in which the oxidant can oxidize molecular mercury that is present in the process that proceeds with the formation of mercury, not necessarily where these target species are elemental mercury or its derivatives, and optionally where the specified oxidizing agent represents at least one of the following compounds: a thermolabile molecular halogen, calcium bromide, or a halogen-containing compound. Methods of mercury oxidation are described in the patents US 6808692 and US 6878358, which is given here as a reference.

In another embodiment of the processing of the polymer is carried out at a temperature of 300°C or below, preferably at 250°C or lower.

The following examples are not intended to limit the invention.

Examples

A. preparation of polymer

Example 1

Methyl acrylate/Tetraethylenepentamine polymer main chain, which is then modified dithiocarbamate groups.

and. Synthesis of methyl acrylate/Tetraethylenepentamine polymer main chain

Tetraethylenepentamine (TERA) (18,275 wt.%) was charged to a glass reactor equipped with mechanical stirrer and condenser. Filling the free space with nitrogen and stirring, dropwise over 30 min was added methyl acrylate (16,636 wt.%), while maintaining a temperature in the range of 25-31°C when adding � within 1 h after addition. Then carried out the second download of TERA (18,275 wt.%), and the obtained reaction mixture was heated at 130°C. This temperature was maintained for ~3 hours, collecting the condensate in a trap Dean-stark. At this time, the molten polymer was allowed to cool down to 120°C and then slowly diluted with deionized (DI) water (46,814 wt.%), maintaining the temperature above 90°C in the dilution process. Received ~50 wt.% the polymer solution is then cooled to room temperature. The average molecular weight of the polymer was 7500 according to gel chromatography and polysaccharide standards.

b. Getting dithiocarbamate polymer

The second stage was to add the polymer methyl acrylate/TERA (35,327 wt.%), DI water (28,262 wt.%) and Dowfax 2A1 (0,120 wt.%), Dow Chemical Company Midland, MI 48674, USA, in a round bottom flask equipped with a mechanical stirrer. Then to the stirred reaction mixture was added 50% NaOH (9,556 wt.%). The mixture was heated and kept at 40°C, was added dropwise carbon disulfide (17,179 wt.%) within 2 hours. One hour after the addition of carbon disulfide was uploaded additional amount of 50% NaOH (9,556 wt.%). The reaction mixture was held at 40°C for 2 hours. Then the reaction mixture was cooled to room temperature and was filtered through filter paper to obtain ~40 wt.% polymer diti�carbamate product.

Example 2

Acrylic acid/Tetraethylenepentamine polymer main chain, which is then modified dithiocarbamate groups

and. Synthesis of acrylic acid/Tetraethylenepentamine polymer main chain

Tetraethylenepentamine (TERA) (37,556 wt.%) and sulfuric acid (0,199 wt.%) was charged to a glass reactor equipped with mechanical stirrer and condenser. Filling the free space with nitrogen and stirring, dropwise over 30 min was added acrylic acid (14,304 wt.%), while maintaining a temperature in the range of 130-140°C in the process of adding, allowing eksterne an acid-base reaction to reach the desired temperature. Then, the resulting reaction mixture was heated to 160°C. This temperature was maintained for 4.5 hours, collecting the condensate in the trap Dean-stark. At this time, the polymer melt was left to cool to 120°C and then slowly diluted with DI water (47,941 wt.%), maintaining the temperature above 90°C in the dilution process. Received 50 wt.% the polymer solution is then cooled to room temperature. The average molecular weight of the polymer was about 4700 according to gel chromatography and polysaccharide standards.

b. Getting dithiocarbamate polymer

The second stage was to add polymer acrylic acid/TERA (31,477 wt.%), DI water (36,825 wt.%) and Dowfa A (amount of 0.118 wt.%) in a round bottom flask, equipped with a mechanical stirrer. Then to the stirred reaction mixture was added 50% NaOH (8,393 wt.%). The mixture was heated and kept at 40°C, was added dropwise carbon disulfide (14,794 wt.%) within 2 hours. One hour after the addition of carbon disulfide was uploaded additional amount of 50% NaOH (8,393 wt.%). The reaction mixture was held at 40°C for 2 hours. Then the reaction mixture was cooled to room temperature and was filtered through filter paper to obtain ~35 wt.% polymer dithiocarbamate product.

