Process of preparing cationic latex with hollow polymeric particles

FIELD: polymer materials.

SUBSTANCE: invention relates to preparing aqueous cationic latexes with hollow polymeric particles serving as multifunctional additives used when preparing polymer compositions, paintwork materials, coatings (including paper coatings), and in other applications as white pigment and filler reducing density of material and internal stresses arising during formation of coatings or polymer materials. Process comprises at least three following stages: (A) preparing functional core copolymer, (B) preparing particles with core-shell morphology, and (C) ionization of functional groups of core copolymer. All process stages are carried out as a series of consecutive transformations in the same reactor without discharge of intermediate products. As monomer containing functional groups in stage A, vinylbenzyl chloride is used, and stage C represents amination of vinylbenzyl chloride units with tertiary aliphatic amines, pyridine, or derivatives of the latter.

EFFECT: improved and simplified technology and improved characteristics of cationic latex.

10 cl, 6 ex

 

The invention relates to the production of an aqueous latex hollow polymer particles. Hollow polymer particles are multifunctional additives used in the preparation of polymer compositions, paints and varnishes, coatings on paper and in other areas as white pigment, filler, which reduces the density of the material, and additives that reduce internal stresses during formation of the coating or polymer product. The use of hollow polymer particles in the aqueous latex is the most convenient form, especially the "water technologies", such as paper production, water-dispersion paints, coatings or polymer compositions based on water prepolymers (precondensation) thermosetting resins.

The number of known methods for producing latex hollow polymer particles, based on the technology, including at least three stages:

A. Water-emulsion (co)polymerization Ethylenediamine monomers, one of which contains a functional group capable of when certain chemicals to ionize.

B. Copolymerization in the presence of latex particles obtained in stage A, Ethylenediamine monomers with the formation of particles with the morphology of the nucleus(copolymer obtained in stage a)to the shell(the copolymer obtained in studies).

C. Chemical treatment of functional groups of the core, causing them ionization, hydration, swelling of the copolymer core and a shell extension, leading to the formation of particles with one Central cavity [1].

In several patents [2, 3, 4] describes how to obtain latexes with hollow particles in which at the stage And as the functional monomer is used unsaturated carboxylic acid, and the stage is the ionization of the carboxyl groups by neutralization with base.

The disadvantages of the method include the difficulties associated with the implementation of the morphology of the particles core-shell (stage B). The morphology of the obtained particles used in this method is thermodynamically unfavorable, due to the high hydrophilicity of the polymer core (acrylic copolymer containing a large number of carboxyl groups) and the hydrophobicity of the copolymer shell. It requires very careful control of the dispensing of the monomers in the reaction mixture at the stage B, excluding the possibility of their diffusion in the volume of the nucleus. In some cases, even be necessary to create an intermediate shell having affinity to the polymer core and polymer shell [5].

In all of these patents latexes had the anionic nature, because the synthesis was carried out in the presence of anionic surfactants and initiators that form when according to the terms anion-radicals. The negative charge of the particles eliminates the possibility of their application in such areas as obtaining polymer compositions based on thermosetting resins, curable in the presence of acidic catalysts. When using hollow polymer particles in paper production at the stage of preparation of the slurry of cationic latexes have an advantage over anionic, because the hollow particle with a positive charge in addition to the basic functions of a pigment, increasing the whiteness and opacity of the paper, and filler, which reduces its density, can perform the function of retaining additives, binding and reducing losses of other ingredients, the particles are in the aquatic environment have a negative charge.

In patent applications [6, 7] describes how to obtain cationic latexes with hollow particles methods of recharge anionic latexes cationic surfactants or cationic, melamine-formaldehyde resin. These methods are not free from disadvantages of methods of obtaining anionic latexes with hollow particles, because they include a step for anionic latex. In addition, they include an additional stage - reload anionic latex. At this stage there is a risk of coagulation of the latex. To avoid this, it is necessary to use special techniques, complicating techno is Ohio.

