RU2156775C2 - Latex system and method of preparation thereof - Google Patents

Abstract

FIELD: polymer production. SUBSTANCE: preparation of latex system includes aqueous-emulsion (co)polymerization of at least one ethylenically- unsaturated monomer in presence of (i) latex system stabilization- effective amount of water-soluble protective colloid selected from group including carboxymethylcellulose and its derivatives with lower limit of carboxyl substitution degree ca. 0.7; hydroxymethylcellulose, ethylhydroxymethylcellulose, methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, hydrophobically substituted cellulose ethers; polyacrylic acid and its alkali metal salts; oxyethylated starch derivatives; sodium and other alkali metal polyacrylates; water-soluble starch glue; gelatin, water-soluble alginates, casein, agar, natural and synthetic gums, partially or completely hydrolyzed polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, and methyl vinyl ether/maleic anhydride copolymer; and also (ii) polymerization initiator. Invention is distinguished by that (i) above-said ethylenically-unsaturated monomer is monomer selected from group including acrylic acid, butyl acrylate, methyl methacrylate, acrylic acid esters, styrene, vinyl ethers, vinyl and vinylidene halides, N- vinylpyrrolidone, ethylene, C₃-C₂₄-alpha-olefins, allylamines, saturated monocarboxylic acid esters and amides, propylene, 1-butene, 1-pentene, 1-hexene, 1-decene, allyl acetate, allyl propionate, allyl lactate, corresponding amides, and their mixtures, and (ii) above-said water- soluble protective has weight-average molecular weight below approximately 75000. EFFECT: improved mechanical stability of latex. 63 cl, 6 tbl, 23 ex

Description

 The present invention relates to aqueous polymer dispersions obtained from ethylenically unsaturated monomers in the presence of a water-soluble protective colloid, and to methods for their preparation. In industrial emulsion polymerization processes, surfactants are usually used either alone or in combination with polymer protective colloids. The disadvantage of this is that surfactants must be used to prepare shear-resistant latexes, which is uneconomical and can cause unwanted side effects. For example, the presence of surfactants in latex systems can have a negative effect on sensitivity to water and cause foaming of the final products. In addition, in commonly used amounts, surfactants do not give these end products sufficient mechanical stability.

 It is known in the art that the presence of protective colloids as joint stabilizers, such as hydroxyethyl cellulose (HEC) and polyvinyl alcohol (PVO), in the emulsion polymerization of ethylenically unsaturated monomers, including vinyl monomers, vinyl monomers together with an acrylic monomer, such as acrylic esters, methacrylic esters or mixtures thereof, provides latexes with a submicrometric particle size having improved rheology, stability and performance characteristics ISTIC. These aqueous polymer dispersions can be used to prepare latex paints, binders for non-woven textile materials, water-based printing inks, paper coating products and water adhesives, such as pressure sensitive adhesives.

 In processes of emulsion polymerization of monomers, including acrylic compounds or styrene, either individually or in combination with other monomers, protective colloids such as cellulosic materials or PVA cannot always be used as joint stabilizers. When known protective colloids are used in acrylic or styrene-based latex systems, intense flocculation occurs, which is a sign of a lack of mechanical stability. This flocculation is due to the high tendency of the protective colloid to penetrate directly into the polymer chain involved in the reaction. Such a phenomenon is commonly known as graft copolymerization.

 It must be borne in mind that grafting onto the chain and grafted copolymerization alone cannot be completely eliminated. The quantitatively grafted graft copolymerization does not cause flocculation; moreover, it increases the stability of latex systems, which has long been known for vinyl acetate copolymer latexes. Coagulation is caused by a combination of excessive grafted copolymerization with the possibility of the formation of bridging compounds between particles. The formation of bridging compounds between particles is determined not only by one amount of grafted material or particle sizes, but also depends on the amount of water-soluble polymer contained in the aqueous phase, the molecular weight of the protective colloid, dry matter content, etc.

 In any case, depending on the particular latex system, the lack of mechanical stability can be eliminated using large amounts of surfactant individually or in combination with a protective colloid. For example, in vinyl acetate-based systems, a large amount of the protective colloid is used in combination with a surfactant, while in acrylic-based systems, the surfactant is used in large quantities on its own. However, latexes prepared using such large quantities of surfactants are characterized by the above disadvantages associated with operational properties.

 Thus, in this industry there is a need to eliminate the inherent disadvantages of known latex systems associated with the use of large quantities of surfactants or known protective colloids.

 One approach to solving this problem, described in US Pat. No. 4,684,704 to Craig ('704), consists of using from about 0.01 to about 1.7% by weight (of the total amount of the monomer component) of hydrophobically modified hydroxyethyl cellulose ( HMHEC), which is easily and successfully introduced into dispersions or latexes by emulsion polymerization of monomers characterized by a low ability to graft copolymerization with a protective colloid. The resulting latexes have a particle size of less than 1.0 micrometer and are characterized by excellent mechanical stability.

 Another solution to the polymerization of acrylic monomer systems described in US Pat. No. 4,845,175 to Lo is to use 0.02-2.0 wt.% Hydrophobically modified hydroxyethyl cellulose as a protective colloid.

 Another solution related to the polymerization of acrylic monomer systems and described in US Pat. No. 4,659,771 to Craig ('771) consists in using, in addition to the protective colloid, from about 0.1 to 5% by weight of an almost completely water-soluble conjugated unsaturated monomer, such as furancarboxylic acid, styrene sulfonic acid, metal salts, amine salts, ammonium salts and quaternary ammonium salts of rosin acids and acids containing 4-36 carbon atoms.

 The method of producing the latex system described in this patent, which is the closest analogue of the claimed invention, consists in water emulsion (co) polymerization of ethylenically unsaturated monomers, with a small amount of water-soluble conjugated unsaturated copolymer in the presence of a protective colloid.

 An object of the present invention is to provide a latex characterized by improved mechanical stability.

The problem is solved by a method of preparing a latex system characterized by improved mechanical stability, including aqueous emulsion (co) polymerization of at least one ethylenically unsaturated monomer in the presence of an effective amount of a water-soluble protective colloid selected from the group consisting of carboxymethyl cellulose and its derivatives, to stabilize the latex system. the limit of the degree of carboxyl substitution of which is approximately 0.7, hydroxyethyl cellulose, ethyl hydro ethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose, hydroxypropyl cellulose, hydrophobically modified cellulose ethers, polyacrylic acid and its alkali metal salts, hydroxyethylated starch derivatives, sodium polyacrylates and other alkali metals, water-soluble starch glue, natural gum, gelatin, gelatin, gelatin, gelatin, gelatin, , partially and completely hydrolyzed polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and methyl vinyl copolymer ether and maleic anhydride, as well as a polymerization initiator, in which according to the invention as an ethylenically unsaturated monomer a monomer selected from the group consisting of acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, acrylic esters, styrene, vinyl ethers, vinyl-, vinylidene halides, N-vinyl pyrrolidone, ethylene, C ₃ -C ₂₄ alpha-olefins, allyl amines, allyl esters of saturated monocarboxylic acids, their amides, and mixtures thereof, propylene, 1-butene, 1-pentene, 1-hexene, 1-decene, ALL latsetata, allyl propionate, allillaktata, their amides, and water-soluble protective colloid used has a weight average molecular weight less than about 75,000.

 The problem is also solved by a method of preparing a latex system characterized by improved mechanical stability, including aqueous emulsion (co) polymerization of at least one ethylenically unsaturated monomer in the presence of an effective amount of a water-soluble protective colloid selected from the group consisting of hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, and stabilize the latex system. methyl hydroxypropyl cellulose, hydroxypropyl cellulose, hydrophobically modified cellulose ethers, ethoxylated starch derivatives, partially and fully hydrolyzed polyvinyl alcohol, polyacrylic acid, sodium polyacrylates and other alkali metals, polyacrylamide, a copolymer of methyl vinyl ether, maleic anhydride, polyvinyl pyrrolidone, water-soluble agara, starch, starch natural and synthetic gums and their derivatives and a polymerization initiator in which, according to the invention, a protective colloid with non-mass molecular weight less than approximately 75,000.

