Latex system and the method of its preparation (options)


C08L1/04 - Oxycellulose; Hydrocellulose

 

(57) Abstract:

Describes the method of preparation of the latex system, which is characterized by improved mechanical stability, it includes water emulsion (co)polymerization of at least one ethyleneamines monomer in the presence of effective to stabilize the latex system number of water-soluble protective colloid selected from the group consisting of carboxymethyl cellulose and its derivatives, the lower limit of the degree of carboxyl substitution which is approximately 0.7, hydroxyethyl cellulose, metilgidroxiatilzelllozu, methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, hydrophobically modified ethers of cellulose, polyacrylic acid and its alkali metal salts, ethoxylated starch derivatives, polyacrylates, sodium and other alkali metals, water-soluble starch glue, gelatin, the water-soluble alginates, casein, agar, natural and sinteticheskih gums, partially and fully hydrolyzed polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and copolymers metilfenidato ether and maleic anhydride and initiator of polymerization. dust, consisting of acrylic acid, butyl acrylate, methyl methacrylate, acrylic esters, styrene, vinyl ethers, vinyl, vinylidenechloride, N-vinylpyrrolidone, ethylene, C3- C24alpha-olefins, allylamine, allyl esters of saturated monocarboxylic acids and their amides, propylene, 1-butene, 1-pentene, 1-hexene, 1-mission ZIOC scientists arylpropionate of allylacetate, their amides and their mixtures, and used water-soluble protective colloid has a mass-average molecular mass of less than approximately 75,000. The technical result - obtaining latex with improved mechanical stability. 9 C. and 54 C.p. f-crystals, 6 PL.

The present invention relates to aqueous polymer dispersions obtained from ethanobotany monomers in the presence of water-soluble protective colloid, and to methods for their preparation. In industrial processes emulsion polymerization surface-active substances are usually used either alone or in combination with a polymeric protective colloids. The disadvantage of this is that the surfactant must be used for the preparation of latexes that are resistant to shear, which is uneconomical and may cause Ah can have a negative effect on the sensitivity to water and to cause foaming of the final products. In addition, commonly used quantities of surface-active substances do not give these final products sufficient mechanical stability.

In the art it is known that the presence of protective colloids as joint stabilizers, such as hydroxyethylcellulose (SCE) and polyvinyl alcohol (AA), in the process of emulsion polymerization ethanobotany monomers, including vinyl monomers, vinyl monomers together with acrylic monomer, such as acrylic esters, methacrylic esters, or mixtures thereof, provide latexes with submicrometric particle size having improved rheology, stability and performance. These aqueous polymer dispersions can be used for the preparation of latex paints, binders for non-woven textile materials, printing inks, water-based, means for coating paper and aqueous adhesives such as pressure-sensitive adhesives.

In the processes of emulsion polymerization of monomers comprising acrylic compounds or styrene, either individually or in combination with other monomers, as joint stabilizers is etnie colloids used in latex systems on acrylic or styrene-based, there is intense flocculation, which is a sign of a lack of mechanical stability. This flocculation due to the high tendency of the protective colloid to the introduction of directly participating in the reaction, the polymer chain. This phenomenon is commonly known as graft copolymerization.

Be aware that the vaccine on the chain by itself grafted copolymerization cannot be completely eliminated. Minor in quantitative terms grafted copolymerization does not cause flocculation; moreover, it improves the stability of latex systems that have long been known for vinyl acetate copolymer latexes. Coagulation is caused by the combination of excessive graft copolymerization with the possibility of formation of bridging connections between particles. Education bridging connections between particles is determined not only by one number grafted material or particle size, but also depends on the amount of water-soluble polymer contained in the aqueous phase, the molecular weight of protective colloid, dry matter content, etc.

In any case, depending on the particular latex systems lack mechanochemical or in combination with a protective colloid. For example, in systems on acetate the basis of a large amount of protective colloid used in combination with surface-active substance, whereas in systems acrylic-based surfactant used in large quantities by yourself. However, the latexes prepared using such large quantities of surface-active substances peculiar to the above-mentioned disadvantages associated with operational properties.

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

One approach to solving this problem is described in U.S. patent 4684704, issued in the name of Craig ('704), is to use from about 0.01 to about 1.7 wt.% (from the total amount of monomer component) hydrophobically modified hydroxyethyl cellulose (GMAC), which easily and successfully injected into the dispersion or latex by the emulsion polymerization of monomers with low ability to graft copolymerization with a protective colloid. Get tx2">

Another solution polymerization of acrylic monomer systems described in U.S. patent 4845175, issued in the name of Lo, is to use the 0.02 to 2.0 wt.% hydrophobically modified hydroxyethyl cellulose as a protective colloid.

Another solution associated with the polymerization of acrylic monomer systems and are described in U.S. patent 4659771, issued in the name of Craig ('771), is to use in addition to the protective colloid from about 0.1 to 5 wt.% almost completely water-soluble conjugated unsaturated monomer, such as francebuy acid, styrelseledamot, metal salts, salts of amines, ammonium salts and Quaternary ammonium salts of rosin acids and acid containing 4-36 carbon atoms.