Example 3

and. Synthesis of acrylamide/Tetraethylenepentamine polymer main chain

Tetraethylenepentamine (TERA) (14,581 wt.%) was charged to a glass reactor equipped with mechanical stirrer and condenser. Filling the free space with nitrogen and stirring, was added dropwise to 48.6% solution of acrylamide (30,441 wt.%) in for 1 hour, during which the preset temperature is reached and maintained in the range of 65-75°C. After loading acrylamide temperature maintained for a further 1 hour. Then carried out the second download of TERA (14,581 wt.%), and the obtained reaction mixture was heated to 160°C, collecting the distilled water using a Dean stark trap. This temperature was maintained for ~4 hours, continuing to collect the condensate in a trap D�on stark, and capturing the released ammonia by-product. At this time, the polymer melt was left to cool to 120°C and then slowly diluted with DI water (40,397 wt.%), maintaining the temperature above 90°C in the dilution process. Received ~50 wt.% the polymer solution is then cooled to room temperature. The average molecular weight of the polymer amounted to 4500 according to gel chromatography and polysaccharide standards.

b. Getting dithiocarbamate polymer

The second stage was to add the acrylamide/TERA polymer (34,004 wt.%), DI water (36,518 wt.%) and Dowfax 2A1 (0,122 wt.%) in a round bottom flask equipped with a mechanical stirrer. Then to the stirred reaction mixture was added 50% NaOH (7,763 wt.%). The mixture was heated and kept at 40°C, was added dropwise carbon disulfide (13,830 wt.%) within 2 hours. One hour after addition of the carbon disulfide was uploaded additional amount of 50% NaOH (7,763 wt.%). The reaction mixture was held at 40°C for 2 hours. Then the reaction mixture was cooled to room temperature and was filtered through filter paper to obtain ~35 wt.% polymer dithiocarbamate product.

V. Analysis of wastewater

As stated above, a standard method to determine the number and potential effectiveness of polymers to collect meta�l in the water treatment process is the analysis of the vessel.

1. An example of using the method with typical waste water with 20 ppm of Cu, using the analysis in a vessel

Usually all polymers were obtained in the form of a 12 wt.% polymer solutions in DI water, and obtained fresh on the day of testing. Containing copper water used for testing.

Six samples of 300 ml (vessel) of wastewater were placed in beakers with a volume of 500 ml and was placed in group a stirrer. Samples of wastewater were mixed at 150 revolutions per minute (rpm), introducing the polymer in the samples. Used a dosage of 0.50 g, 0,63 g, 0.75 g, 0.88 g and 1.00 g of the polymer solution obtained as described above. Stirring at 150 rpm was continued for 10 minutes. Then slowly stirred (35 rpm) for 10 minutes. After stirring the precipitate was allowed to settle, without shaking, for an additional 10 minutes. Then the water samples were filtered through a 0.45 μm filter. Then the filtrate was acidified with to pH=2 using concentrated nitric acid, to stop further deposition of copper. Residual dissolved copper was determined in filtered-water samples by atomic absorption analysis using a copper reference standards. One set of vessels were used for each tested polymer. Conducted duplicates for several polymers and confirmed the results obtained.

�should be noted, that the observed rate of filtration, generally accounted for less than 1 minute to contaminated water, treated with the polymer, while the rate of filtration for water treated with low-molecular-weight precipitating metals such as dimercapto-S-triazine or a dithiocarbamate, was usually more than 2 minutes.

2. An example of using the method with typical wastewater with Nd, using the analysis in a vessel

Usually all polymers were obtained in the form of a 5 wt.% polymer solutions in DI water and obtained fresh on the day of testing. Mercury-containing water used for testing.