In addition, the task is also solved by the latex system, including an aqueous emulsion containing
(a) (co) a polymer of at least one ethylenically unsaturated monomer; and
(b) an effective amount of a water-soluble protective colloid to stabilize this latex system selected from the group consisting of carboxymethyl cellulose and its derivatives, the lower limit of the degree of carboxyl substitution of which is approximately 0.7, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose, hydroxy acid and hydroxypropyl cellulose, hydroxy its alkali metal salts, ethoxylated starch derivatives, sodium polyacrylates and other alkali metals, hydrogen soluble starch glue, gelatin, water-soluble alginates, casein, agar, natural and synthetic gums, partially and completely hydrolyzed polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and a copolymer of methyl vinyl ether and maleic anhydride, of which one is selected from the group consisting of ethylene and , methacrylic acid, butyl acrylate, methyl methacrylate, acrylic esters, styrene, vinyl ethers, vinyl, vinylidene halides, N-vinylp rrolidona, ethylene, C ₃ -C ₂₄ alpha-olefins, allyl esters of saturated monocarboxylic acids, their amides, and mixtures thereof, propylene, 1-butene, 1-pentene, 1-hexene, 1-decene, allyl acetate, allyl propionate, allillaktata, their amides, and the water-soluble protective colloid has a weight average molecular weight of less than about 75,000.

 The latex system according to the invention is included in the composition of the latex paint, comprising additionally at least one product selected from the group consisting of pigment and filler.

 In the latex paint composition, preferably the latex is solvent free.

 Advantageously, in the latex paint composition, the (co) polymer comprises particles whose average size is less than about 500 nanometers.

 Moreover, the composition of the latex paint preferably include a paint for glossy coatings, the volume concentration of the pigment in which is less than about 50, or paint for matte coatings, the volume concentration of the pigment in which is about 50 or more.

 The latex system according to the invention is included in the composition of a water-based ink, comprising, in addition to the latex system, at least another component of the ink.

 The latex system according to the invention is included in a paper coating composition comprising, in addition to the latex system, at least another component of the paper coating composition.

 The dextrin-free adhesive composition includes the latex system of the invention and at least another dextrin-free adhesive component.

 A binder for nonwoven textile materials includes the above latex system and at least another component of the binder.

Another embodiment of the latex system according to the invention is a latex system characterized by improved mechanical stability, including an aqueous emulsion containing
(a) (co) a polymer of at least one ethylenically unsaturated monomer, and
(b) an effective amount of a water-soluble protective colloid to stabilize this latex system selected from the group consisting of hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose, hydroxypropyl cellulose, hydroxyethylated starch derivatives, partially and fully hydrolysed polyvalent polyvalent metal , polyacrylamide, copolymer of methyl vinyl ether and maleic anhydride, polyvinylpyrrolidone, in soluble starch glue, gelatin, water-soluble alginates, casein, agar, natural and synthetic gums and their derivatives, in which according to the invention, the water-soluble protective colloid has a weight average molecular weight of less than about 75,000.

 It has been unexpectedly found that the use of a low molecular weight protective colloid in the emulsion polymerization process of ethylenically unsaturated monomers gives the resulting polymer excellent mechanical stability. The upper limit of the weight average molecular weight of such a protective colloid is about 75,000, preferably about 50,000, and most preferably about 20,000. The lower limit of the weight average molecular weight of this protective colloid is about 5,000, preferably about 10,000, and most preferably about 15,000.

 The present invention is particularly effective with respect to acrylic or styrene latex systems. As indicated above, for known latex systems on an acrylic and styrene basis, the use of technically recommended amounts of a protective colloid is impractical due to the high degree of flocculation. The use of large amounts of surfactant to solve this problem can lead to a negative effect on sensitivity to water and cause foaming of finished products. In addition, in commonly used concentrations, surfactants do not provide the finished products with sufficient mechanical stability. It has been unexpectedly found that the use of a low molecular weight protective colloid in latex systems on acrylic and styrene based can reduce the content of surfactant or even eliminate it. Finished products, as a rule, are characterized by reduced sensitivity to water, less foaming and greater mechanical stability in comparison with known systems. Mechanical stability as such can manifest itself in greater vitality. In addition, when used in the composition of paints, these latter show a weakened tendency to sagging and improved filling.

 A preferred polysaccharide protective colloid is a water-soluble cellulose ether, which is prepared using ethylene oxide, methyl chloride, propylene oxide, monochloracetic acid, etc. or mixtures thereof. Particularly preferred are carboxymethyl cellulose (CMC) and its derivatives, the degree of carboxyl substitution (C3) of which is from about 0.7 to about 2.9, more preferably from about 0.7 to about 1.5, and most preferably from about 1.0 to about 1.4. Suitable carboxymethyl cellulose derivatives include methyl carboxymethyl cellulose, ethyl carboxymethyl cellulose, hydroxyethyl carboxymethyl cellulose, hydroxypropyl carboxymethyl cellulose, methoxyethyl carboxymethyl cellulose and ethoxyethyl carboxymethyl cellulose dimethyl cellulose.

 Hydroxyethyl cellulose (HEC) may also be used, with a preferred degree of hydroxyethyl molar substitution (MOH) of from about 1.6 to about 4.0, more preferably from about 1.8 to about 3.5, and most preferably from about 1.8 to approximately 2.9.

 In addition, hydrophobically modified cellulose ethers may be used. Suitable hydrophobically modified cellulose ethers are cellulose ethers which are substituted with a hydrocarbon containing 4-25 carbon atoms, the mass amount of this hydrocarbon being from about 0.1 to about 3.0 wt.%, More preferably from about 0.1 to about 2.0 wt.% of the total amount of hydrophobically modified cellulose ether.

 A preferred hydrophobically modified cellulose ether is hydrophobically modified hydroxyethyl cellulose (HMHEC). A hydrophobically modified hydroxyethyl cellulose that can be used to practice the present invention is hydroxyethyl cellulose, which is further substituted with a hydrocarbon containing 4-25 carbon atoms, the mass amount of this hydrocarbon being from about 0.1 to about 3.0%, more preferably from about 0.1 to about 2.0% of the total hydrophobically modified hydroxyethyl cellulose of the total. In a preferred embodiment, the degree of hydroxyethyl MoH of this HMHEC is from about 2.9 to about 4.0, more preferably from about 2.9 to about 3.5.

 Other cellulose ethers, for example those that can be used as protective colloids of the present invention, include ethyl hydroxyethyl cellulose (EHEC), methyl cellulose (MC), methyl hydroxypropyl cellulose (MHPC) and hydroxypropyl cellulose (GPC).

 Other polysaccharides and materials that can be used as protective colloids according to the present invention are ethoxylated starch derivatives, partially and fully hydrolyzed polyvinyl alcohol, polyacrylic acid, alkali metal polyacrylates (potassium, sodium, etc.), polyacrylates, polyacrylamide , a copolymer of methyl vinyl ether and maleic anhydride, polyvinylpyrrolidone, water-soluble starch glue, gelatin, water-soluble alginates, casein, agar and natural and artificial gums.

 In a preferred embodiment, the protective colloid is used in an amount effective to stabilize the latex system. In this context, an effective amount is that amount which serves to stabilize the latex system during aqueous emulsion polymerization and after completion of this polymerization.

 In particular, the concentration of the protective colloid during the implementation of the emulsion polymerization process of the present invention can be varied over a wide range, the upper limit being determined only by economic and practical considerations based on what properties the final product should have. In a preferred embodiment, the upper limit is about 5.0 wt.%, More preferably 3.5 wt.% And most preferably about 2.5 wt.% Of the total amount of ethylenically unsaturated monomers in the reaction mass. A preferred lower limit is about 0.005% by weight. A more preferred lower limit is about 0.05 wt.% And a most preferred lower limit is about 0.1 wt.% Of the total amount of ethylenically unsaturated monomer component.

 The protective colloid of the invention can be used either individually or in combination with other protective colloids or surfactants. For example, the CMC derivative can be used as the sole stabilizer or in combination with one or more surfactants. The CMC used in the present invention is marketed by the Aqualon Company, Wilmington, pc. Delaware, in the form of water-soluble polymers under the trademarks "Ambergum" types 1221 and 3021. Acceptable hydrophobically modified hydroxyethyl cellulose is marketed by Hercules Incorporated, Wilmington, pc. Delaware, under the trademark "Natrosol Plus".

 In addition, monomers used in accordance with the present invention include at least one ethylenically unsaturated monomer, such as vinyl esters or ethers, styrene and others. Acrylates that use the present invention include acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate and other acrylate and methacrylate esters.