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

The present invention is to obtain latex, characterized by improved mechanical stabilise improved mechanical stability, including water emulsion (co)polymerization of at least one ethyleneamines monomer in the presence of effective to stabilize the latex system number of water-soluble protective colloid selected from the group consisting of carboxymethyl cellulose and its derivatives, the lower limit of the degree of carboxyl substitution which is approximately 0.7, hydroxyethyl cellulose, metilgidroxiatilzelllozu, methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, hydrophobically modified ethers of cellulose, polyacrylic acid and its alkali metal salts, ethoxylated starch derivatives, polyacrylates, sodium and other alkali metals, water-soluble starch glue, gelatin, of a water-soluble alginates, casein, agar, natural and synthetic gums, partially and fully hydrolyzed polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and copolymers metilfenidato ether and maleic anhydride and initiator of polymerization, in which according to the invention as ethylenevinylacetate monomer using a monomer selected from the group consisting of acrylic acid, methacrylic acid, bidou, N-vinylpyrrolidone, ethylene, C3-C24alpha-olefins, allylamine, allyl esters of saturated monocarboxylic acids, their amides and their mixtures, propylene, 1-butene, 1-pentene, 1-hexene, 1-mission ZIOC scientists arylpropionate, allylacetate, their amides, and used water-soluble protective colloid has a mass-average molecular mass of less than approximately 75,000.

The task is also solved by a method of preparation of the latex system, which is characterized by improved mechanical stability, includes water emulsion (co)polymerization of at least one ethyleneamines monomer in the presence of effective to stabilize the latex system number of water-soluble protective colloid selected from the group consisting of hydroxyethyl cellulose, metilgidroxiatilzelllozu, methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, hydrophobically modified ethers of cellulose, ethoxylated starch derivatives, partially and fully hydrolyzed polyvinyl alcohol, polyacrylic acid, polyacrylate sodium and other alkali metals, polyacrylamide, copolymer metilfenidato ether and maleic, is asaina, agar, natural and synthetic gums and derivatives thereof, and an initiator of polymerization, in which according to the invention using a protective colloid with mass-average molecular mass of less than approximately 75,000.

In addition, the problem is solved also latex system including an aqueous emulsion containing

(a) a (co)polymer of at least one ethyleneamines monomer and

(b) effective for stabilization of the latex system the amount of water-soluble protective colloid selected from the group consisting of carboxymethyl cellulose and its derivatives, the lower limit of the degree of carboxyl substitution which is approximately 0.7, hydroxyethyl cellulose, metilgidroxiatilzelllozu, methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, polyacrylic acid and its alkali metal salts, ethoxylated starch derivatives, polyacrylates, sodium and other alkali metals, water-soluble starch glue, gelatin, of a water-soluble alginates, casein, agar, natural and synthetic gums, partially and fully hydrolyzed polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and apolinar selected from the group consisting of acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, acrylic esters, styrene, vinyl ethers, vinyl, vinylidenechloride, N-vinylpyrrolidone, ethylene, C3-C24alpha-olefins, allyl esters of saturated monocarboxylic acids, their amides and their mixtures, propylene, 1-butene, 1-pentene, 1-hexene, 1-mission ZIOC scientists arylpropionate, allylacetate, their amides, and water-soluble protective colloid has a mass-average molecular mass of less than approximately 75,000.

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

In the latex paint composition preferably latex does not contain solvent.

Mainly in the composition of latex paint (co)polymer comprises particles of average size less than about 500 nanometers.

Moreover, the latex paint composition preferably include paint for a glossy coating, the volume concentration of the pigment is less than about 50, paint or matte coatings, three-dimensional con is obreteniyu included in the composition of the printing ink, water based, includes in addition to the latex system at least another component of printing ink.

Latex system according to the invention includes a composition for coating paper, comprising in addition to the latex system at least another component of the composition for coating paper.

Not containing dextrin adhesive composition includes a latex system according to the invention and at least the other not containing dextrin component glue.

The binder for non-woven textile material includes the above-described latex system and at least another component of the binder.

Another option latex system according to the invention is a latex system, which is characterized by improved mechanical stability, includes water emulsion containing

(a) a (co)polymer of at least one ethyleneamines monomer, and

(b) effective for stabilization of the latex system the amount of water-soluble protective colloid selected from the group consisting of hydroxyethyl cellulose, metilgidroxiatilzelllozu, methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, ethoxylated about the acrylate sodium and other alkali metals, polyacrylamide, copolymer metilfenidato ether and maleic anhydride, polyvinylpyrrolidone, water-soluble starch glue, gelatin, of a water-soluble alginates, casein, agar, natural and synthetic gums and their derivatives, which according to the invention water-soluble protective colloid has a mass-average molecular mass of less than approximately 75,000.

It has been unexpectedly found that the use of low molecular weight protective colloid in the emulsion polymerization process ethanobotany monomers attached to the obtained polymer excellent mechanical stability. The upper limit of the mass-average molecular weight of such a protective colloid is approximately 75,000, preferably about 50,000 and most preferably about 20,000. The lower limit of the mass-average molecular weight of the protective colloid is about 5000, preferably about 10,000 and most preferably about 15,000.