Closest to the claimed method according to essential features is a direct method of obtaining cationic latex with hollow particles described in the patent [8]. The method includes three main stages:

A) obtaining functional copolymer kernel;

B) obtaining particles with the morphology of core-shell;

C) the ionization of the functional groups of the kernel.

Stage And represented the emulsion copolymerization of methyl methacrylate, 3-(dimethylamino)prophylatically and a small amount of cross-linkable co monomer (0.5% by weight of comonomers) - 1,3-butyleneglycol in the presence of 3-(methacrylamido)propyltrimethylammonium role stabilizer latex. The copolymerization initiate the redox system of the tert-butyl hydroperoxide - FeSO4·10H2On-formaldehydeinduced sodium. At the stage B get latex with particles of core-shell polymerization of isobutylacetate in the presence of latex particles obtained in stage A. Stabilization of latex and initiating the polymerization is carried out by the same components that were used in stage A. stage In the amino group contained in the copolymer core, neutralized with acid (e.g. acetic acid), resulting in swelling of the copolymer core and the formation of hollow particles.

1. At the stage B is formed very large amount of coagulum. About half loaded monomer during polymerization into coagulum. The resulting latex has a dry residue of less than 8%.

2. The degree of swelling of the copolymer kernel when neutralization is too small that it is not possible to obtain particles with a large volume of the cavity. In example 2 it is shown that the obtained particles have a diameter of 329 nm in diameter cavity 150 nm, which corresponds to the relative volume of the cavity 0.095 (volume of the cavity, referred to the total particle volume).

The technical result, which provides the present invention is the simplification of technology for the cationic latex with hollow particles and to improve the performance of hollow particles (increasing the relative volume of the cavity).

This technical result is achieved due to the fact that in a method of producing cationic latex with hollow particles comprising at least three stages:

A) water-emulsion (co)polymerization Ethylenediamine monomers, one of which contains a functional group capable of when certain chemicals to ionize;

B) the (co)polymerization in the presence of latex particles obtained in stage A, Ethylenediamine monomers with the formation of particles with the morphology of the nucleus(copolymer, receiving the hydrated on stage And shell(copolymer, obtained in stage B);

C) chemical treatment of functional groups of the core, causing them ionization, hydration, swelling of the copolymer core and a shell extension, leading to the formation of particles with a single Central cavity, as a monomer containing a functional group on the stage And use vinylbenzoic and stage represents amination vinylbenzoate parts of tertiary aliphatic amines, pyridine or its derivatives.

Stage And getting the latex particles of the nucleus is carried out by emulsion (co)polymerization of vinylbenzoate, universitymanila, alkyl(meth)acrylate and Acrylonitrile at a mass ratio 48-98/2-3/0-50/0-10V, respectively, in the presence of water-soluble azoinitiators when the mass ratio of the monomer/water 10-15/85-90.

As the alkyl(meth)acrylates use methyl methacrylate, n-butyl acrylate, and other (meth)acrylic monomers. It is preferable to use alkyl(meth)acrylates, reducing the glass transition temperature of the resulting copolymer.

The inventors have found that stable colloidal latex on stage And occurs if universitymanila is introduced into the aqueous phase.

The described technology stage And allows you to get ultimately hollow particles with a diameter of not more than 450 nm when classifies the flax the volume of the cavity is not less than 0.5. To increase the size of the hollow particles while maintaining the relative volume of the cavity is not less than 0.5 particle diameter of the core is increased to 200-250 nm due to the stage in two steps. Initially, at stage 1 get latex copolymers kernel on the above technologies, and then hold the stage And as the seed copolymerization of vinylbenzoate, n-butyl acrylate and Acrylonitrile at a mass ratio of 50/40/10, respectively, using as a seed latex obtained by 1 stage, when the mass ratio of the monomer/polymer seed from 3 to 6 in the presence of cationic surfactants of the type tetraalkylammonium in the amount of 0.25 to 0.50% by weight of comonomers.