 In general, any ethylenically unsaturated monomer that may optionally be cyclic and which may be polymerized with a free radical initiator may be used to practice the present invention. Preferred ethylenically unsaturated monomers include monomers that contain up to 23 carbon atoms.

Examples of suitable monomers include vinyl esters, vinyl ethers, vinyl and vinylidene halides, N-vinyl pyrrolidone, ethylene, C ₃ -C ₂₄ alpha olefins, allylamines, saturated monocarboxylic acid allyl esters and their amides, as well as dienes and their derivatives.

 Appropriate vinyl esters include aliphatic vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl caproate and vinyl versatate.

 Typical examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether and n-butyl vinyl ether.

Suitable C ₃ and higher molecular weight alpha olefins include propylene, 1-butene, 1-pentene, cyclopentene, 1-hexene, cyclohexene and 1-decene.

 Examples of typical allylamines are allylamine itself and N-substituted allylamines.

 Suitable dienes include butadiene, cyclopentadiene and dicyclopentadiene.

 Suitable allyl esters of saturated monocarboxylic acids may include allyl acetate, allyl propionate and allyl lactate, as well as, in particular, their amides.

 The polymers of the invention can be prepared from one or more ethylenically unsaturated monomers. In this regard, it should be noted that the term "polymer" also includes homopolymers and copolymers that are obtained by polymerization of two or more different monomers.

 For acrylic and styrene-based latexes, low molecular weight CMCs are preferred. For vinyl acetate-acrylate systems, predominantly low molecular weight HMHECs are used, but low molecular weight HECs and low molecular weight CMCs can also be used. When acrylic acid or methacrylic acid is used in the polymerization process, its preferred content is from about 0.005 to about 2 wt.%, More preferably from about 0.05 to about 1 wt.% Of the total amount of ethylenically unsaturated monomer component.

Polymers of the invention with a relatively high glass transition temperature (for example, from about 50 to about 150 ^° C.) can be described as “solid”, and polymers with a relatively low glass transition temperature (for example, from about -100 to about -3 ^° C.) be classified as "soft." A factor affecting the degree of hardness and softness is determined by the properties of the particular ethylenically unsaturated monomers that are used.

 The differences between ethylenically unsaturated monomers give rise to varying degrees of hardness or softness, which is why they are known as “hard” and “soft” monomers. The relative hardness and softness of various monomers is known in the art. Thus, the hardness or softness of the polymer is affected by the hardness or softness of the monomers forming the polymer and the relative ratios between these monomers.

 In preparing the copolymer latex system, the ratios between the “hard” and “soft” monomers are selected so that a continuous latex film is formed at the temperature created. Styrene-acrylic products can be obtained by containing styrene units in the resulting copolymer in the range from about 0.005 to about 70 wt.%. Vinyl acrylate products can be obtained in the range of weight ratios between the units of vinyl acetate and acrylate monomers from about 1: 1 to about 10: 1, preferably from about 7: 3 to about 9: 1.

 The resulting dispersions obtained in accordance with the present invention significantly improve the scratch resistance of latex paints prepared with their use. Latex paints include paints for glossy coatings and matte coatings, wherein the volume concentration of pigment in the paint for glossy coatings is less than about 50, and the volumetric concentration of pigment in the paint for matte coatings is about 50 or more.

For the practical implementation of the present invention, anionic, cationic, nonionic and amphoteric surfactants known in the art can be used, as well as mixtures thereof. Suitable surfactants include polyglycol ethers, sulfonated paraffinic hydrocarbons, higher alkyl sulfates such as lauryl sulfate, alkali metal salts of fatty acids such as sodium stearate and sodium oleate, sulfuric acid esters of fatty alcohols, ethoxylated C ₄ -C ₅₀ alkyl phenols and their sulfonation products, such as nonylphenol ethoxylated with 4-50, more preferably 10-20 ethylene oxide units, ethoxylated c ₄ -C ₅₀ alkanols and their sulfonation products, and also sulfosuccinic esters sour you, such as sodium dioctylsulfosuccinate, and mixtures thereof. These surfactants or emulsifiers are optional, and their use is not always required, but if used, their amount is usually 0.1-5.0 wt.%, Preferably 0.1-2.0 wt.% Of the total number of ethylenically unsaturated monomers introduced into the process.

 You can apply any of the known methods of emulsion polymerization, including batch, semi-periodic and continuous thermal or redox technology. Preferably, the semi-batch addition of monomer with the addition of initiator or catalyst is either in a single portion or continuously. The polymerization process can also be carried out with a large shear force, which means, for example, the possibility of using a reactor with circulation for carrying out the reaction. In a preferred embodiment, in the first portion loaded into the reactor, ethylenically unsaturated monomer or monomers are introduced in an amount of from about 0 to about 40 wt.%, More preferably from about 1 to about 25 wt.% And most preferably from about 5 to about 15 wt. % Also, in a preferred embodiment, from the initial portion loaded into the reactor, the initiator is introduced from about 0 to about 60 wt.%, More preferably from about 50 to about 60 wt.%. The continuous supply of any reaction component or components is usually carried out over a period of from about 2 to about 5 hours. The initiator or catalyst may be administered in a single portion or in a slow mode, although this is not necessary for the practical implementation of the present invention.

Typically, the monomers are polymerized by aqueous emulsion polymerization at a temperature of from about 20 to about 120 ^° C, preferably from about 45 to about 95 ^° C, in the presence of a free radical polymerization initiator, preferably a water-soluble peroxide, for example, hydrogen peroxide, persulfates such as persulfates potassium, sodium and ammonium, or in some cases perborates. Other methods known in the art can also be used to polymerize monomers, such as, for example, using redox polymerization catalyst systems such as potassium persulfate and sodium bisulfite. The initiator is used in a concentration of 0.2-2.0 wt.% By weight of the monomer (s), preferably in an amount of 0.3-1.0 wt.%.

 The product prepared according to the invention is a latex system comprising particles of a polymer thus obtained dispersed as a dispersed phase in an aqueous continuous phase, and also comprising a protective colloid. In a preferred embodiment, the average particle size of these particles is less than about 500 nanometers, more preferably less than about 300 nanometers, and most preferably less than about 200 nanometers.

 The latex system of the present invention has excellent shear resistance. In accordance with the above description, it can be used in latex paint compositions. In a preferred embodiment, these ink compositions further include at least one pigment and a filler, and additional components, including thickeners, may also be added to the latex paint compositions.

 In addition, the latex system of the present invention can be used in compositions of water-based printing inks, paper coating agents, binders for non-woven textile materials and adhesive compositions, in particular dextrin-free adhesive compositions.

 In this description, in all cases, unless otherwise specified, the quantities are indicated in mass parts or percent.

 Below the invention is illustrated in more detail by examples, which are presented only to illustrate its essence and do not limit the scope of the invention.

Examples
Mw was determined using the method of high-resolution chromatography with size displacement (HVR), consisting in the following.

 Instrumentation: A Varian 5010 LC instrument equipped with a Waters Associates R401 differential refractometer and a Keep and Zonen Model BD 40 recorder was used for HVR analysis. In order to be able to periodically flush the reference side of the cell between the sample exit lines and the inlet of the reference sample, a 3-way lever valve Rheodyne model 5302 was installed between the sample exit lines. However, during the analysis, the stationary mobile phase was contained on the reference side of the refractometer. Inlet was performed using a Rheodyne Model 7010 valve equipped with a 50 microliter sample inlet tube.

[5 см х 4,1 мм (внутренний диаметр), серия N 227904], двух ГПХ-аналитических колонок с размерами пор насадки

[25 см х 4,6 мм (внутренний диаметр), серии N 222033, 49201] и ГПХ-аналитической колонки с размерами пор насадки

[25 см х 4,6 мм (внутренний диаметр), серия N 48205]. Эти колонки подключали последовательно в указанном порядке.Chromatographic columns: Synchrom, Inc. HVR columns were used. (Linken, Indiana); they contained a chemically bonded glyceryl propyl phase on silica. The set of columns used consisted of a preliminary column for GPC with nozzle pore sizes

[5 cm x 4.1 mm (inner diameter), series N 227904], two GPC analytical columns with nozzle pore sizes

[25 cm x 4.6 mm (inner diameter), series N 222033, 49201] and GPC analytical columns with nozzle pore sizes

[25 cm x 4.6 mm (inner diameter), series N 48205]. These columns were connected in series in that order.