Six samples of 500 ml (vessels) of wastewater were placed in beakers with a volume of 1 l and was placed in group a stirrer. Samples of wastewater were mixed at 300 rpm by injecting the polymer samples. Used dosage 0.050 g, 0,100 g, 0,150 0,250 g and g of the polymer solution obtained as described above. Stirring at 300 rpm was continued for 25 minutes. Was then added 5 parts per million of a cationic flocculant, and then slowly stirred (15 rpm) for 5 minutes. After stirring the precipitate was allowed to settle, without shaking, for an additional 45 minutes. Then the water samples were filtered through a 0.45 μm filter. Residual mercury content was determined in samples of filtered water in accordance with method 1631 United States EPA. Od�n the set of vessels were used for each tested polymer. Conducted duplicates for several polymers and confirmed the results obtained.

It should be noted that the observed filtration rate was usually higher than for water, purified low molecular weight precipitating metals such as dimercapto-3-triazine or dithiocarbamate.

3. An example implementation of the model wastewater containing Cu, using the analysis in a vessel

The residual copper content (ppm) in the polluted water.
The polymer dosage (mg)/100 ml of wastewater
Example06,88,510,211,9
1b19,18,04,82,10,3
The polymer dosage (mg)/100 ml of wastewater
Example07,08,8 10,512,3
2b18,67,84,52,610,2
The polymer dosage (mg)/100 ml of wastewater
Example06,88,510,211,9
3b19,17,85,22,50,7

C. a General method of use of polymers in wastewater treatment

Figure 1 shows a General diagram of the wastewater treatment process. At this shape the scheme of sewage treatment based on treatment of flue gas desulfurization chloride purification plant. The polymers of the present invention can be applied, at least for stages of deposition, coagulation and flocculation.

The combinations of features described in the patent application

In one�the approach to the implementation of the composition of the claimed substances include various combinations of the polymer components, such as molecular weight, functional group, the monomer components and the molar quantity of the specified components. In another embodiment of the claimed compositions comprise a combination according to the dependent claims. In another embodiment, the implementation of a range or the equivalent of a certain component comprises a separate component (components) within the limits or ranges of this range.

In another embodiment of the inventive method of application includes various combinations of the polymer components, such as molecular weight, functional group, the monomer components and the molar quantity of the specified components. In another embodiment of the claimed uses include combinations according to the dependent claims. In another embodiment, the implementation of a range or the equivalent of a certain component comprises a separate component (components) within the limits or ranges of this range.

1. The polymer obtained by the reaction of the condensation polymerization of at least two monomers: acrylic monomer and alkyl amine where the specified acrylic monomer has the following formula:

where X=OR, where R represents an alkyl or aryl group,
where R1represent H or ALK�flax or aryl group, moreover, the molecular weight of the specified polymer is from 500 to 200,000, and where the specified polymer is modified so that it comprises a group dithiocarbamate salt, capable of cleaning one or more compositions containing one or more metals.

2. The polymer according to claim 1, which contains from 5 to 100 mol.% group dithiocarbamate salt.

3. The polymer according to claim 1, wherein the alkyl amine is at least one of the following alkyl amines: the ethyleneamine, polyethylene polyamine, Ethylenediamine (EDA), Diethylenetriamine (DETA), Triethylenetetramine (TETA) and Tetraethylenepentamine (TERA) and pentamethylenebis (REN).

4. The polymer according to claim 1, wherein the acrylic monomer represents at least one of the following groups: methyl acrylate, methyl methacrylate, acrylate and methacrylate, propylacetate and papermaterial.

5. The polymer according to claim 1, wherein the acrylic monomer is an acrylic ester, and the alkyl amine is a WREN or TERA or DETA or TETA or EDA, and the molar ratio between the acrylic monomer and the alkyl amine is from 0.85 to 1.5.

6. The polymer according to claim 5, in which the molecular weight of the specified polymer can cover the range from 1500 to 8000, and where the polymer is modified so that it contains more than 55 mol.% dithiocarbamates acid and its salts.