Stage B is a seed (co)polymerization of the obtained at the stage And the seed latex alkyl(meth)acrylates or vinylaromatic monomers, Acrylonitrile, and cross-linking of the co monomer in a mass ratio 74-99,5/0-25/0,5-1,0, respectively. The ratio of the comonomers is selected so that the glass transition temperature of the copolymer membranes was in the range of 70-105°C. as cross-linking of the comonomers used etilenglikolevykh or divinylbenzene. As the alkyl(meth)acrylates use methyl methacrylate, n-butyl acrylate, n-butylmethacrylate and other (meth)acrylic monomers.

With the exception of the stage B to obtain a copolymer shell latex particles using cationic surfactants of the type tetraalkylammonium in the amount of 0.25 to 0.50% by weight of comonomers and water-soluble azoinitiator.

The copolymerization stage B is carried out in semi-continuous mode, i.e. in the seed latex simultaneously dispense two threads monomer mixture and the aqueous solution containing azoinitiator and cationic surfactant.

As the water-soluble azoinitiator at stages a and B using 2,2'-azobis(2-methylpropionamidine)dihydrochloride or 2-azobis[2-(imidazoline-2)propane]dihydrochloride in the amount of from 1.5 to 3.0% by weight of comonomers.

The copolymerization processes in the stages a and B is carried out at temperatures of 60-80°C.

The formation of the structure of the latex particles is conducted so that the mass ratio of the copolymer of the shell and the kernel was in the range of from 3 to 14, preferably from 8 to 10.

Stage represents interaction of amines with vinylbenzoate links (co)polymer core latex particles.

As a result of this reaction is the ionization benzylchloride groups becoming Quaternary, much hydratious ammonium group. Hydration causes swelling of the polymer core and the expansion of the polymer shell latex particles. The result is a polymer particle with a single Central cavity filled with water. When the drying of the particles, the water diffuses through the membrane and the cavity is filled with air the om without deformation of the shell particles.

Amination of benzylchloride groups of the copolymer kernel spend tertiary aliphatic amine at 70°if the glass transition temperature of the copolymer shell does not exceed 75°and pyridine or its derivatives at 80-100°if the glass transition temperature of the copolymer shell above 75°Since, when the molar ratio of amine/benzylchloride group from 1 to 4 for 1-3 hours. Amin is loaded into the reaction mixture slowly over 20-30 minutes

As tertiary aliphatic amines using trimethylamine, triethylamine, and other similar tertiary amines.

As derivatives of pyridine use picoline or quinoline. Before aminating on stage In latex injected cationic surfactant type tetraalkylammonium in the amount of 1-4% by weight of the copolymer.

All the process stages a, B and C are conducted as a series of successive transformations in a single reactor without intermediate unloading of product. The amount of coagulum formed does not exceed 2%.

As a result of transformations forms a cationic latex with hollow particles with a dry matter content of 11-25% wt. with particle diameters varying between 250 and 600 nm and the relative volume of the cavity from 0.50 to 0.85.

Properties of the obtained latex hollow polymer particles was determined as follows:

1. The residue was determined according to GOST 5709-83.

2. The content of the coagulum was measured according to GOST 24923-81.

3. The diameter of the particles was measured by electron microscopy using electron microscope Hitachi H-300. Samples were applied to the coated formarum copper grid. When getting photos of latex particles based on acrylic copolymers with a glass transition temperature less than 100°particles were subjected to treatment with hydrazinehydrate, and then chetyrehokisi OS. Electron micrograph obtained at magnification of 30,000. Particle diameter was determined on the basis of measurements performed for 300 particles for each sample. The coefficient of polydispersity defined as the ratio of the volumetric average to srednecenovom diameter of the latex particles. The relative volume of the cavity V was calculated by the formula

where dB- the diameter of the particles obtained in stage B, dIn- the diameter of the hollow particles obtained in stage C.