 Preparation of the mobile phase: An acetate buffer solution of 0.7 M ionic strength with a pH value of 3.7 was used as the mobile phase in the analyzes. A mobile phase with a pH of 3.7 was prepared by first introducing 60 ml of a 4 M solution of sodium acetate and 440 ml of 4 M acetic acid into a one-liter volumetric flask and adding distilled deionized water to its full volume. As a result, an ionic strength buffer of 0.24 M was formed with a pH value of 3.7. Further, the ionic strength of this solution was increased to 1.44 M by the addition of 0.4 mol of sodium sulfate in 1 liter of a 0.24 M acetate solution. Such a solution of ionic strength of 1.44 M was used in the preparation of the sample to minimize inconsistencies with the mobile phase. The final mobile phase was prepared by diluting a 1.44 M double strength solution with distilled deionized water in a 1: 1 ratio and filtering through a Millipore Type GS membrane with a pore size of 0.22 μm.

 Sample preparation: All samples were prepared by dissolving 0.150 g of the polymer (adjusted for dry matter by moisture content) in distilled deionized water to bring the total volume to 25 ml, obtaining an initial concentration of 6 mg / ml. Further, these aqueous solutions were diluted in a 1: 1 ratio with a 1.4 M double strength acetate buffer solution to a concentration of 3 mg / ml, which approximately corresponded to the composition of the mobile phase. Prior to injection, all sample solutions were filtered through Millex-HV disposable filter devices (Millipore).

колонки

(Synchropack)
Подвижная фаза: - 0,7 М ацетатный буфер с pH 3,7
Скорость потока: - 0,5 мл/мин (по данным измерений, 0,51 мл/мин)
Давление: - ≈135-140 атм
Скорость движения диаграммной бумаги: - 1 см/мин
Концентрация пробы: - 1,5-2,0 мг/мл
Загрубление ДПП: - 2-кратное
В вышеописанных условиях производили многократный ввод проб. Для сравнения с графиком для Mw стандарта кривые строили наложением данных ХВР-хроматограмм.Analysis conditions
Set of columns: - GPC-preliminary,

speakers

(Synchropack)
Mobile phase: - 0.7 M acetate buffer with a pH of 3.7
Flow rate: - 0.5 ml / min (according to measurements, 0.51 ml / min)
Pressure: - ≈135-140 atm
Graph paper speed: - 1 cm / min
Sample concentration: - 1.5-2.0 mg / ml
Roughness of the DPP: - 2-fold
Under the conditions described above, repeated injection of samples was performed. For comparison with the graph for the Mw standard, the curves were constructed by superimposing data from HVR chromatograms.

 Calibration: Using the previous volume (size), a number of dextran standards from various Mw from American Polymer Standards Corporation (DXTKIT) were analyzed. The standard with the lowest molecular weight (DXT-180 Mw), which was mainly eluted with a common leakage limit, was also used as an internal standard.

Method for determination of average molecular weight Mw
Example 1
Fully acrylic materials stabilized with low molecular weight CMC
This example presents one of the variants of aqueous dispersions of the present invention and the method of their preparation.

The polymerization was carried out in a 2-liter glass reaction vessel, which was equipped with a thermocouple, reflux condenser, monomer inlet means, initiator inlet means and an anchor mixer. 16.6 g of a protective colloid [carboxymethyl cellulose (CMC) marketed by Aqualon Company under the trademark Ambergum 3021, average molecular weight (Mw) from about 7000 to 11000, degree of substitution of carboxyl groups of about 1.2, was dissolved in 461 g of demineralized water. , the concentration of the solution is 29.6% with a Brookfield viscosity of 630 mPa • s at 25 ^o C] together with 1.6 g of sodium bicarbonate. After complete dissolution, the temperature was raised to 85 ^o C using a water bath. Then, a 40% initiator solution (1.5 g of potassium persulfate in 50 g of demineralized water) was uniformly added over 30 s. After one minute, the monomer was started. A monomer mixture (248.6 g of butyl acrylate, 248.6 g of methyl methacrylate and 2.8 g of methacrylic acid) was added at an initial rate of 54.5 g / h, and during the first hour of the reaction this speed was gradually increased to 163.5 g / h . When the temperature returned to a level of 85 ^° C, approximately 95% of the remainder of the initiator solution was added, and the remaining 5% initiator solution was added thereafter after the total amount of monomer was added. The indicated 95% of the remaining initiator was introduced during the same period of time as the monomer input, the initiator feed rate being adjusted in accordance with the monomer feed rate so that the addition of the monomer and the indicated 95% initiator residue was completed simultaneously. The monomer, as well as the initiator, was injected within 3.5-4 hours using a plunger pump and a hose pump, respectively.

The reaction temperature was maintained at 85 ^o C. The polymerization was completed, maintaining the temperature at 85 ^o C, within 1 hour after the introduction of the initiator and monomer. Next, the resulting latexes were cooled to room temperature. During the reactions, the stirring speed was 200 rpm.

Comparative Example A
Fully acrylic materials stabilized with high molecular weight CMC
This comparative example illustrates the need to add a low molecular weight protective colloid. The formulation and the same method as described in Example 1, except for the following changes: instead of using 16.6 g of Ambergum ^® 3021 product were used 10 g of CMC 12M8R [a Brookfield viscosity of 430 mPa • s (2% solution at 25 ^o C)] with Mw of approximately 300,000. To bring the dry matter content in the resulting latex to the same level, in this case, the amount of demineralized water was brought to 473 g.

Comparative Example B
Fully acrylic materials stabilized with a nonionic surfactant
This comparative example illustrates the need to use a large amount of nonionic surfactant to produce shear-resistant latexes, and this example is intended to be compared with the data of the invention. The same composition and the same method were used as described in Example 1, except that instead of 16.6 g of the protective colloid, 20 g of a nonionic surfactant were used (ethoxylated nonylphenol with 10 ethylene oxide units: Intrasol NP10, 100% active substance , Stockhausen), which was dissolved in 433 g of demineralized water.

Comparative Example B
Fully acrylic materials stabilized with both anionic and nonionic surfactants
This comparative example illustrates the need to use a large amount of surfactant in fully acrylic latexes without the use of a protective colloid to produce shear-resistant latexes. The same composition and the same method were used as described in Example 1, except that instead of 16.6 g of the protective colloid, 10 g of a nonionic surfactant was used (ethoxylated nonylphenol with 10 ethylene oxide units: Intrasol NP10, 100% active substance ), together with 10 g of anionic surfactant (dioctyl sulfosuccinate: Aerosol OT-75, 75% active, Cyanamid), which were dissolved in 472 g of demineralized water.

Example 2
Surfactant-free styrene-acrylic materials stabilized with low molecular weight CMC
This example presents another embodiment of the invention. Polymerization processes were carried out in a 2-liter glass reaction vessel, which was equipped with a thermocouple, a reflux condenser, a monomer inlet means, an initiator inlet means and an anchor mixer. In 450 g of demineralized water were dissolved 33 grams of the protective colloid (CMC Ambergum ^® 3021 solution at a concentration of 29.6%, a viscosity of 630 mPa • s at 25 ^o C) and 1.6 g of sodium bicarbonate. After complete dissolution, the temperature was raised to 85 ^o C using a water bath. Then, a 40% initiator solution (1.5 g of potassium persulfate in 50 g of demineralized water) was uniformly added over 30 s. After one minute, the monomer was started. The monomer mixture (245 g of butyl acrylate, 245 g of styrene and 10 g of methacrylic acid) was introduced at an initial rate of 54.5 g / h and during the first hour of the reaction this speed was gradually increased to 163.5 g / h. The rest of the polymerization method was similar to that described in example 1.

Comparative Example D
Styrene-acrylic materials stabilized with anionic and nonionic surfactants
This comparative example illustrates the need to use low molecular weight CMC as a stabilizer at low concentrations of surfactants to obtain stable latexes. The same composition and the same method were used as described in Example 2, except that instead of 33 g of the protective colloid, 15 g of the anionic surfactant was used (alkylaryl sulfate ester: Disponil AES 60, 33% active substance, Henkel GmbH, Dusseldorf, Germany) together with 5 g of nonionic surfactant (ethoxylated nonylphenol with 10 ethylene oxide units: Intrasol NP10, 100% active substance) in 463 g of water. The monomer mixture in this case included 248.6 g of butyl acrylate, 248.6 g of styrene and 2.8 g of methacrylic acid.