7. The polymer obtained by the reaction �condensational polymerization, at least two monomers: acrylic monomer and alkyl amine where the specified acrylic monomer has the following formula:

where X=HE, and its salts, or NHR2and where R1and R2represent H or alkyl or aryl group, where R represents an alkyl or aryl group, wherein the molecular weight of the specified polymer is from 500 to 200,000, and where the specified polymer is modified so that it comprises a group dithiocarbamate salt, capable of cleaning one or more compositions containing one or more metals.

8. The polymer according to claim 1, which contains from 5 to 100 mol.% group dithiocarbamate salt.

9. The polymer according to claim 7, in which the alkyl amine is at least one of the following alkyl amines: the ethyleneamine, polyethylene polyamine, Ethylenediamine (EDA), Diethylenetriamine (DETA), Triethylenetetramine (TETA) and Tetraethylenepentamine (TERA) and pentamethylenebis (REN).

10. The polymer according to claim 7 in which the acrylic monomer is an acrylic ester, and the alkyl amine is a WREN or TERA or DETA or TETA or EDA, and the molar ratio between the acrylic monomer and the alkyl amine is from 0.85 to 1.5.

11. The polymer according to claim 1, wherein the molecular weight of the specified polymer can cover the range from 1500 to 8000, and where the polymer is modified so�m, that contains more than 55 mol.% dithiocarbamates acid and its salts.

12. The polymer according to claim 7 in which the acrylic monomer is an acrylic ester, and the alkyl amine is a WREN or TERA or DETA or TETA or EDA, and the molar ratio between the acrylic monomer and the alkyl amine is from 0.85 to 1.5.

13. The polymer according to claim 12, in which the molecular weight of the specified polymer can cover the range from 1500 to 8000, and where the polymer is modified so that it contains more than 55 mol.% group dithiocarbamate salt.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention can be used to purify natural water and waste water from oil refineries. The polyacrylamide-based flocculant includes polyacrylamide used in the form of an aqueous solution with molecular weight of 30 million, with hydrolysis degree of 70% and operating pH 5-11, wherein the polymer has swollen in water at room temperature for 1 day, a modifying agent - propylene glycol and water, with the following ratio of components, wt %: polyacrylamide 0.5-0.7; propylene glycol 0.15-0.3; water - the balance. To prepare the flocculant, propylene glycol is added to an aqueous polyacrylamide solution with said characteristics at room temperature while stirring in the disclosed ratio of components and then used to flocculate contaminated water.

EFFECT: flocculant provides faster and improved clarification of waste water owing to improved flocculating power of the composition of the reagent.

1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a composite moisture-retaining material, which can be used in crop production for the improvement of water-air and nutritional mode of soil, as well as for the recovery of vegetation on soils of various types. The composite moisture-retaining material is made on the base of acryl copolymer and filler. The acryl copolymer is made on the base of acrylamide and acrylic acid salts with a ratio of 20/80-80/20 mol. % in the presence of a cross-linking agent N,N'-methylene-bis-acrylamide and a polymerisation initiator. As the filler used is a mixture of wastes of biocatalytic productions of acryl monomers and acids of humic acids with a ratio of 99/70-1/30 wt % by dry substance in the form of a water paste or a dry powder-like form. The total content of the filler constitutes to 60 wt %. A method of obtaining the composite moisture-retaining material is described.

EFFECT: reduced cost of the moisture-retaining material, presence of an additional source of plant nutrition, simplification of technology of a filled gel manufacturing with the preservation of water-sorption properties at the level of existing filled and non-filled analogues.

