Patent for the preparation of organic anionic polyelectrolyte
(54) METHOD FOR PRODUCING ORGANIC ANIONIC POLYELECTROLYTES
(57) Summary:
The way of receiving organic anion polyelectrolyte including education of the stable return of a number of acrylamides of monomeric emulsions in the presence of inorganic salts and the regulator of polymerization, the subsequent polymerization with participation of peroxide initiators and hydrolysis of organic educations in the presence of water solution of a hydroxide of sodium is described and as inorganic salts use salts of metals of 1 group in number of 10-13% of the mass of a water phase, as the regulator of molecular weight use the monoaminocarbonic amino acids containing methyl-sulfgidrill group in number of 0,1-0,25% of the mass of monomer, as a dispersive phase use the low-stiffening hydrocarbonic oil, as emulsifier — mix of air of fatty acids with trietanolamine, at the same time education, the structure and temperature of the return water oil emulsion are leveled by means of turbulent emulsification and a simultaneous cold of an emulsion and the furnace charge of the water dissolved monomer which is fractionally entered into an emulsion, inorganic salts and the regulator, emulsion polymerization in a water oil emulsion is conducted in the adiabatic mode at a temperature from 5 to 60°C in the presence of the peroxide initiator taken in the ratio to monomer providing its full conversion, and also organic anion polyelectrolyte — the high-molecular copolymer containing links of an arkilamid approximately from 50 to about 80 Mas. % and an akrilata of sodium approximately from 20 to about 50 Mas. %, in terms of the mass of copolymer, with characteristic viscosity of copolymer 20-10, having high solubility in water where the specified copolymer shows ionic activity as it is determined by measurements of a hydrogen indicator, a component rn 7-9,5, presented in the emulsion form in hydrocarbonic oil keeping thermo — both frost resistance and stability in the range of temperatures from +175 to -35°C and mobility at a temperature up to -35°C. The invention belongs to ways of receiving synthetic high-molecular polyelectrolytes — polymers and copolymers on the basis of a number of acrylamides which part of macromolecules the groups capable to ionization in solution are, applied when cleaning natural and sewage, for flotation, as additives when drilling in the complicated conditions, during creation of artificial structure of soils. 2 pages and 5 z.p. branches, 2 tab. The invention belongs to ways of receiving synthetic high-molecular polyelectrolytes — polymers and copolymers on the basis of a number of acrylamides which part of macromolecules the groups capable to ionization in solution are, applied when cleaning natural and sewage, for flotation, as additives when drilling in the complicated conditions, during creation of artificial structure of soils. The way of receiving water-soluble polyelectrolyte by radical polymerization of acrylic acid in the presence of derivative urea in solution under the influence of hydrogen peroxide is known at 60-70°C, with the subsequent processing of the received copolymer solution of alkali [1]. A lack of such way is use of rather expensive reagents and need of conducting process at external heating, rather small product yield. The way of receiving a polyacrylamide flocculant for polymerization of monomer in water solution in the presence of the polyacrylamide [2] which is previously dispersed in water solution gel or granulated is known. A lack of the known way is rather low content of the polymerized monomers, actually polyacrylamide in the received polymeric gel and, as a result, insufficiently high operational quality of a product and a limited circle of its application. The way of receiving high-molecular polyacrylamide in the return emulsions in the presence of inorganic salts of metals II and III of groups [3] is known. A lack of such way is formation of a quantity of a coagulant that speaks about existence of incomplete aggregate stability of monomeric emulsions during polymerization, stability of polymeric emulsions of a ready-made product, incomplete conversion of monomer. The invention purpose creation of a way of receiving organic copolymer polymerization of acrylamide and its derivatives in the form of high-disperse return emulsions with the increased