Example 3
Styrene-acrylic materials stabilized with both surfactants and low molecular weight CMC
The composition and method described in Example 2 were used, except that in addition to the Ambergum ^® solution, 15 g of anionic surfactant (alkylaryl sulfate ester: Disponil AES 60, 33% active substance) and 5 g of nonionic surfactant were used for stabilization (ethoxylated nonylphenol with 10 ethylene oxide units: Intrasol NP10, 100% active substance) in 450 g of water.

Example 4
Styrene-acrylic materials stabilized with both surfactants and low molecular weight CMC
The formulation and procedure described in take 2 except that instead of using 33 g of 16.6 g Ambergum ^® 3021 product combined with 5.9 g of an anionic surfactant (sodium dicyclohexyl: Aerosol A196, 85% active ), 5 g of a nonionic surfactant (ethoxylated nonylphenol with 4 ethylene oxide units: Surfonic N40, 100% active substance) in 463 g of water. The monomer mixture in this case included 248.6 g of butyl acrylate, 248.6 g of styrene and 2.8 g of methacrylic acid. To improve monomer conversion, the amount of initiator was increased. The initiator solution contained 3 g of potassium persulfate in 100 g of water.

Example 5
Vinyl acetate-acrylic materials with low molecular weight CMC
This example illustrates the possibility of preparing a vinyl-acrylic dispersion containing no surfactants with a relatively large amount of butyl acrylate in the monomer composition.

Polymerization processes were carried out in a 2-liter glass reaction vessel equipped with a thermocouple, reflux condenser, monomer inlet means, initiator inlet means and anchor stirrer. In 397 g of demineralized water were dissolved 33 grams of the protective colloid (CMC Ambergum ^® 3021 solution at a concentration of 29.6%, Brookfield viscosity of which was 630 mPa • s at 25 ^o C) and 2.0 g of sodium bicarbonate. After complete dissolution, the temperature was raised to 80 ^o C using a water bath.

Then, a 40% initiator solution (1.5 g of potassium persulfate in 50 g of demineralized water) was uniformly added over 30 s. After one minute, monomer was added. The monomer mixture (350 g of vinyl acetate and 150 g of butyl acrylate) was initially added at a rate of 54.5 grams per hour, and this rate was gradually increased to 163.5 grams per hour during the first hour of the reaction. When the temperature reached 80 ^° C. again, 95% of the rest of the initiator solution was added. The remaining 5% initiator solution was added after adding the entire amount of monomer. The initiator was introduced during the same period of time as the monomer, and the feed rate of the initiator was regulated in accordance with the feed rate of the monomer. The monomer, as well as the initiator, was injected within 3.5-4 hours using a plunger pump and a hose pump, respectively. The reaction temperature was maintained at 80 ^° C. The polymerization was completed while maintaining the temperature at 80 ^° C. for 1 hour after the introduction of the initiator and the monomer. Then the latexes were cooled to room temperature. During the reaction, the stirring speed was 200 rpm.

Example 6
Vinyl acetate-acrylic materials with both a surfactant and low molecular weight CMC
The formulation and procedure described in Example 5, except for the following changes: instead of 33 g of CMC Ambergum ^® 3021 in 363 g of demineralized water was dissolved 67 g of Ambergum ^® 1521 product (14.7% solution concentration with a Brookfield viscosity at 25 ^o C 1540 MPa • s, Mw from about 35,000 to 50,000, degree of substitution of carboxyl groups of about 1.2) together with 17 g of anionic surfactant (sulfonated ethoxylated nonylphenol with 30 ethylene oxide units: Fenopon EP 120 product; 30% active substance) and 7 , 1 g of nonionic surfactant of substance (ethoxylated nonylphenol: Antarox CO 897, 70% active material). The rest of the composition was similar to that described in example 4.

Example 7 Vinyl Acetate-Acrylic Materials with Both Surfactant and Low Molecular Weight CMC
The composition and method described in Example 5 were used, except that in this case also surfactants, a protective colloid and a buffer were added, which were dissolved in 397 g of water together with 5 g of a nonionic surfactant (ethoxylated nonylphenol with 20 ethylene oxide units: Tergitol NP40, 100% active substance) and 17 g of anionic surfactant (sulfonated ethoxylated nonylphenol with 30 ethylene oxide units: Fenopon EP 120; 30% active substance).

Example 8
Vinyl acetate-acrylic materials with both a surfactant and a low molecular weight SCE
The composition and method described in Example 1 were used, except that 12.5 g of anionic surfactant (Disponil MGS 156, 40% active substance) mixed with 7.1 g of nonionic surfactant was dissolved in 397 g of demineralized water. active substance (ethoxylated nonylphenol: Antarox CO 897, 70% active substance), 33 g of low molecular weight SCE (solution of a concentration of 29.1% with Brookfield viscosity at 25 ^° C 260 mPa · s) with Mw from about 7000 to about 11000 and 2 8 g of sodium bicarbonate. The reaction temperature was 80 ^° C, and the monomer mixture included 350 g of vinyl acetate and 150 g of butyl acrylate.

Example 9
Vinyl acetate-acrylic materials with both a surfactant and low molecular weight HMHEC (according to the invention)
The composition and method described in Example 8 were used, except that instead of the low molecular weight CMC, 47.4 g of the low molecular weight HMEC Natrosol Plus was used (a concentration solution of 21.1%, the Brookfield viscosity of which at 25 ^° C. was 28.5 MPa · s ) The weight average molecular weight of this protective colloid was approximately 25,000. The amount of water was adjusted to achieve the same dry matter content as latex. Surfactants, a buffer (in this case, 2.0 g) and a protective colloid were dissolved in 383 g of demineralized water.

Example 10
Vinyl acetate-acrylic materials with both a surfactant and low molecular weight HMHEC
The composition and method used were similar to those described in Example 8, except that they did not use low molecular weight CMC, but 10 g of low molecular weight HMEC Natrosol Plus (2% solution, whose viscosity at 4 ^° C was 4 MPa · s, with a weight average molecular weight material weight of approximately 25,000). Regulated the amount of water. Surfactants, 2.0 g of buffer and protective colloid were dissolved in 383 g of demineralized water.

Comparative Example D
Surfactant stabilized vinyl acetate-acrylic materials
In this example, the same composition and the same method were used as described in Example 9, except that a protective colloid was not used, and a mixture of surfactants and a buffer were dissolved in 420 g of water. Obviously, if only surfactants are used, the monomer conversion is worse and the latex viscosity is very low.

Example 11
Vinyl acetate-ethylene material stabilized with a surfactant and low molecular weight CMC
The polymerization was carried out in a 2-liter stainless steel reaction vessel equipped with a thermocouple, monomer inlet means, initiator inlet means, and an anchor stirrer. In 337 g of demineralized water were dissolved 33 grams of the protective colloid (CMC Ambergum ^® 3021 solution at a concentration of 29.6%, a viscosity of 630 mPa • s at 25 ^o C) and 1.25 g of sodium bicarbonate. Next, 21.5 g of EHSS [bis (ethylhexyl) sulfosuccinate sodium salt with 100% active substance] and 3.6 g of Antarox CO 897 (nonylphenol 40EO) were added. After complete dissolution, the temperature was raised to 80 ^° C. Then, a 15% initiator solution (2.5 g of potassium persulfate in 100 g of demineralized water) was uniformly added over 30 s. After one minute, the monomer and the remainder of the initiator solution were started. Over the course of 120 minutes, 445 g of vinyl acetate was gradually added, keeping the ethylene pressure in the reaction vessel at 21 bar. The initiator was administered over the same period of time as the monomer. The reaction temperature was maintained at a level of 80 ^o C. The polymerization was completed, maintaining a temperature of 80 ^o C for 1 hour after completion of the introduction of the initiator and monomer. Then the latexes were cooled to room temperature.

Example 12
Vinyl acetate-butyl acrylate material stabilized with surfactants and low molecular weight CMC; high shear polymerization
This example illustrates the possibility of using high shear during the reaction when a low molecular weight protective colloid is used.