The present invention is especially effective in respect of acrylic or styrene latex systems. As indicated above, known for latex systems on acrylic and styrene-based application featured with technical t the Use of large quantities of surfactants to resolve this problem can lead to negative effects on sensitivity to water and to cause foaming of the finished products. In addition, the commonly used concentrations of surfactants does not give the finished product a sufficient mechanical stability. It has been unexpectedly found that the use of low molecular weight protective colloid in latex systems on acrylic and styrene-based to reduce the content of surface-active substances or even eliminate it. The finished products generally exhibit low sensitivity to water, less foaming and greater mechanical stability in comparison with known systems. Mechanical stability as such can result in a greater vitality. In addition, in the case of use in the paint this last show a weak tendency towards the formation of streaks and improved filling.

Preferred polysaccharide protective colloid is a simple water-soluble cellulose ether, which is obtained using ethylene oxide, methyl chloride, propylene oxide, monochloracetic acid, etc. or mixtures thereof. Especially preferred are carboxymethylcellulose (CMC) and its derivatives, the degree of carboxyl substitution (Sz) which is from about 0.7 to primer is 1,4. Acceptable derivatives of carboxymethylcellulose include methylcarboxymethylcellulose, ethylcarboxylate, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, methoxyethoxymethyl, amoxicillinamoxicillin and diethylaminoethylcellulose.

You can also use the hydroxyethyl cellulose (SCE), and the preferred degree hydroxyethylene molar substitution (MOH) is 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 about 2.9.

Additionally, there may be used a hydrophobic modified ethers of cellulose. The corresponding hydrophobic modified ethers of cellulose are cellulose ethers which are substituted by hydrocarbon containing 4-25 carbon atoms, and the mass number of this hydrocarbon is from about 0.1 to about 3.0 wt.%, more preferably from about 0.1 to about 2.0 wt.% of the total number of hydrophobic modified simple cellulose ether.

Preferred hydrophobically modified cellulose ether is soboleski, which can be used for practical implementation of the present invention is hydroxyethylcellulose, which is optionally substituted by a hydrocarbon containing 4-25 carbon atoms, and the mass number of this hydrocarbon is from about 0.1 to about 3.0%, and more preferably from about 0.1 to about 2.0% of the total number of hydrophobically modified hydroxyethyl cellulose of the total number. In a preferred embodiment, the degree hydroxyethylene MOH this GMGEC is from about 2.9 to about 4.0, more preferably from about 2.9 to about 3.5.

Other simple esters of cellulose, such as those that can be used according to the present invention as protective colloids include metilgidroxiatilzelllozu (AGEC), methylcellulose (MC), methylhydroxypropylcellulose (MHPC) and hydroxypropylcellulose (GOC).

Other polysaccharides and materials according to the present invention can be used as protective colloids, are ethoxylated derivatives of starch, partially and fully hydrolyzed polyvinyl alcohol, polyacrylic acid, polyacrylates alkaline metaid, polyvinylpyrrolidone, water-soluble starch glue, gelatin, water soluble alginates, casein, agar, natural and artificial gums.

In a preferred embodiment of the invention, 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 water emulsion polymerization and after polymerization.

In particular, the concentration of the protective colloid in the process of emulsion polymerization according to the present invention can be varied in a wide range, and the upper limit is determined only by economic and practical considerations, based on what properties should have the final product. In a preferred embodiment, the upper limit is approximately 5.0 wt.%, more preferably 3.5 wt.% and most preferably about 2.5 wt.% of the total number ethanobotany monomers in the reaction mass. The preferred lower limit is approximately 0.005 wt.%. A more preferred lower limit is approximately 0.05 wt.% and Nai is nomernogo component.

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

In addition, used in accordance with the present invention the monomers include at least one ethanobotany monomer, such as vinyl complex or simple esters, styrene, etc. To the acrylate, which is used in the present invention include acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate and other acrylate and methacrylate esters.

In General, for practical implementation of the present invention can be used any ethanobotany monologically polymerization. Preferred ethylenevinylacetate monomers include monomers, which contain up to 23 carbon atoms.

Examples of usable monomers include vinyl esters, vinyl ethers, vinyl and vinylidenechloride, N-vinyl pyrrolidone, ethylene, C3-C24alpha-olefins, allylamine, allyl esters of saturated monocarboxylic acids and their amides, and dieny and their derivatives.

To the corresponding vinyl esters include aliphatic vinyl esters such as wikiformat, vinyl acetate, finalproject, vinylboronate, minimizebutton, vinylacetat, vinilmarket and vinylistic.

Typical examples of vinyl ethers include metilidinovy ether, ethylenically ether and n-butylvinyl ether.

The corresponding C3and more high molecular weight alpha-olefins include propylene, 1-butene, 1-penten, cyclopentene, 1-hexene, cyclohexene and 1 of the mission.

Examples of typical allylamino are allylamine and N-substituted allylamine.

To fit dianam include butadiene, cyclopentadiene and Dicyclopentadiene.

Acceptable allyl esters of saturated monocarboxylic acids could the invention can be obtained from one or more ethanobotany monomers. In this regard it should be noted that the term "polymer" includes homopolymers and copolymers obtained by polymerization of two or more different monomers.