stability, achievements of full conversion of monomer. The technical result of the invention — is created a way of receiving organic anion polyelectrolyte by polymerization of water-soluble monomer in a high-disperse return water oil emulsion. The specified technical result is achieved by influence of the following facts. Preparation of the initial furnace charge of monomer including water solution of monomer, inorganic salt of alkaline metal I of group of periodic table of elements and in addition the regulator — the monoaminomonocarboxylic amino acids containing methyl-sulfgidrill group with full dissolution, when hashing, cooling up to the temperature, on 2-3°C exceeding furnace charge solution turbidity temperature, and removal of the air oxygen which is present at burdening material a purge inert gas. Formation of a high-disperse stable return water oil monomeric emulsion, in the presence of inorganic salts and the regulator, part of initial furnace charge, emulsifier, in the high-speed mixing devices, turbomixer or the mixer which preferably have a gap between walls and the bottom of the device and its blade no more than 2-3 mm providing the movement of liquid with centrifugal criterion Reynolds not less than 2,3*10^3, with use of in addition hydrocarbonic low-stiffening oils. Polymerization of monomer is carried out in the formed micelles of the return water oil monomeric emulsion, at the adiabatic mode which temperature in reactionary system is provided with fractional giving of part of initial furnace charge, with participation of peroxide initiators, for example persulphate of ammonium or potassium in solutions, before full conversion of monomer. Hydrolysis of an emulsion of high-molecular polymer with release of water-soluble organic anion polyelectrolyte — the copolymer containing links of an acridamide and an acrylate of the sodium showing ability to ionization in solution. The way of receiving the organic anion polyelectrolyte in the return water oil emulsions containing links of the acrylamide and an acrylate of the sodium possessing high water solubility, showing ability to ionization in solution includes stages:
(a) monomer furnace charge preparation by hashing, before full dissolution, when cooling up to the temperature, on 2-3°C exceeding solution turbidity temperature and the purge inert gas containing:
(I) monomer from a number of acrylamide in water solution,
(II) inorganic salt of alkaline metal I of group of periodic table of elements and
(III) the monoaminomonocarboxylic amino acid containing methyl-sulfgidrill group;
(b) formations of the return water oil emulsion and preparation of reactionary mix turbulent dispergating, fractional giving of part of furnace charge of monomer, during the cooling and maintenance of a monomeric emulsion at a temperature not above 10°C and a purge inert gas containing:
(I) the low-stiffening hydrocarbonic oil,
(II) emulsifier — mix of air of fatty acids with trietanolamine and
(III) monomer furnace charge;
(c) polymerization of the specified reactionary mix when hashing, at a temperature from 5 to 60°C maintained by fractional giving of part of furnace charge of monomer with participation:
(I) peroxide intsiator;
(d) endurance of the received emulsion of copolymers at a temperature of 45 
50°C and hydrolysis, a purge inert gas at presence:
(I) water solution of a hydroxide.
Monomer of acrylamide is chosen from a number of amides containing acrylamide, methacrylamide, N — alkylacrylamide, N, N-dialkylacrylamide. As emulsifier use mix of air of fatty acids from a row olein, linoleic, linolenic and/or stearin and/or resin acids and/or tallove oil with trietanolamine and/or emultat. Apply to creation of a dispersive phase of the return water oil emulsion selective cleaning distillate hydrocarbonic oils with a temperature of hardening of-40 -70°C, kinematic viscosity 2 16 mm 2 / with at 50°C (a dispersive phase — it is the dispersive environment). The present invention is illustrated by the examples given below which do not limit the invention at all, and are presented only as examples of the best option of creation of organic polyelectrolyte. Example 1. Prepare monomeric return water oil emulsions. Place in a mixer 230 g of water 35% of solution of acrylamide, 18 g of sodium of chloride, 0,2 g 
— amino-