4. The glass transition temperature of the copolymers was calculated by the equation Fox:

1/Tc=n1/T1+n2/T2+...,

where Twiththe glass transition temperature of the copolymer;

T1, T2the glass transition temperature of the homopolymers;

n1n2mass fractions of units of comonomers in the copolymer.

5. ζ - potential was measured by the method of microelectrophoresis on installing Barton using lat the KSA, having a concentration of 7 wt.%, and 0 025N aqueous solution of potassium chloride as a side fluid.

ζ - potential was calculated by the equation Helmholtz-Smoluchowski

where

η and D is the viscosity and permittivity of the dispersion medium (water)0.1 SDR and 81, respectively, of a Uo- electrophoretic mobility of the particles, determined in accordance with the equation

where

U is the velocity of the displacement boundary latex/side fluid, E is the potential difference of 100 V, l is the distance between the electrodes of the cell (24 cm).

The invention is illustrated by the following examples.

Example 1. The process is carried out in a glass reactor with a volume of 700 cm3equipped with stirrer, reflux condenser, and a pump for feeding the monomer mixture and the aqueous phase. The process is carried out at a constant speed stirring (180 rpm). The synthesis of the polymer is carried out in a current of inert gas.

Stage A. Obtaining a copolymer kernel simultaneous loading of components.

Charged to the reactor 65 g of distilled water, 5 g of 3,6%-aqueous solution of universitymanila (WBAH) (0.18 g calculated on the pure substance) and give a current of inert gas. After 30 min load 4.5 g of vinylbenzoate (WBH), 3.6 g of n-butyl acrylate (BA) and 0.9 g of Acrylonitrile (an) (mass is the rate of VBAH/VBH/BA/EN respectively 2/49/39,2/9,8) and heated the reaction mixture for 30 min to 70° C. and Then charged to the reactor 0.27 g of 2-azobis(2-methylpropionamidine)dihydrochloride (3% by weight of comonomers), dissolved in 5 ml of water. The process of emulsion copolymerization is carried out for 5 hours.

Feature latex:

The dry residue 10.9% wt.

The diameter of the polymer particles 134 nm.

The coefficient of polydispersity 1,06.

Stage B. Obtaining latex with particles of core-shell.

Into the reactor containing the latex obtained at the stage And perform simultaneous loading of Monomeric mixtures containing at 55.6 g of methyl methacrylate (MMA) and 0.3 g of etilenglikolevykh (EGDM) (mass ratio of 99.5/0.5) and 0.14 g of didecyldimethylammoniumchloride (TMAH) and 1.12 g of 2-azobis(2-methylpropionamidine)dihydrochloride (respectively 0.25 and 2.0% of the weight of the dosed monomers), dissolved in 293 g of water for 347 minutes After boot latex was incubated for 30 minutes

Characteristics of latex:

The dry residue of the latex and 15.3% wt.

The glass transition temperature of the shell ˜105°C.

The diameter of the polymer particles 151 nm.

Stage C. stage amination.

Into the reactor containing the latex obtained at stage B, enter 2,6 g TMAH (4% dry weight) in 100 g of water, stirred for 15 minutes Then give 9.4 g of pyridine (molar ratio of pyridine / VBG equal to 4) for 20 min and incubated for 3 hours at 10° C. thereafter, the latex is cooled to 30-40°, discharged and filtered.

Characteristics of latex:

The dry residue of 13.5% wt.

Particle diameter of 276.5 nm.

The relative volume of the cavity 0,84.

ζ - potential + 52 mV.

Example 2. The process is carried out analogously to example 1, but in a reactor with a volume of 500 cm3at other concentrations of the reactants and the temperature.

Stage A. charged To the reactor 65 g of distilled water, 7.5 g of a solution UBAH (0.27 g calculated on the pure substance), 8,73 g VBH (mass ratio VBAH/VBH respectively 3/97) and heated to 80°C. Then uploading is 0.135 g of 2-azobis(2-methylpropionamidine)dihydrochloride (1.5% of the weight of the monomers).

Characteristics of latex:

The dry residue 11% wt.

The diameter of the polymer particles 155 nm.