The composition and method described in Example 5 were used, except that in this example a mixture of 12.5 g of anionic surfactant (Disponil MGS 156, 40% active substance), 7.1 g of nonionic was dissolved in 397 g of demineralized water surfactant (ethoxylated nonylphenol: Antarox CO 897, 70% active substance), 33 g of a protective colloid (CMC Ambergum ^® 3021, a solution concentration of 29.6%, Brookfield viscosity at 25 ^o C was 630 MPa · s) and 2.0 g of sodium bicarbonate. The agitator rotation speed in this example was 400 rpm (circumferential speed of the tip of the blade 2.72 m / s).

Example E
Surfactant stabilized vinyl acetate-butyl acrylate material; high shear polymerization
This comparative example illustrates the need to use a protective colloid during polymerization when high shear is used.

 In this example, the same composition and the same method was used as described in example 5, except that in this case a mixture of 12.5 g of anionic surfactant was dissolved in 420 g of demineralized water (Disponil MGS 156, 40% active substances), 7.1 g of a nonionic surfactant (ethoxylated nonylphenol: Antarox CO 897, 70% of the active substance) and 2.0 g of sodium bicarbonate. The agitator rotation speed in this example was 400 rpm (circumferential speed of the tip of the blade 2.72 m / s).

Example 13
Completely acrylic latex, characterized by a low minimum film-forming temperature and stabilized by CMC
The polymerization was carried out according to example 1, with the exception of the following changes. Instead of 16.6 g of the Ambergum ^® 3021 CMC product, 33 g of Ambergum ^® 3021 CMC together with 6.25 g of dihexyl sulfosuccinate (Disponil SUS IC 680, 80% active substance), 5 g of ethoxylated nonylphenol with 4 ethylene oxide units were dissolved in 450 g of demineralized water ( Sulfonic N40, 100% active) and 1.6 g of sodium bicarbonate. The monomer mixture included 200 g of methyl methacrylate, 300 g of butyl acrylate and 2.8 g of methacrylic acid.

Example G
Fully acrylic latex with a low minimum film-forming temperature and stabilized with surfactants
The polymerization in this comparative example was carried out analogously to Example 13, except that there was used Ambergum ^® polymer for stabilization. Therefore, surfactants and a buffer were dissolved in 473 g of water.

Example 14
Vinyl acetate-acrylic latex characterized by a low minimum film-forming temperature and stabilized by ultra-low molecular weight HMHEC
The polymerization was carried out according to example 10, with the exception of the following changes. 12.7 g of mixed anionic surfactants (Disponil MGS 156, 40% active substance), 7.7 g of ethoxylated fatty alcohol (Disponil APE 257, 65% active substance), 1.6 g of bicarbonate were dissolved in 422 g of demineralized water. sodium and 10 g of low molecular weight HMEC Natrosol Plus. The monomer mixture included 200 g of vinyl acetate and 300 g of butyl acrylate.

Example 15
Product latex vinyl acetate / VeoVa-10, characterized by an average minimum film formation temperature and stabilized by CMC
The polymerization was carried out in a 2 liter glass reaction vessel equipped with a thermocouple, reflux condenser, monomer inlet means, initiator inlet means, and an anchor stirrer.

In 432 g of demineralized water were dissolved 40 grams of the protective colloid (CMC Ambergum ^® 3021 solution at a concentration of 29.6%, Brookfield viscosity of which was 630 mPa • s at 25 ^o C) together with 1.6 g of sodium bicarbonate, 7.5 g of dihexyl sulfosuccinate (Disponil SUS IC 680, 80% active substance) and 6 g of a nonionic surfactant (ATPOL E 5720). After complete dissolution, the temperature was raised to 80 ^o C using a water bath. Next, 5% of the total monomer was added over 1 min. After 2 minutes, a 25% initiator solution (1.8 g of potassium persulfate in 60 g of demineralized water) was added. When the temperature reached 72 ^° C. again, monomer was started. The monomer mixture was added at a flow rate of 180 grams per hour (300 g of vinyl acetate, 300 g of VeoVa-10 monomer). VeoVa is a trademark of Shell Chemical Company, a marketer of vinyl transversate products. After 5 minutes the temperature was raised to 80 ^o C and the mixture was kept at this temperature. The flow rate of the initiator solution was adjusted in accordance with the flow rate of the monomer. During the reaction, the speed of the stirrer was 200 rpm. Within 1 h after the addition of the initiator and the monomer, the polymerization was completed while maintaining the temperature at 80 ^° C. After that, the polymerized mass was cooled to room temperature.

Example 3
Product latex vinyl acetate / VeoVa-10 with an average minimum film-forming temperature and stabilized with surfactants
The polymerization in this comparative example was carried out in accordance with example 15, except that no protective colloid was used. The amount of water, therefore, was adjusted to 460 g.

Example 16
Latex methyl methacrylate / VeoVa-9 / butyl acrylate material stabilized with CMC and surfactants
The polymerization was carried out in accordance with Example 13, except that the monomer mixture included 100 g of methyl methacrylate, 100 g of VeoVa-9 monomer, 300 g of butyl acrylate and 2.8 g of methacrylic acid.

Example 17
Latex methyl methacrylate / VeoVa-9 / butyl acrylate material, stabilized CMC without surfactants
The polymerization was carried out in accordance with example 16, except that surfactants were excluded.

Example 18
Ultra-low molecular weight methyl methacrylate / butyl acrylate latex stabilized with hydroxypropyl cellulose
Polymerization was conducted by the method described in Example 1. As a protective colloid in place of 16.6 g of CMC Ambergum ^® 3021 was used 16.5 g of a 30% solution of ultra low molecular weight hydroxypropylcellulose (Mw of 6500), whose cloud point temperature was 90 ^o C .

 The properties of the latexes from the above examples and comparative examples are presented below in tables 1 and 2.

The dry matter content was determined gravimetrically by weighing a certain amount of latex, drying this portion at 120 ^o C, re-weighing the dried portion and then dividing the dry weight by wet weight. The content of fine solid particles was determined as a fraction, the particle size of which exceeded 200 #, by passing a weighed portion of latex through a No. 200 sieve. The film properties were determined on latex films with a wet thickness of 200 micrometers (μm) on a glass substrate during water spot tests and on Lenet's sheets during gloss measurements. Latex films were dried both at 20 and at 45 ^o C. The gloss of the films was measured using a Beak gloss meter at an angle of 60 ^o .

Water resistance was measured by applying a few drops of water to the films. After 5 minutes, the appearance of the films was evaluated. Moreover, the assessment was made on the following scale:
10 transparent
8 slightly cloudy
6 muddy
5 dairy
2 white
0 film is re-emulsified
Particle size was determined on a Joyce Lebl disc centrifuge.

Example 19
Paint with a volume concentration of pigment (OKP) 65, prepared from vinyl acetate-butyl acrylate latex stabilized with surfactants and low molecular weight HMHEC
According to this example, latex stabilized with a protective colloid, with a discrete (heterogeneous) polymer phase, characterized by a small particle size (in this case, approximately 200 nanometers), exhibits excellent properties in that the paint has a good film-forming ability. In the presence of such fine particles of paint can be prepared in the form of systems with a higher filler content.

 In the paint with OKP 65 used latex according to example 9, as shown in table 3.

Comparative Example And
Paint with OKP 65 prepared using technical latexes based on vinyl acetate-VeoVa material (Mowilith DM 21)
As shown in table 3, the composition with OKP 65 used technical latex Mowilith DM 21. This paint was stabilized with surfactants and low molecular weight Natrosol Plus HMEC.

Example 20
Paint with OKP 80, prepared on the basis of vinyl acetate-butyl acrylate latex stabilized with surfactants and low molecular weight HMEC
In the paint with OKP 80 used latex according to example 9, as shown in table 3.

Example 21
Paint with OKP 80, prepared on the basis of styrene-acrylate latex, stabilized with surfactants and low molecular weight CMC
As shown in Table 3, in latex paint with function 80 performed OKP latex described in Example 4, except that used as a protective colloid solution 33 g Ambergum ^® 3021 (instead of 16.6 g).

Comparative Example K
Paint with OKP, prepared on the basis of technical styrene-acrylate latex (Acronal 290 D)
Also, in accordance with the data presented in table 3 in the composition with OKP 80 used technical latex (Acronal 290 D).