— methylthiooleic acid, mix before full dissolution, cool solution of furnace charge of monomer up to the temperature of 6-8°C, exempt from oxygen blowing off by nitrogen within 30 min. In the mixer mix 200 ml of mineral oil with a temperature of hardening of -55°C, 3 with a density of 0,865 g/cm, 6 g of air of olein, linoleic, stearin acids with trietanolamine and 1/3 part of the cooled monomer furnace charge solution. Mix at a temperature of 4-10°C is emulsified in the turbulent mode at 3000-5000 rpm, providing high-dispersion of the environment. When stirring bring 0,2 g of the initiator persulphate of the ammonium dissolved in 2 ml of the distilled water in the created return water oil emulsion. After the induction period temperature in the reactor begins to increase. Synthesis is carried out at a temperature not above 45-60°C, maintaining the set temperature fractional giving of the rest of the cooled monomer furnace charge solution. Upon termination of synthesis the oil-water emulsion of polyacrylamide is maintained at a temperature of 50-60°C within an hour, then add 30 g of water 48% of solution of a hydroxide of sodium and hydrolyzed at a temperature of 40-50°C with a purge emulsion nitrogen before complete cessation of release of ammonia. The received polyelectrolyte, anion, high-molecular, represents soluble in water, the return water oil emulsion of organic copolymer, steady, free from the koagulyum, containing acrylamide links 50-80 Mas. % and akrilata of sodium 50-20 Mas. %. Conversion of monomer of 100%. Characteristic viscosity of the polymer besieged in isopropyl alcohol and acetone in 2N sodium chloride solution makes 20-10 dl/g. The return water oil emulsion of polymer looks as low-viscous fluid liquideous substance, from white till beige color, 3 with an average density of 0,95-1,05 g/cm, with a slight specific smell, a grudnogoryucha. The emulsion is not defended and does not change the mobility during long period of storage, not less than one year and more. Examples 2-5. Prepare emulsions by an example 1, using inorganic salts of alkaline metals I of group of periodic table of elements — potassium chloride, sodium sulfate, potassium sulfate, sodium acetate, in number of 10-13% of the mass of a water phase. As the initiator persulphate of potassium or persulphate of ammonium is applied. Characteristic viscosity of the polymers from 10 to 20 dl/g received thus. Hydrogen indicator rn 7-9,5. Examples are characterized by tab. 1. Comparative stability of a water oil emulsion is characterized by quantity of the allocated koagulyum. Examples 6-7. Prepare polymer by an example 1, on the basis of a methacrylamide or N-alkylacrylamide, or other monomers of a number of acrylamides, using as the regulator methionine fodder in accordance with GOST 23423-89 or pharmaceutical (the Register. 71/273/40 of 11.01.99, it is approved by Pharmacy State committee), in number of 0,1 and 0,2% of the mass of monomer respectively. Characteristic viscosity of polymer 19-11 and 18-10 of units respectively. Example 8-11. Prepare polymer by an example 1, using air of fatty acids and resin acids as a part of emulsifier. Examples are characterized by tab. 2. The received products have sufficient characteristic viscosity and other positive properties. Conversion of monomer in all examples of 100%. The synthetic anion polyelectrolytes received according to the invention on the basis of a number of acrylamides represent high-molecular copolymers of acrylamide and an akrilat of sodium in a high-disperse return water oil emulsion, well soluble in the water capable to the ionization in solution keeping mobility at a temperature up to -35°C thermo — both frost resistance and stability in the range of temperatures from +175 to -35°C. Stability of an emulsion was determined according to a test method by TU 6-14-1035-91: «item 4. 3. Determination of stability of an emulsion». Water traces at determination of stability of an emulsion were not. Operational properties of organic anion polyelectrolyte in the form of a high-disperse return water oil emulsion, their good solubility in water, ability to ionization, allow to apply polymer at sewage treatment, to flotation, as additives when drilling. The product is packed up and delivered in a polymeric container of 25 dm 3 and more.
Information sources:
1. Aut. sv. USSR 1641831, cl. С 08 F 220/10, 220/56, 2/16, 1989.2. Patent RF 1678010, cl. С 08 F 120/56, 1989.3. Patent RF 2043997, cl. С 08 F 120/56, 2/32, 1992.