For latexes of acrylic and styrene-based preferred low molecular weight CMC. For vinyl acetate-acrylate systems use mainly low-molecular GMGEC, but can also be used low molecular weight SCE and low molecular weight CMC. When the polymerization process used acrylic acid or methacrylic acid, the preferred content ranges from roughly 0.005 to about 2 wt.%, more preferably from about 0.05 to about 1 wt.% of the total number ethyleneamines Monomeric component.

The polymers according to the invention with a relatively high glass transition temperature (for example, from about 50 to about 150oC) can be characterized as "hard", and polymers with a relatively low glass transition temperature (for example, from about -100 to about -3oC) can be classified as "soft". The factor affecting the degree of hardness and softness, is determined by the properties of a particular ethanobotany monomers that apply.

The difference is they have known as "hard" and "soft" monomers. The relative hardness and softness of different monomers in the art known. Thus, the hardness or softness of the polymer is affected by the hardness or softness of the monomers forming the polymer, and the relative ratio between the two monomers.

When preparing a copolymer latex system balance between "hard" and "soft" monomers are chosen so that when the temperature of the formed continuous latex film. Styrolene-acrylic products can be obtained when the content of styrene units in the resulting copolymer in the range from about 0.005-about 70 wt.%. Vinyl-acrylic products can be obtained in the range of mass ratios between the parts 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 dispersion obtained in accordance with the present invention significantly improves the resistance to scratching prepared with their use in latex paints. Latex paints include paints for glossy and matte coatings coatings, and the volume concentration of the pigment in the paint for a glossy coating is less than S="ptx2">

For the practical implementation of the present invention can be used are known in the art of anionic, cationic, nonionic and amphoteric surfactants, and mixtures thereof. Acceptable surfactants include polyglycolide esters, sulfonated paraffin hydrocarbons, higher alkyl sulphates, such as lauryl sulphate, alkali metal salts of fatty acids such as sodium stearate and sodium oleate esters of sulfuric acid and fatty alcohols, ethoxylated C4-C50ALKYLPHENOLS and their products of sulfonation, such as ethoxylated Nonylphenol with 4-50, more preferably 10-20 ethylenoxide links, ethoxylated C4-C50the alkanols and products of sulfonation, as well as esters sulfonterol acid, such as dioctylsulfosuccinate sodium and mixtures thereof. These surfactants or emulsifiers is optional, and their use is not always required, however, if they are used, their amount is usually 0.1 to 5.0 wt.%, preferably 0.1-2.0 wt.% of the total number ethanobotany monomers introduced into the process.

You can apply any of the known methods of emulsion polymer is ing technology. Preferably paliperidonesee adding monomer with the addition of the initiator or catalyst, either in one portion or continuously. The polymerization process can also be carried out with a large shear force, which means, for example, the possibility of applying for the reaction of the reactor with circulation. In a preferred embodiment, the first portion loaded into the reactor, ethanobotany monomer or monomers 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 the preferred embodiment, in the initial portion loaded into the reactor, the initiator is injected from about 0 to about 60 wt.%, more preferably from about 50 to about 60 wt.%. A continuous supply of any of the reaction component or components is usually carried out over a period of time from about 2 to about 5 hours, the Initiator or the catalyst can be introduced in a single portion or in slow mode, although for practical implementation of the present invention it is not necessary.

Typically, the monomers will polimerizuet method aqueous emulsion polymerization at a temperature of from pravoradikalnoy polymerization, preferably water-soluble peroxides, e.g. hydrogen peroxide, persulfates, such as persulfates such as potassium, sodium and ammonium, or in some cases perborates. For polymerization of the monomers can be also used other methods known in the art, such as with the use of a redox polymerization catalyst systems, such as potassium persulfate and sodium bisulfite. The initiator is used at a concentration of 0.2-2.0 wt.% by weight of monomer(s), preferably in quantities of from 0.3 to 1.0 wt.%.

Prepared according to the invention the product is a latex system, including particles thus obtained polymer, dispersed as a dispersed phase in an aqueous continuous phase, and also includes a protective colloid. In a preferred embodiment, the average 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.

Latex system according to the present invention has excellent resistance to shear. In accordance with the above description it can be used in the compositions of latex cu and filler, and also the composition of latex paints can be introduced additional components, including thickeners.

In addition, the latex system of the present invention can be used in the compositions of inks, water-based, means for coating paper, binders for non-woven textile material and adhesive compositions, in particular bestextreme adhesive compositions.

In this description and in all cases, unless otherwise stated, amounts are indicated in mass units or percent.

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

Examples

Mw was determined using the method of high resolution chromatography preemptive size (HVR), consisting of the following.

Equipment: For HVR analysis used the instrument Varian 5010 LC, equipped with a differential Refractometer R401 firms Waters Associates and recording device models BD 40 firms Keep and Zonen. To enable periodically rinse with a strong stream of fluid reference side of the cell between the output lines of the sample and the reference sample inlet was ustensiles stationary mobile phase. The input produced by the valve Rheodyne model 7010, equipped with a 50-Microlitre tube for input samples.

Chromatographic column: Used HVR speakers firms SynChrom, Inc. (Linken, PCs Indiana); they contain chemically bound glycerolphosphate phase on the silicon dioxide. Used set of speakers consisted of pre-columns for GPC with a pore size of nozzles [5 cm x 4.1 mm (inner diameter), the series N 227904], two civil-analytical columns with pore sizes of nozzles [25 cm x 4.6 mm (inner diameter), series N 222033, 49201] and GPC analytical column with a pore size of nozzle [25 cm x 4.6 mm (inner diameter), the series N 48205]. These columns were connected in series in that order.