Example 22
Paint with OKP 15, prepared on the basis of acrylic latex stabilized with low molecular weight CMC
In the paint for coatings with high gloss with OKP 15 used, as shown in table 3, latex described in example 1.

Comparative Example L
Paint with OKP 15, prepared on the basis of technical acrylic latex (Primal AC 507)
In the composition with OKP 15, as shown in table 3, used technical latex Primal AC 507.

 The properties of the paints according to examples 19-21 and comparative examples K and L are shown in tables 4 and 5.

 Regarding the thickeners given in Tables 4 and 5, it should be noted that Natrosol MBR and Natrosol HBR are used as non-associative thickeners, and Natrosol Plus and Primal RMB are used as associative thickeners. Natrosol MBR and Natrosol HBR, as well as Natrosol Plus, are marketed by Hercules Incorporated, Wilmington, pc. Delaware; Primal RMB is marketed by Rohm & Haas, Philadelphia. Pennsylvania.

Example 23
Solvent-free latex paint for matt coatings was prepared using the following components, including, as indicated, latex according to example 13.

Component - Amount (grams)
Water - 197
Calgon N - 1.0
Pigment Disperser Pigmentverteiler A - 2.0
CA24 - 2.0
Agitan 280 - 1.6
Natrosol 250 MBR - 5.0
Ammonia (25%) - 0.4
Kronos RN 57 - 159
Omyalite 90 - 114
Durcal 5 - 159
Talc AT 200 - 23
Latex (according to example 13) - 167
Water - 150
The properties of the paint according to example 23 are presented in table 6.

 Although the present invention is described with reference to specific methods, materials and options for its implementation, it is obvious that its scope is not limited to the described features, since they include all possible equivalents defined by the claims.

Claims (62)