The coefficient of polydispersity 1,04.

Stage B. Load 30,58 g MMA, of 5.06 g of BA, 0.36 g of EGDM (mass ratio of MMA/BA/AGDM respectively 85/14/1) and 0,145 g TMAH and 0.72 g azobis(2-methylpropionamide)dihydrochloride (0.4 and 2% by weight of monomers) in 200 g of water for 255 minutes

Characteristics of latex:

The dry residue of the latex 14,3% wt.

The glass transition temperature of the shell 70°C.

The diameter of the polymer particles 180 nm.

Stage Century. Enter 0,93 g DTMF (2% by weight of dry matter) in 100 g of water, then of 13.6 g of a 50% solution of trimethylamine (the molar ratio of trimethylamine / VBG equal to 2) for 30 min and granted the claim for 2 hours at a temperature of 70° C.

Feature latex:

The dry residue of 11.6% wt.

The diameter of the particles to 290.5 nm.

The relative volume of the cavity of 0.75.

ζ - potential + 39 mV.

Example 3. The process is carried out analogously to example 1, but at other concentrations of the reactants and the temperature.

Stage A. In the reactor load of 40.5 g of distilled water and 5 g of the solution UBAH (0.18 g calculated on the pure substance), to 4.23 g VBH and to 4.41 g of MMA (mass ratio VBAH/VBH/MMA respectively 2/48/50) and heated to 60°C. Then uploading is 0.135 g of 2-azobis[2-(imidazoline-2)propane]dihydrochloride (1.5% of the weight of the monomers).

Characteristics of latex:

The dry residue of 16.5% wt.

The diameter of the polymer particles 140 nm.

The coefficient of polydispersity of 1.05.

Stage B and C carried out analogously to example 1, but using in stage B 2-azobis[2-(imidazoline-2)propane]dihydrochloride, as azoinitiator.

Characteristics of latex:

The dry residue of 14.5 wt.%.

The diameter of the polymer particles of 250 nm.

The relative volume of the cavity 0,6.

ζ - potential of + 50 mV.

Example 4. The process is carried out analogously to example 3, but at other concentrations of the reactants.

Stage A. the Process is carried out analogously to example 3.

Stage B. Load 111,8 g MMA, 15,4 g BA and 1.28 g of EGDM (mass ratio 87/12/1) and 0.64 g TMAH and 3.2 g azobis(2-methylpropionamide)dihydrochloride (0.5 and 2.5% of the mass of the monomers) in 374 g of water for 950 minutes

Characteristics of latex:

The dry residue 24,8% wt.

The glass transition temperature of the shell 78°C.

The diameter of the polymer particles 360 nm.

Stage Century. Injected 2.8 g DTMF (2% by weight of dry matter) in 20 g of water, then 15.2 g of a 50% solution of quinoline (molar ratio quinoline / VBG equal to 2) and incubated for 2 hours at a temperature of 80°C.

Feature latex:

The dry residue of the latex 25,0% wt.

The particle diameter of 448 nm.

The relative volume of the cavity of 0.5.

ζ - potential of + 40 mV.

Example 5.

Stage A. Obtaining a copolymer core with increased particle size.

In a reactor with a volume of 500 cm3containing latex As obtained in example 1, carried out simultaneous loading of a Monomeric mixture containing 14 g VBH, 11.2 g BA and 2.8 g EN (mass ratio of 50/40/10) and the aqueous phase containing 0.07 g TMAH and 0.7 g of 2-azobis[2-(imidazoline-2)propane]dihydrochloride (0.25 and 2.5 percent by weight of the dosed monomers)dissolved in 260 g of water within 328,6 minutes

Then latex incubated 30 min, cooled to 30-40°and unload. For the Department of latex coagulum is filtered.

Feature latex:

The dry residue of the latex 10,0% wt.

The diameter of the polymer particles is 200 nm.

The coefficient of polydispersity of 1.02.