Preparation of mobile phase: the mobile phase analyses used an acetate buffer solution ionic strength 0.7 M with a pH of 3.7. Mobile phase with a pH value of 3.7 was prepared by first input 60 ml of 4 M sodium acetate solution and 440 ml of 4 M acetic acid in one litre volumetric flask and addition to its volume of distilled deionized water. Which resulted in formation of the buffer ionic strength of 0.24 M with a pH of 3.7. Next, the ionic strength of this solution was increased to 1.44 M by the addition of 0.4 e tests to minimize inconsistencies in the mobile phase. The final mobile phase was prepared by diluting the 1.44 M solution of double-strength distilled deionized water at a ratio of 1: 1 and filtered through a Millipore membrane type GS with a pore size of 0.22 μm.

Sample preparation: All samples were prepared by dissolving 0,150 g of polymer (adjusted quantity of dry matter moisture content) in distilled deionized water to bring the total volume to 25 ml, receiving an initial concentration of 6 mg/ml Further, these aqueous solutions were diluted in the ratio 1: 1 to 1.4 M acetate buffer solution double strength concentrations up to 3 mg/ml, which approximately corresponded to the composition of the mobile phase. Before entering all solution samples were filtered through a disposable filtration device Millex-HV, Millipore).

Conditions analysis

Set columns: - civil-preliminary, column (Synchropack)

Mobile phase: - 0.7 M acetate buffer with a pH of 3.7

Flow rate: 0.5 ml/min (according to the dimensions of 0.51 ml/min)

Pressure: - 135-140 ATM

The speed of movement of the chart paper: 1 cm/min

Concentration of sample: - 1.5-2.0 mg/ml

Coarsening DPP: - 2x

Under these conditions produced multiple input samples. For comparison with hafnium previous volume (size) analyzed a number of dextranomer standards with different Mw American Polymer Standards Corporation (DXTKIT). As the internal standard used is also standard with the lowest molecular weight (DXT-180 Mw), which was mainly elyuirovaniya with a total limit seepage.

The method of determining the average molecular weight Mw

Example 1

Fully acrylic materials, stable low molecular weight CMC

This example presents one of the options aqueous dispersions of the present invention and methods for their preparation.

The polymerization was carried out in 2-liter glass reaction vessel which was equipped with a thermocouple, reflux condenser, means for inlet of the monomers, by means of the inlet initiator and an anchor stirrer. In 461 g of demineralized water was dissolved 16.6 g of protective colloid [carboxymethylcellulose (CMC), supplied to the market by the company Aqualon Company under the trademark Ambergum 3021, average molecular weight (Mw) from about 7000 to 11000, the degree of substitution of carboxyl groups of approximately 1.2, the concentration of the solution of 29.6% viscosity Brookfield 630 mPas at 25oC] together with 1.6 g of sodium bicarbonate. After complete dissolution, the temperature was raised to 85oC using a water bath. During the next 30 to uniformly added a 40% solution of initiator (1,5 the ect (248,6 g of butyl acrylate, 248,6 g of methyl methacrylate and 2.8 g of methacrylic acid) was added with an initial velocity of 54.5 g/h, and within the first hour of reaction the rate was gradually increased to 163,5 g/h When the temperature was returned to level 85oC, was added approximately 95% of the remainder of the initiator solution, and the remaining 5% solution of initiator was added after adding the total amount of monomer. Enter the specified 95% of the remaining initiator was carried out during the same time period as the input of the monomer, and the feed rate of the initiator regulated in accordance with the feed rate of the monomer so that the addition of the monomer and of these 95% of the residue of the initiator was completed at the same time. The monomer and the initiator were introduced within 3.5-4 hours by a plunger pump and a peristaltic pump.

The reaction temperature was maintained at a level of 85oC. the Polymerization was completed, maintaining the temperature at 85oC, within 1 hour after entering the initiator and monomer. Next, the resulting latex was cooled to room temperature. During the reaction, the stirring speed was 200 rpm

Comparative example AND

Palestestinian the need to add low molecular weight protective colloid. Used the same composition and the same method described in example 1, except for the following changes: instead of 16.6 g of the product Ambergum3021 used 10 g of CMC MR [viscosity by Brookfield 430 mPas (2% solution at 25oC)] with Mw of about 300000. To bring the dry matter content in the resulting latex to the same level in this case, the amount of demineralized water were brought to 473,

Comparative example B

Fully acrylic materials, stable nonionic surface-active agent

In this comparative example illustrates the necessity of using large quantities of nonionic surfactants to obtain resistant to the shift of latexes, and this example is intended for comparison with the data according to the invention. Used the same composition and the same method described in example 1, except that instead of 16.6 g of protective colloid used 20 g of nonionic surfactant (ethoxylated Nonylphenol with 10 ethylenoxide links: Intrasol NP10, 100% active substance, the company Stockhausen), which was dissolved in 433 g of demineralized water.