2 cl, 1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: polyacryleamides are obtained by heterophase copolymerisation of vinyl monomers. First, n-dodecyclacrylamide is added to water solution of sodium dodecylsulfate, applied as stabiliser, with mixing. Then, water solution of acryleamide and acrylic acid is added to obtained dispersion. Reaction is carried out in alkaline medium at pH 9.5 with general concentration of copolymers from 3.0 to 3.8 mol/l. After that, particles of magnetic filler are added to obtained mixture with mixing in atmosphere of inert gas with gradual increase of reaction mass temperature from 20 to 55°C. Water solution of initiator, such as potassium persulphate or ammonium persulphate is added to obtained water dispersion to concentration 3.5-4.2 mmol/l. After that, obtained product is separated by known methods. As magnetic filler, applied is magnetite with particle size from 50 to 1000 nm or acicular particles of magnemite from 200 to 800 nm long with diameter from 20 to 50 nm. Magnetic liquid includes liquid phase - water or its mixture with organic solvents, such as ethanol methanol, and magnetic solid phase - upper said polyacryleamide.

EFFECT: invention makes it possible to obtain polyacryleamide by more technological economic method in absence of highly-toxic solvents and obtain magnetic liquid, which preserves sedimentation stability in magnetic field.

4 cl, 1 dwg, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: polyacrylamide-based flocculant modification method includes using microwave radiation directed on the starting crystalline polyacrylamide product. The microwave radiation has the following properties: frequency 2.45 GHz, power 700 W, duration of irradiating crystals of the starting flocculant 5-7 s.

EFFECT: method creates conditions for further interaction of macromolecules with each other and increase in molecular weight thereof, which improves the process.

1 tbl, 2 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: composite material can be used to produce sheet decorating and heat-insulating materials in residential, agricultural and industrial construction, as well as for producing moulded packaging elements and containers susceptible to biodegradation, i.e., having biodegradable properties. The polymer composite material consists of, wt %: fibre filler - waste cardboard and/or paper 11.0-12.0, cationic-anionic polyacrylamide resin Ultrarez DS-150 56.0-57.0, polyvinyl alcohol in form of a 15 wt % aqueous solution 27.0-28.0, sodium tetraborate 6.0-3.0. Described is a method of producing a composite material which involves separating fibres of the fibre filler on a rotary disperser with rotor speed of 2500-3000 rpm, wherein the polyvinyl alcohol is added at the mixing step in form of a 15 wt % aqueous solution together with the cationic-anionic polyacrylamide resin Ultrarez DS-150 and sodium tetraborate, pressing and drying.

EFFECT: improved physical and mechanical properties of the polymer composite material while simplifying the production technique.

2 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: composite material consists of the following, wt %: polyethylene 277 50-55 and a copper polyacrylamide polycomplex 50-45. The copper polyacrylamide polycomplex is obtained by dissolving copper powder in ammonia solution, mixing the obtained solution with aqueous polyacrylamide solution and separating the polycomplex from the solution with acetone or ethyl alcohol.

EFFECT: longer service life of friction assemblies operating in a dry environment, high hardness of articles.

2 tbl

FIELD: oil and gas industry.

SUBSTANCE: suspension-emulsion composition of anti-turbulent additive contains the following, wt %: polyacrylamide with "м.м." 5.5·106 and particle size of not more than 200 mcm - 30-20, polyethyleneglycol - 11-13, stearic acid - 2, ethanol - 42-50 and glycerin - 15.

EFFECT: anti-turbulent additive has decreased viscosity and provides reduction of hydrodynamic friction in oil flow.

8 ex

FIELD: oil and gas production.

SUBSTANCE: method to stabilise an aqueous solution of polyacrylamide consists in preparation of polyacrylamide in water with concentration from 0.15 to 0.30 wt %. Then polyacrylamide is dispersed by mixing of the produced solution with angular speed from 14000 rpm to 17000 rpm.

EFFECT: method makes it possible to reduce energy intensity and time for solution preparation, to preserve rheological properties of a solution within a long period of time, to increase efficiency of using the produced solution due to stabilisation of its dynamic viscosity.

3 dwg

FIELD: chemistry.

SUBSTANCE: method of producing hybrid organic-inorganic material comprises the following steps: (a) peptisation of material of inorganic particles selected from oxides, sulphides, sulphates, phosphates, arsenides and arsenates of noble metals and mixtures thereof, in anhydrous sulphuric acid or hydrogen fluoride, to obtain a solution of material of inorganic particles; (b) fractionation of the solution obtained at step (a) to obtain a solution of inorganic particles having particle size ranging from 5 nm to 100 nm; (c) mixing the fractionated solution obtained at step (b) with an organic solvent; (d) reacting the mixture from step (c) with a solution of a reactive organic monomer with silane functional groups in an organic solvent.