1. A method of preparing a latex system characterized by improved mechanical stability, comprising aqueous emulsion (co) polymerization of at least one ethylenically unsaturated monomer in the presence of an effective amount of a water-soluble protective colloid selected from the group consisting of carboxymethyl cellulose and its derivatives to stabilize the latex system. the degree of carboxyl substitution of which is approximately 0.7, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose s, methylhydroxypropyl cellulose, hydroxypropyl cellulose, hydrophobically modified cellulose ethers, polyacrylic acid and its alkali metal salts, ethoxylated starch derivatives, sodium polyacrylates and other alkali metals, water-soluble starch glue, gelatin, partially soluble synthetic agglomerates, natural solvents, kaz and fully hydrolyzed polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and a copolymer of methyl vinyl ether and maleic anhydride yes, as well as a polymerization initiator, characterized in that the ethylene unsaturated monomer is a monomer selected from the group consisting of acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, acrylic esters, styrene, vinyl ethers, vinyl, vinylidene halides, N- vinylpyrrolidone, ethylene, C ₃ -C ₂₄ alpha olefins, allylamines, allyl ethers of saturated monocarboxylic acids, their amides, propylene, 1-butene, 1-pentene, 1-hexene, 1-decene, allyl acetate, allyl propionate, allyl lactate, their amides and mixtures thereof, and the water-soluble protective colloid used has a weight average molecular weight of less than about 75,000.  2. The method according to claim 1, characterized in that also use from about 0.1 to about 5.0 wt.% Surfactant from the total content of ethylenically unsaturated monomer.  3. The method according to claim 2, characterized in that the surfactant is selected from the group consisting of anionic, cationic, nonionic and amphoteric surfactants and mixtures thereof. 4. The method according to claim 3, characterized in that the surfactant is selected from the group consisting of simple polyglycol ethers, sulfonated paraffinic hydrocarbons, higher alkyl sulfates, alkali metal salts of fatty acids, sulfuric acid esters and fatty alcohols, ethoxylated C ₄ - C ₅₀ alkylphenols and their sulfonation products, hydroxyethylated C ₄ -C ₅₀ alkanols and their sulfonation products, sulfosuccinic acid esters and mixtures thereof.  5. The method according to claim 4, characterized in that the surfactant is selected from the group consisting of nonylphenoloxyethylate with 4-50 ethylene oxide units of sodium dioctyl sulfosuccinate, lauryl sulfate, sodium stearate, sodium oleate and mixtures thereof.  6. The method according to p. 1, characterized in that the protective colloid is selected from the group consisting of hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, the lower limit of the degree of carboxyl substitution of which is approximately 0.7, methyl cellulose, methyl hydroxypropyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl fully hydrolyzed polyvinyl alcohol, polyacrylic acid, sodium polyacrylates and other alkali metals, polyacrylamide, methyl vinyl copolymer ether and maleic anhydride, polyvinylpyrrolidone, water soluble starch glue, gelatin, water soluble alginates, casein, agar and natural and synthetic gums.  7. The method according to claim 1, characterized in that the upper limit of the mass-average molecular weight of the protective colloid is approximately 50,000.  8. The method according to claim 1, characterized in that the protective colloid is a cellulose ether selected from the group consisting of hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, the lower limit of the degree of carboxyl substitution of which is approximately 0.7, methyl cellulose, methyl hydroxypropyl cellulose and hydroxypropyl cellulose.  9. The method according to claim 1, characterized in that the upper limit of the mass-average molecular weight of the protective colloid is approximately 20,000.  10. The method according to claim 1, characterized in that the degree of carboxyl substitution of carboxymethyl cellulose is approximately 0.7 to 2.9.  11. The method according to claim 1, characterized in that the upper limit of the hydroxyethyl molar substitution of hydroxyethyl cellulose is 4.0.  12. The method according to claim 11, characterized in that the lower limit of the hydroxyethyl molar substitution of hydroxyethyl cellulose is approximately 1.6.  13. The method according to p. 1, characterized in that the hydrophobically modified cellulose ethers are cellulose ethers that are additionally substituted with a hydrocarbon containing 4 to 25 carbon atoms, and the mass amount of this hydrocarbon is from about 0.1 to about 3 wt. % of the total amount of hydrophobically modified cellulose ether.  14. The method according to item 13, wherein the hydrophobically modified cellulose ether is a hydrophobically modified hydroxyethyl cellulose.  15. The method according to 14, where the upper limit of hydroxyethyl molar substitution of hydrophobically modified hydroxyethyl cellulose is approximately 4.0.  16. The method according to clause 15, where the lower limit of hydroxyethyl molar substitution of hydrophobically modified hydroxyethyl cellulose is approximately 2.9.  17. The method according to claim 1, characterized in that the initiator is selected from the group consisting of water-soluble peroxides, persulfates and perborates.  18. The method according to 17, characterized in that the initiator is selected from the group consisting of hydrogen peroxide, potassium, sodium and ammonium persulfates and sodium perborate.  19. The method according to p. 1, characterized in that the (co) polymerization is carried out semi-continuously with the introduction at the beginning of the reaction from about 0 to about 60% of the total amount of initiator and from about 0 to about 40% of the total amount of at least one ethylenically unsaturated monomer.  20. The method according to claim 1, characterized in that (co) polymerization is carried out continuously.  21. The method according to claim 1, characterized in that (co) polymerization is carried out in a loop reactor.  22. A method of preparing a latex system characterized by improved mechanical stability, comprising aqueous emulsion (co) polymerization of at least one ethylenically unsaturated monomer in the presence of an effective amount of a water-soluble protective colloid selected from the group consisting of hydroxyethyl cellulose, methylhydroxyethyl cellulose methyl, cellulose, methyl hydroxypropyl cellulose, hydrophobically modified cellulose ethers, hydroxy starch derivatives of starch, partially and fully hydrolyzed polyvinyl alcohol, polyacrylic acid, sodium polyacrylates and other alkali metals, polyacrylamide, a copolymer of methyl vinyl ether and maleic anhydride, polyvinylpyrrolidone, water-soluble starch glue, natural gelatin, karate, alginine, water, gelatin, water gelatin, water gelatin, their derivatives and polymerization initiator, characterized in that they use a protective colloid with a mass average molecular weight of less than approx. 75,000 total.  23. The method according to item 22, wherein the surfactant is additionally used in an amount of from about 0.1 to about 5.0 wt.% Of the total amount of ethylenically unsaturated monomer component.  24. The method according to item 23, wherein the surfactant is selected from the group consisting of anionic, cationic, nonionic and amphoteric surfactants and mixtures thereof. 25. The method according to item 23, wherein the surfactant is selected from the group consisting of simple polyglycol ethers, sulfonated paraffinic hydrocarbons, higher alkyl sulfates, alkali metal salts of fatty acids, sulfuric acid esters and fatty alcohols, ethoxylated C ₄ - C ₅₀ alkylphenols and their sulfonation products, hydroxyethylated C ₄ -C ₅₀ alkanols and their sulfonation products, sulfosuccinic acid esters and mixtures thereof.  26. The method according A.25, characterized in that the surfactant is selected from the group consisting of nonylphenoloxyethylate with 4 to 50 ethylene oxide units of sodium dioctyl sulfosuccinate, lauryl sulfate, sodium stearate, sodium oleate and mixtures thereof.  27. The method according to item 22, wherein the at least one ethylenically unsaturated monomer is selected from the group consisting of acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, acrylic esters, styrene and mixtures thereof. 28. The method according to item 22, wherein the at least one ethylenically unsaturated monomer is selected from the group consisting of vinyl esters, vinyl ethers, vinyl, vinylidene halides, N-vinylpyrrolidone, ethylene, C ₃ -C ₂₄ alpha olefins, allylamines, allyl ethers of saturated monocarboxylic acids, their amides and their mixtures.  29. The method according to item 22, wherein the upper limit of the mass-average molecular weight of the protective colloid is approximately 50,000.  30. The method according to item 22, wherein the upper limit of the mass-average molecular weight of the protective colloid is approximately 20,000.  31. The method according to item 22, wherein the protective colloid is a cellulose ether selected from the group consisting of hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose and hydroxypropyl cellulose.  32. The method according to item 22, wherein the upper limit of the hydroxyethyl molar substitution of hydroxyethyl cellulose is 4.0.  33. The method according to p, characterized in that the lower limit of the hydroxyethyl molar substitution of hydroxyethyl cellulose is approximately 1.6.  34. The method according to item 22, wherein the hydrophobically modified cellulose ethers are hydrophobically modified cellulose ethers, which are replaced by a hydrocarbon containing 4 to 25 carbon atoms, and the mass amount of this hydrocarbon is from about 0.1 to about 3 wt.% of the total amount of hydrophobically modified cellulose ether.  35. The method according to clause 34, wherein the hydrophobically modified cellulose ether is a hydrophobically modified hydroxyethyl cellulose.  36. The method according to clause 35, wherein the upper limit of the hydroxyethyl molar substitution of hydrophobically modified hydroxyethyl cellulose is approximately 4.0.  37. The method according to clause 36, wherein the lower limit of hydroxyethyl molar substitution of hydrophobically modified hydroxyethyl cellulose is approximately 2.9.  38. The method according to item 22, wherein the initiator is selected from the group consisting of water-soluble peroxides, persulfates and perborates.  39. The method according to § 38, wherein the initiator is selected from the group consisting of hydrogen peroxide, potassium, sodium and ammonium persulfates and sodium perborate.  40. The method according to p. 22, wherein the (co) polymerization is carried out semi-continuously with the introduction of from the beginning of the reaction from about 0 to about 60% of the total amount of initiator and from about 0 to about 40% of the total amount of at least one ethylenically unsaturated monomer.  41. The method according to item 22, wherein the (co) polymerization is carried out continuously.  42. The method according to item 22, wherein the (co) polymerization is carried out in a loop reactor. 43. A latex system characterized by improved mechanical stability, comprising an aqueous emulsion containing (a) (co) a polymer of at least one ethylenically unsaturated monomer and (b) an amount of a water-soluble protective colloid selected from the group consisting of carboxymethyl cellulose effective to stabilize this latex system and its derivatives, the lower limit of the degree of carboxyl substitution of which is approximately 0.7, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose, methyl hydroxy propyl cellulose, hydroxypropyl cellulose, polyacrylic acid and its alkali metal salts, ethoxylated starch derivatives, sodium polyacrylates and other alkali metals, water-soluble starch glue, gelatin, water-soluble alginates, casein, agar, natural and synthetic gums, partially and fully hydrolysed, hydrolysis polyvinylpyrrolidone and a copolymer of methyl vinyl ether and maleic anhydride, characterized in that the ethylenically unsaturated monomer is selected from nN consisting of acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, acrylic esters, styrene, vinyl ethers, vinyl, vinylidene halides, N-vinyl pyrrolidone, ethylene, C ₃ -C ₂₄ alpha-olefins, allyl amines, allyl esters of saturated monocarboxylic acids, their amides, propylene, 1-butene, 1-pentene, 1-hexene, 1-decene, allyl acetate, allyl propionate, allyllactate, their amides and mixtures thereof, and the water-soluble protective colloid has a weight average molecular weight of less than about 75,000.  44. The latex system according to item 43, wherein the (co) polymer is obtained by aqueous emulsion (co) polymerization in the presence of a water-soluble protective colloid.  45. The latex system according to item 43, wherein it further comprises from about 0.1 to about 5.0 wt.% Surfactant of the total amount of ethylenically unsaturated monomer component.  46. The latex system according to claim 43, characterized in that the upper limit of the mass-average molecular weight of the protective colloid is approximately 50,000.  47. The latex system according to item 43, wherein the (co) polymer is a dispersed phase, characterized by an average particle size of less than about 300 nanometers.  48. A latex paint composition comprising at least one product selected from the group consisting of a pigment and a filler, and a latex system, characterized in that it contains the latex system according to item 43.  49. The latex paint composition according to claim 48, wherein the latex is solvent free.  50 The latex paint composition of claim 48, wherein the (co) polymer comprises particles whose average size is less than about 500 nanometers.  51. The composition of the latex paint according to § 48, wherein the paint is a paint for glossy coatings, the volume concentration of the pigment in which is less than about 50.  52. The composition of the latex paint according p, characterized in that the paint is a paint for matte coatings, the volume concentration of the pigment in which is approximately 50 or more.  53. The composition of the water-based ink, comprising the latex system and at least another component of the ink, characterized in that as the latex system contains a latex system according to item 43.  54. Composition for coating paper, comprising a latex system and at least another component of the composition for coating paper, characterized in that as a latex system contains a latex system according to item 43.  55. A dextrin-free adhesive composition comprising a latex system and at least another dextrin-free adhesive component, characterized in that it contains a latex system according to claim 43 as a latex system.  56. A binder for non-woven textile materials, comprising a latex system and at least another component of the binder, characterized in that as the latex system contains a latex system according to item 43.  57. A latex system characterized by improved mechanical stability, comprising an aqueous emulsion containing (a) (co) a polymer of at least one ethylenically unsaturated monomer and (b) an amount of a water-soluble protective colloid selected from the group consisting of hydroxyethyl cellulose effective to stabilize this latex system , ethyl hydroxyethyl cellulose, methyl cellulose, methyl hydroxypropyl cellulose, hydroxypropyl cellulose, hydroxyethylated starch derivatives, partially and fully hydrolyzed poly vinyl alcohol, polyacrylic acid, sodium polyacrylates and other alkali metals, polyacrylamide, a copolymer of methyl vinyl ether and maleic anhydride, polyvinylpyrrolidone, water-soluble starch glue, gelatin, water-soluble alginates, casein, agar, natural and synthetic, and natural and synthetic, the protective colloid has a weight average molecular weight of less than about 75,000.  58. The latex system according to clause 57, wherein the (co) polymer is obtained by aqueous emulsion (co) polymerization in the presence of a water-soluble protective colloid.  59. The latex system according to claim 57, characterized in that it further comprises from about 0.01 to about 4.0 wt.% Surfactant of the total amount of ethylenically unsaturated monomer component.  60. The latex system according to clause 57, wherein the upper limit of the mass-average molecular weight of the protective colloid is approximately 50,000.  61. The latex system according to clause 57, wherein the at least one ethylenically unsaturated monomer is selected from the group consisting of acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, acrylic esters, styrene and mixtures thereof. 62. The latex system of claim 57, wherein the at least one ethylenically unsaturated monomer is selected from the group consisting of vinyl esters, vinyl ethers, vinyl, vinylidene halides, N-vinylpyrrolidone, ethylene, C ₃ -C ₂₄ alpha -olefins, allylamines, allyl ethers of saturated monocarboxylic acids, their amides and their mixtures.  63. The latex system according to p. 57, characterized in that the upper limit of the mass-average molecular weight of the protective colloid is approximately 20,000.

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