Comparative example

In the properties

In this comparative example illustrates the necessity of using a large number of surfactants in the fully-acrylic latexes without the use of a protective colloid to obtain resistant to the shift of the latexes. Used the same composition and the same method described in example 1, except that instead of 16.6 g of protective colloid used 10 g of nonionic surfactant (ethoxylated Nonylphenol with 10 ethylenoxide links: Intrasol NP10, 100% active substance), together with 10 g of anionic surfactant (dioctylsulfosuccinate: Aerosol OT-75, 75% of the active substance Cyanamid company), which was dissolved in 472 g of demineralized water.

Example 2

Contains no surfactants styrene-acrylic materials, stable low molecular weight CMC

This example presents another embodiment of the invention. The polymerization processes conducted in 2-liter glass reaction vessel which was equipped with a thermocouple, reflux condenser, means for inlet of the monomers, by means of the inlet initiator and an anchor stirrer. 450 g of demineralized water was dissolved 33 g of protective colloid and 1.6 g of sodium bicarbonate. After complete dissolution, the temperature was raised to 85oC using a water bath. During the next 30 to uniformly added a 40% solution of initiator (1.5 g of potassium persulfate in 50 g of demineralized water). After one minute, began to enter the monomer. A Monomeric mixture of 245 g of butyl acrylate, 245 g of styrene and 10 g of methacrylic acid) was administered with an initial velocity of 54.5 g/h and within the first hour of reaction the rate was gradually increased to 163,5 g/H. the Remainder of the method of polymerization was similar to that described in example 1.

Comparative example D

Styrene-acrylic materials, stable anionic and nonionic surfactants

In this comparative example illustrates the necessity of using low molecular weight CMC as a stabilizer at low concentrations of surfactants to obtain a stable latex. Used the same composition and the same method described in example 2, except that instead of 33 g of protective colloid used 15 g of anionic surfactant (ether alkylarylsulfonate: Disponil AES 60, 33% of the active substance, the firm Henkel GmbH, düsseldorf, Germany) together with 5 g of nonionic on the th substance) in 463 g of water. Monomeric mixture in this case included 248,6 g of butyl acrylate, 248,6 g of styrene, 2.8 g of methacrylic acid.

Example 3

Styrene-acrylic stabilized materials as surfactants and low molecular weight CMC

Applied composition and method described in example 2, except that in addition to solution Ambergumfor stabilization used 15 g of anionic surfactant (ether alkylarylsulfonate: Disponil AES 60, 33% of active substance) and 5 g of nonionic surfactant (ethoxylated Nonylphenol with 10 ethylenoxide links: Intrasol NP10, 100% active substance) in 450 g of water.

Example 4

Styrene-acrylic stabilized materials as surfactants and low molecular weight CMC

Applied composition and method described in take 2, except that instead of 33 g used 16.6 g of product Ambergum3021 in combination with 5.9 g of anionic surfactant (dicyclohexylphosphino sodium: Aerosol A196, 85% active material), 5 g of nonionic surfactant (ethoxylated Nonylphenol with 4 ethylenoxide links: Surfonic N40, 100% active oscillate. To improve the conversion of the monomer, the amount of initiator was increased. The initiator solution contained 3 g of potassium persulfate in 100 g of water.

Example 5

The vinyl acetate-acrylic materials with low molecular weight CMC

This example illustrates the possibility of preparation of vinyl-acrylic dispersions that do not contain surface-active substances, with a relatively large number of butyl acrylate in the monomer composition.

The polymerization processes conducted in 2-liter glass reaction vessel equipped with a thermocouple, reflux condenser, means for inlet of the monomers, by means of the inlet initiator and an anchor stirrer. In 397 g of demineralized water was dissolved 33 g of protective colloid (CMC Ambergum3021 when the concentration of the solution of 29.6%, the viscosity of which Brookfield has approximately 630 mPas at 25oC) and 2.0 g of sodium bicarbonate. After complete dissolution, the temperature was raised to 80oC using a water bath.

During the next 30 to uniformly added a 40% solution of initiator (1.5 g of potassium persulfate in 50 g of demineralized water). After one minute has started to add the monomer. A Monomeric mixture of 350 g of vinyl acetate and 150 g of butyl acrylate) first dobavlja per hour. When the temperature again reached 80oC, was added 95% of the remainder of the initiator solution. The remaining 5% solution of initiator was added after adding the total amount of monomer. The initiator was introduced during the same time period as the monomer, and the feed rate of the initiator regulated in accordance with the feed rate of the monomer. The monomer and the initiator were introduced within 3.5-4 hours by a plunger pump and a peristaltic pump. The reaction temperature was maintained at 80oC. the Polymerization was completed, maintaining the temperature 80oC within 1 hour after entering the initiator and monomer. Further, the latex was cooled to room temperature. During the reaction, the stirring speed was 200 rpm

Example 6

The vinyl acetate-acrylic materials with surface-active agent and a low molecular weight CMC

Applied composition and method described in example 5, except for the following changes: instead of 33 g of CMC Ambergum3021 in 363 g of demineralized water was dissolved 67 g of the product Ambergum1521 (solution concentration of 14.7% with a viscosity according to Brookfield at 25oC 1540 mPas, Mw from about 35000 to 50000, the degree Saltimbanco of Nonylphenol ethoxylated with 30 ethylenoxide links: product Fenopon EP 120; 30% of active substance) and 7.1 g of nonionic surfactant (of ethoxylated Nonylphenol: Antarox CO 897, 70% of active substance). The remainder of the composition was similar to that described in example 4.