EFFECT: method of obtaining hybrid organic-inorganic monomer material enables to obtain monomer materials which combine desired products of material of inorganic particles and an organic monomer, in addition to unique nanoparticle properties.

15 cl

FIELD: physics.

SUBSTANCE: disclosed is use of a) polyalkyl(meth)acrylate and b) a compound of formula (I), wherein residues R1 and R2 independently denote an alkyl or cycloalkyl with 1-20 carbon atoms, to make solar cell modules, primarily for making light concentrators of solar cell modules. (I). Also disclosed is a solar cell module and a version of said module. The solar cell module has operating temperature of 80°C or higher; full light transmission of moulding compounds in the wavelength range from 400 to 500 nm is preferably at least 90%; full light transmission of moulding compounds in the wavelength range from 500 to 1000 nm is preferably at least 80%.

EFFECT: improved properties of the module.

16 cl, 4 dwg

Laminate // 2428315

FIELD: process engineering.

SUBSTANCE: invention relates to laminate used in glass panels, lenses etc. Proposed laminate comprises base made up of polycarbonate resin, first layer resulted from hardening acrylic resin hardening, second layer produced by thermal hardening of organosiloxane resin. Acrylic resin composition comprises (A) acrylic copolymer containing at least 70 mol % of repeating link of formula (A)

,

where X is hydrogen or methyl, Y is methyl, ethyl, cycloalkyl or hydroxyalkyl with the number of atoms of 2 to 5, or residue of UV radiation absorber based on triazine; blocked polyisocyanate compound; hardening catalyst; and (D) UV radiation absorber based on triazine. Note here that total content of UV radiation absorber based on triazine in formula (A) and as component (D) varies from 1 to 40 wt %. Composition of organosiloxane resin in proposed laminate comprises (E) colloidal silicon dioxide and (F) hydrolytic condensate of alkoxy silane. Invention covers also window glass made based on said laminate.

EFFECT: higher strength and longer life.

25 cl, 15 tbl, 50 ex

Acrylic mixtures // 2418828

FIELD: chemistry.

SUBSTANCE: invention relates to mixtures of low molecular and high molecular acrylic polymers. The invention discloses an acrylic polymer composition for moulding or extrusion, which contains a mixture in molten thermoplastic high molecular acrylic material (HMAM) and thermoplastic low molecular acrylic material (LMAM). An alkyl(alk)acrylate based (co)polymer accounts for at least 70 wt % of the HMAM and LMAM. The HMAM is characterised by average molecular weight (Mw) between 40000 Da and 1000000 Da, and the LMAM is characterised by Mw ranging from molecular weight of entwinement (Me) (expressed in thousand daltons) to 250000 Da.The invention also discloses a method of preparing an acrylic polymer composition, versions of using and processing the acrylic polymer composition, as well as products made from said composition.

EFFECT: obtaining acrylic polymer compositions with improved processability.

36 cl, 4 dwg, 19 ex

FIELD: chemistry.

SUBSTANCE: invention concerns curable thermoplastic elastomer mixes, their obtaining and application in production of items by cast or extrusion moulding. Curable thermoplastic elastomer mix includes: (a) 15 to 60 wt % of polymer or copolymer represented by complex polyalkylenephthalate polyether, and (b) 40 to 85 wt % of linked poly(met)acrylate or polyethylene/(met)acrylate curing resin combined with free radical peroxide initiation agent and organic diene co-agent in effective amount for linking the resin during extrusion or cast moulding of curable thermoplastic elastomer mix. After linkage the polymer or copolymer represented by complex polyalkylenephthalate polyether is present in the form of continuous phase, while the resin is present in dispersed phase. Such compositions are fit for production of rubber parts with excellent resistance to effect of oil lubricants and greases.