Invention formula:
1. The way of receiving organic anion polyelectrolyte including education of the stable return of a number of acrylamides of monomeric emulsions in the presence of inorganic salts and the regulator of polymerization the subsequent polymerization with participation of peroxide initiators and the hydrolysis of organic educations in the presence of water solution of a hydroxide of sodium differing in what as inorganic salts is used by salts of metals I of group in number of 10-13% of the mass of a water phase as the regulator of molecular weight use the monoaminomonocarboxylic amino acids containing methyl-sulfgidrill group in number of 0,1-0,25% of the mass of monomer, as a dispersive phase use the low-stiffening hydrocarbonic oil, as emulsifier — mix of air of fatty acids with trietanolamine, at the same time education, the structure and temperature of the return water oil emulsion are leveled by means of turbulent emulsification and a simultaneous cold of an emulsion and the furnace charge of the water dissolved monomer which is fractionally entered into an emulsion, inorganic salts and the regulator, emulsion polymerization in a water oil emulsion is conducted in the adiabatic mode at a temperature from 5 to 60°C in the presence of the peroxide initiator taken in the ratio to monomer providing its full conversion.2. A way on item 1 differing in the fact that as monomer use the connection chosen from the row containing acrylamide, methacrylamide, N-alkylacrylamide, N, N-dialkylacrylamide.3. A way on item 1 differing in the fact that as monoaminomonocarboxylic amino acid apply — amino- — methylthiooleic acid or methionine fodder or pharmacy.4. A way according to the item. 1, differing in the fact that as emulsifier mix of air of oleic, linoleic, linolenic and/or stearin acid, and/or resin acids, and/or tallove oil with trietanolamine and/or emultal.5 is used. A way on item 1 differing in the fact that furnace charge and a burdening water oil return emulsion at its education are cold up to the temperature, on 2-3°C exceeding solution turbidity temperature furnace charge.6. A way on item 1 differing in the fact that turbulent emulsification is carried out the high-speed mixing device, a turbomixer or the mixer, preferably, providing the movement of liquid with the centrifugal criterion of Reynolds not less than 2,3 
10 5 having a gap between the blade of a mixer and a wall and the bottom of a vessel no more than 2-3 mm.7. Organic anion polyelectrolyte — the high-molecular copolymer containing acrylamide links approximately from 50 to about 80 Mas. % and an akrilata of sodium approximately from 20 to about 50 Mas. %, in terms of the mass of copolymer, with characteristic viscosity of copolymer 20-10, having high solubility in water where the specified copolymer shows ionic activity as it is determined by measurements of a hydrogen indicator, a component rn 7-9,5, presented in the emulsion form in hydrocarbonic oil keeping thermo — both frost resistance and stability in the range of temperatures from +175 to -35°C and mobility at a temperature up to -35°C.
Table 1.
Influence of the use of different salts on the amount of coagulum formed.
| Name of salt | Sodium chloride | Potassium chloride | Sodium acetate | Sodium sulfate | Potassium sulfate |
| Mass fraction of coagulum % | 0 | 0 | 0.01 | 0.03 | 0.06 |
Table 2.
Influence a composition of emulsifier on the properties of product.
| Example | Name of ethers and composition of emulsifier, mass fraction % | Characteristic viscosity | |||
| Fatty acids | Resin acids | Tall oil by TU 13-0281078-119-89 | Emulsal by TU 6-14-1035-91 | ||
|
8 9 10 11 |
50-80 80-90 0 0 |
50-20 20-10 0 0 |
0 0 100 0 |
0 0 0 100 |
2-3 1.5-2.5 2.5-3.5 2.5-4 |
TK4A — Amendments to publications of data on inventions to the bulletins «Inventions (Applications and Patents)» and «Inventions. Useful models»
Page: 263
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Number and year of the publication of the bulletin: 36-2002
Section code: FG4A
Notice published: 7.01.2005 BI: 03/2005