Example 7 a vinyl Acetate-acrylic materials with surface-active agent and a low molecular weight CMC

Applied composition and method described in example 5, except that in this case we also added a surfactant, a protective colloid and a buffer, which was dissolved in 397 g of water together with 5 g of nonionic surfactant (of Nonylphenol ethoxylated with 20 ethylenoxide links: Tergitol NP40, 100% active substance) and 17 g of anionic surfactant (sulphonated of Nonylphenol ethoxylated with 30 ethylenoxide links: Fenopon EP 120; 30% active substance).

Example 8

The vinyl acetate-acrylic materials with surface-active agent and a low molecular weight SCE

Applied composition and method described in example 1, except that in 397 g of demineralized water was dissolving 12.5 g of anionic surfactant (Disponil MGS 156, 40% active substance), mixed with 7.1 g n is), 33 g of low-molecular SCE (solution concentration of 29.1% viscosity Brookfield at 25oC 260 mPas) with a Mw from about 7000 to about 11000 and 2.8 g of sodium bicarbonate. The reaction temperature was 80oC, and the monomer mixture consisted of 350 g of vinyl acetate and 150 g of butyl acrylate.

Example 9

The vinyl acetate-acrylic materials with surface-active agent and a low molecular weight GMGEC (invention)

Applied composition and method described in example 8, except that instead of a low molecular weight CMC was used to 47.4 g of low-molecular GMGEC Natrosol Plus (solution concentration of 21.1%, the viscosity according to Brookfield which at 25oC was 28.5 mPas). The mass-average molecular weight of the protective colloid was approximately 25000. Regulate the amount of water to achieve the same dry matter content as in latex. Surfactants, buffer (in this case 2.0 g) and the protective colloid was dissolved in 383 g of demineralized water.

Example 10

The vinyl acetate-acrylic materials with surface-active agent and a low molecular weight GMGEC

Applied composition and a method similar to that described in example 8, except for the diamonds which at 25oC was 4 mPas, with srednevekovoi molecular weight material approx 25000). Regulate the amount of water. Surfactant, 2.0 g buffer and protective colloid was dissolved in 383 g of demineralized water.

Comparative example D

The vinyl acetate-acrylic materials, stabilized by surfactants

This example used the same composition and the same method described in example 9, except they did not use protective colloid, and a mixture of surfactants and the buffer was dissolved in 420 g of water. Obviously, in the case of using only surfactants conversion of monomer worse, and the viscosity of the latex is very low.

Example 11

The vinyl acetate-ethylene material, stable surface-active agent and a low molecular weight CMC

Polymerization was performed in a 2-liter reaction vessel of stainless steel, equipped with a thermocouple, means for inlet of the monomers, by means of the inlet initiator and an anchor stirrer. In 337 g of demineralized water was dissolved 33 g of protective colloid (CMC Ambergum3021 when the concentration of the solution of 29.6%, the viscosity of which amounted to 630 mPas is th salts with 100% active substance] and 3.6 g of Antarox CO 897 (Nonylphenol EO). After complete dissolution, the temperature was raised to 80oC. within 30 evenly added a 15% solution of initiator (2.5 g of potassium persulfate in 100 g of demineralized water). After one minute, began to enter the monomer and the remainder of the initiator solution. Within 120 minutes was gradually added 445 g of vinyl acetate, maintaining the pressure of ethylene in the reaction vessel at the level of 21 bar. The initiator was introduced during the same time period as the monomer. The reaction temperature was maintained at 80oC. the Polymerization was completed, maintaining the temperature 80oC for 1 hour after completion of the input of the initiator and monomer. Further, the latex was cooled to room temperature.

Example 12

The vinyl acetate-butyl acrylate material, stabilized by surfactants and low molecular weight CMC; polymerization with high shear

This example illustrates the possibility of using high shear during the reaction, when using low molecular weight protective colloid.

Applied composition and method described in example 5, except that in this example 397 g of demineralized water was dissolved a mixture of 12.5 g of anionic surface-active is p Nonylphenol: Antarox CO 897, 70% of active substance), 33 g of protective colloid (CMC Ambergum3021, the solution concentration of 29.6%, a viscosity according to Brookfield which at 25oC was 630 mPas) and 2.0 g of sodium bicarbonate. The rotation speed of the mixer in this example was 400 rpm (peripheral speed of the end blades of 2.72 m/s).

Example E

The vinyl acetate-butyl acrylate material, stabilized by surfactants; polymerization with high shear

In this comparative example illustrates the use of protective colloid during the polymerization when using high shear.

This example used the same composition and the same method described in example 5, except that in this case, 420 g of demineralised water was dissolved a mixture of 12.5 g of anionic surfactant (Disponil MGS 156, 40% active substance), and 7.1 g of nonionic surfactant (ethoxylated Nonylphenol: Antarox CO 897, 70% active substance) and 2.0 g of sodium bicarbonate. The rotation speed of the mixer in this example was 400 rpm (peripheral speed of the end blades of 2.72 m/s).