Stage B. In the reactor with a volume of 500 cm3download the seed latex obtained at the stage And in the amount of 90 g (content of the W dry matter 9 g), give a current of inert gas and for 30 min heated to 70°then carry out simultaneous loading of Monomeric mixtures containing 71,0 g MMA, 0.32 g EGDN (mass ratio to 95.5/0.5) and 0.36 g of TMAH and 1.73 g 2 azobis[2-(imidazoline-2)propane]dihydrochloride (0.5% and 2.4% of the weight of the dosed monomers), dissolved in 190 g of water for 326 minutes After boot latex was incubated for 30 minutes

Characteristics of latex:

The dry residue of the latex 23,3% wt.

The glass transition temperature of the shell 105°C.

The particle diameter of 395 nm.

Stage C. In the reactor containing the latex obtained at stage B, enter 1,65 g DTMF (2% by weight of dry matter) in 25 g of water, then 4.7 g of pyridine (molar ratio of pyridine / VBG equal to 2) for 30 min and incubated for 1 hour at 100°C.

Characteristics of latex:

The dry residue of 22.2% wt.

The particle diameter of 505 nm.

The relative volume of the cavity 0,52.

ζ - potential + 49 mV.

Example 6. The process is carried out analogously to example 5, but at other concentrations of the reactants and the temperature.

Stage A. Load of 54.8 g of monomer mixture and 0.27 g TMAH and 0.82 g of azo-bis[2-(imidazoline-2)propane]dihydrochloride (0.5 and 1.5% by weight of monomers), dissolved in 285,4 g of water within 480 minutes

Feature latex:

The dry residue 15% wt.

The diameter of the polymer particles 242,5 nm.

Stage B. In the reaction is the PR load 52,3 g of latex (dry matter content of 7.8 g), obtained at the stage And then perform the loading of 58 g of styrene (ST)and 19.6 g EN and 0.78 g of divinylbenzene (DVB) (mass ratio ST/EN/DVB respectively 74/25/1) and 0.2 g DTMF and 2 g of azo-bis[2-(imidazoline-2)propane]dihydrochloride (0.25 and 2.5 percent by weight of monomers) and 246 g of water within 360 minutes the Process is carried out at a temperature of 80°C.

Feature latex:

The dry residue of the latex 23,1% wt.

The glass transition temperature of the shell 100°C.

The diameter of the polymer particles 410 nm.

Stage C. In the reactor is injected 1,02 g TMAH (1% of dry weight) in 25 ml of water, 2.35 g of pyridine (molar ratio of pyridine / VBG equal to 1) for 20 min and incubated for 2 hours at 100°C.

Feature latex:

The dry residue of 22.5% wt.

The particle diameter of 595 nm.

The relative volume of the cavity to 0.67.

ζ - potential + 35,5 MB.

As follows from the above examples, the developed method allows to obtain a cationic latex hollow polymer particles with a dry matter content of 11-25% wt. with a total diameter of particles varying between 250 and 600 nm, the relative volume of the cavity from 0.50 to 0.85 and ζ - potential of the latex particles in the range from +35 to +50 mV.

The claimed invention satisfies the criterion of "novelty", as when you receive a cationic latex with hollow particles first proposed sequence of chemical reactions: (A) emulsion co)polymerization of vinylbenzoate; (B) copolymerization of (meth)acrylates and other comonomers in the presence of the latex obtained in stage (A), and the formation of particles with the morphology of core-shell; (B) amination vinylbenzoate links.

The claimed invention satisfies the criterion of "inventive step", as in the well-known sources of information there are no data from which would be an obvious opportunity for the realization of this sequence of chemical reactions that provide cationic latex with hollow particles with virtually no coagulum with the relative volume of the cavity in the particle to 0.85.

The criterion of "industrial applicability" is proved by the data given in the examples, which show that the method is free from the disadvantages of the prototype and is easy, as is carried out in a single reactor without isolation of intermediate products and can be implemented on existing production of latexes without any reconstruction of the equipment.