EFFECT: optimised residual compression deformation and Shore hardness, increased elastic constant during curing.

12 cl, 3 dwg, 2 tbl, 22 ex

FIELD: copolymers meant for usage in polymer binding agents for covers prone to swelling during heating.

SUBSTANCE: copolymer is described for usage in binding agent or as polymer binding agent in covers prone to swelling during heating, including a mixture of Newton copolymer and network copolymer, selected from a group including thixotropic and pseudo-plastic copolymers, while aforementioned Newton and network copolymers consist of links of substituted styrene and substituted acrylate and contain links of at least p-methylstyrene and 2-ethylhexylacrylate, with grammolecule ratio of p-methylstyrene and 2-ethylhexylacrylate ranging from 100/0 to 50/50. Also described is the cover prone to swelling during heating and method for producing the same, which cover includes polymer binding agent, foam-forming substances, carbon-forming substances and other normally used admixtures, featuring aforementioned copolymer as polymer binding agent.

EFFECT: optimized creation of coal and improved isolating properties of cover.

3 cl, 2 tbl, 8 dwg, 4 ex

FIELD: polymer materials.

SUBSTANCE: invention concerns amorphous light-sensitive cross-linked polymeric structure and provides structure including (i) amorphous cross-linked structure formed from matrix based on acrylate and/or methacrylate compound and cross-linking agent and (ii) photoreactive component capable of undergoing reversible photodimerization reaction. Cross-linked structures are characterized by good properties with shape-memory effect.

EFFECT: increased mechanical strength of material with desired property profile.

21 cl, 4 dwg, 2 tbl, 12 ex

The invention relates to ionomer polymer mixture, in particular the partially crosslinked thermoplastic and elastomeric polyolefin blends having a low hardness
The invention relates to dispersible in water material, which can be used as wipes

The invention relates to a composition for the manufacture of materials such as artificial leather, in particular, for the impregnation of textile bases in the production of fancy material

FIELD: chemistry.

SUBSTANCE: invention relates to a photoreactive polyamide polymer and a copolymer used for photo-alignment of liquid crystals in information display devices such as LCDs, as well as methods of producing a polymer and a copolymer, and an alignment layer containing the polyamide polymer or copolymer. The photoreactive polyamide polymer contains a repeating unit of formula 1: where m ranges from 10 to 1000; n ranges from 2 to 6; and R1 denotes a photoreactive functional group selected from a group comprising a cinnamate-based functional group of formula 1a, a coumarin-based functional group of formula 1b and an azo group-based functional group of formula 1c: Formula 1a Formula 1b Formula 1c where n1 is an integer from 0 to 4; n2 is an integer from 0 to 5. The photoreactive polyamide copolymer contains said unit of formula 1 and a repeating unit of formula 2: where 1 ranges from 10 to 1000; n ranges from 2 to 6; and R2 denotes a hydrogen atom or a substituted or unsubstituted alkyl having 1 to 20 carbon atoms. The method of producing the polymer involves ring-opening polymerisation of polysuccinimide and a compound of formula R1-O-(CH2)n-NH2. The method of producing the copolymer involves ring-opening polymerisation of polysuccinimide and a compound of formula HO-(CH2)n-NH2 and then reacting the obtained polymer with a compound of formula R1-Cl.

EFFECT: invention enables to obtain polymers and copolymers, having high capability of aligning liquid crystals and good electrical properties.

10 cl, 4 dwg, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to aramid polymers and products obtained therefrom. Disclosed is a cross-linked aramid polymer which includes a first aramid backbone chain which is cross-linked at the amide group through poly(meth)acrylic acid with an amide group of a second aramid backbone chain, and in which the aramid backbone chains are not modified by inclusion of monomers to obtain cross-linkable copolymers. Disclosed also is a method of producing the disclosed polymer and article from the disclosed polymer.

EFFECT: disclosed polymer enables to obtain highly oriented fibres with improved physical and mechanical properties.

11 cl, 2 tbl, 1 ex

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