Sources of information taken into account:

1. Vonavona. Hollow polymer spheres submicron size: properties, applications, production methods. High-molecular compounds. Ser. S. T. 46, No. 12, s-2171 (2004).

2. US Patent 4427836, 1984.07.24.

3. US Patent 4594363, 1986.06.10.

4. US Patent 5494971, 1996.02.27.

5. RF patent 2128670, 1999.10.04.

6. WO Patent 0068310, 2000.11.1.

7. WO Patent 0160510 A1, 2001.08.23.

8. US Patent 4469825, 1984.09.04 prototype.

1. A method of obtaining a cationic latex hollow polymer particles, comprising at least three stages:

(A) water-emulsion (co)polymerization Ethylenediamine monomers, one of which contains a functional group capable of when certain chemicals to ionize;

(B) copolymerization Ethylenediamine monomers in the presence of latex particles obtained in stage A, with the formation of particles with the morphology of the nucleus (copolymer obtained in stage a) to the shell (the copolymer obtained in stage B);

(B) chemical treatment of functional groups of the core, causing them ionization, hydration, swelling of the copolymer core and a shell extension, leading to the formation of particles with a single Central cavity, characterized in that as the monomer containing a functional group on the stage And use vinylbenzoic and stage represents amination vinylbenzoate parts of tertiary aliphatic amines, pyridine or its derivatives.

2. The method according to claim 1, characterized in that stage And obtain latex particles of the core is carried out at a mass ratio of monomers vinylbenzoic/universitymanila/alkyl(meth)acrylate/acrylic-nitrile (48-98)/(2-3)/(0-50)/(0-10) according to the state in the presence of water-soluble azoinitiators when the mass ratio of the monomer/water (10-15)/(85-90).

3. The method according to claim 1, characterized in that, during the stage And universitymanila injected into the aqueous phase.

4. The method according to any of claim 1 to 3, characterized in that stage And perform bare copolymerization of vinylbenzoate, n-butyl acrylate and Acrylonitrile at a mass ratio of 50/40/10, respectively, using as the seed latex obtained according to claim 2, when the mass ratio of the monomer/polymer seed from 3 to 6 in the presence of cationic surfactants of the type tetraalkylammonium in the amount of 0.25-0.5% by weight of comonomers.

5. The method according to claim 1, characterized in that stage B is carried out with the use of a seed latex obtained at the stage And, when the mass ratio of monomers of alkyl(meth)acrylate or vinylaromatic monomer/Acrylonitrile/cross-linking of comonomer (74-99,5)/(0-25)/(0.5 to 1.0), respectively, by selecting the ratio of comonomers in such a way that the glass transition temperature of the copolymer membranes was in the range of 70-105°C.

6. The method according to claim 1, characterized in that stage B upon receipt of the copolymer shell use cationic surfactants of the type tetraalkylammonium in the amount of 0.25-0.5% by weight of comonomers and water-soluble azoinitiator.

7. The method according to claim 1, characterized in that as the water-soluble azoinitiators stages a and B using 2,2'-azobis(2-methylpropionamidine)dihydrochloride or 2-azobis[2-(imidazoline-2)propane]dihydrochloride in the amount of from 1.5 to 3.0% by weight of comonomers and copolymerization processes in the stages a and B is carried out at temperatures of 60-80°C.

8. The method according to claim 1, characterized in that the mass ratio of the copolymer of the shell and the kernel is in the range from 3 to 14, preferably from 8 to 10.

9. The method according to claim 1, wherein the amination benzylchloride groups of the copolymer kernel on stage In the conduct of the tertiary aliphatic amine at 70°if the glass transition temperature of the copolymer shell does not exceed 75°and pyridine or its derivatives at 80-100°if the glass transition temperature of the copolymer shell above 75°Since, when the molar ratio of amine/benzylchloride group from 1 to 4.

10. The method according to claim 9, characterized in that before the aminating in latex injected cationic surfactant type tetraalkylammonium in the amount of 1-4% by weight of the copolymer.



 

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