Example 13

Fully acrylic latex, characterized by low to mirimar 1, except for the following changes. Instead of 16.6 g of the product CMC Ambergum3021 450 g of demineralized water was dissolved 33 g of CMC Ambergum3021 together with 6.25 g of dioxincontaminated (Disponil SUS IC 680, 80% of active substance), 5 g of ethoxylated Nonylphenol with 4 ethylenoxide links (Sulfonic N40, 100% active substance) and 1.6 g of sodium bicarbonate. The monomer mixture consisted of 200 g of methyl methacrylate, 300 g of butyl acrylate and 2.8 g of methacrylic acid.

Example G

Fully acrylic latex, characterized by a low minimum temperature of film formation and stabilized by surfactants

The polymerization in this comparative example was carried out similarly to example 13, except that it is not applied polymer Ambergumfor stabilization. Therefore, 473 g of water was dissolved surfactant and a buffer.

Example 14

The vinyl acetate-acrylic latex, characterized by a low minimum temperature of film formation and stable GMGEC ultra low molecular weight

Polymerization was performed according to example 10, except for the following changes. In 422 g of demineralized water was dissolved 12.7 g smeego alcohol (Disponil APE 257, 65% of active substance), 1.6 g of sodium bicarbonate and 10 g of low-molecular GMGEC Natrosol Plus. The monomer mixture consisted of 200 g of vinyl acetate and 300 g of butyl acrylate.

Example 15

The latex product of a vinyl acetate/VeoVa-10, characterized by average minimum temperature of film formation and stable CMC

The polymerization was carried out in 2-liter glass reaction vessel equipped with a thermocouple, reflux condenser, means for inlet of the monomers, by means of the inlet initiator and an anchor stirrer.

In 432 g of demineralized water were dissolved 40 g of protective colloid (CMC Ambergum3021 when the concentration of the solution of 29.6%, the viscosity of which Brookfield has approximately 630 mPas at 25oC) together with 1.6 g of sodium bicarbonate, 7.5 g of dioxincontaminated (Disponil SUS IC 680, 80% of active substance) and 6 g of nonionic surfactant (ATPOL E 5720). After complete dissolution, the temperature was raised to 80oC using a water bath. Then for 1 min was added 5% of the total number of monomer. After 2 min was added a 25% solution of initiator (1.8 g of potassium persulfate in 60 g of demineralized water). When the temperature again reached 72oC, began to enter the monomer. eoVa is a trademark of Shell Chemical Company, providing the market uiniversity products. After 5 min the temperature was raised to 80oC and the mixture was stirred at this temperature. The flow rate of the initiator solution was regulated in accordance with the flow rate of the monomer. During the reaction, the mixer rotation speed was 200 rpm for 1 h after the addition of initiator and monomer polymerization was completed, maintaining the temperature at 80oC. the polymerized mass was cooled to room temperature.

Example C

The latex product of a vinyl acetate/VeoVa-10 with an average minimum temperature of film formation and stabilized by surfactants

The polymerization in this comparative example was carried out in accordance with example 15, except that the protective colloid is not used. The amount of water, therefore, brought up to 460,

Example 16

Latex, methyl methacrylate/VeoVa-9/butyl acrylate material, stable CMC and surface-active substances

The polymerization was carried out in accordance with example 13, except that the monomer mixture consisted of 100 g of methyl methacrylate, 100 g of the monomer VeoVa-9, 300 g of butyl acrylate and 2.8 g of methacrylic acid is C without surfactants

The polymerization was carried out in accordance with example 16, except that the surfactant was removed.

Example 18

The methyl methacrylate/butyl acrylate latex, stable hydroxypropylcellulose ultralow molecular weight

The polymerization was carried out according to the method described in example 1. As a protective colloid instead of 16.6 g of CMC Ambergum3021 used 16.5 g of 30% aqueous solution hydroxypropylcellulose ultra-low molecular weight (Mw 6500), the turbidity of which accounted for more than 90oC.

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

Dry matter content was determined gravimetrically by weighing a quantity of latex, drying the portion 120oC, re-weighing the dried portions and further dividing the dry weight to wet weight. The content of small solid particles was determined as a fraction, particle size exceeding 200 #, passing the weighted portion of the latex through a sieve N 200. Film properties were determined on latex films with thickness in the wet state 200 micrometers (μm) on a glass substrate in B20, and at 45oC. the Gloss of the films was measured by using a gloss meter Bika at an angle of 60o.

The resistance was measured by applying a few drops of water on the film. After 5 min was assessed by the appearance of the films. The evaluation was made according to the following scale:

10 transparent

8 slightly muddy

6 muddy

5 milk

2 white

0 film re-emulsify

Particle size was determined by the disc centrifuge Joyce of Lable.

Example 19

Paint with a volume concentration of pigment (GST) 65 prepared from a vinyl acetate-butyl acrylate latex stabilized by surfactants and low molecular weight GMGEC

According to this example, the latex is stabilized with a protective colloid, with discrete (heterogeneous) polymer phase, characterized by small particle size (in this case approximately 200 nanometers), shows excellent properties in that the paint has good film-forming ability. When such fine particles of paint can be prepared in the form of systems with higher filler contents.

In the paint with PCOS 65 used latex according to example 9, as shown in TA is latex-based material is a vinyl acetate-VeoVa (Mowilith DM 21)

As shown in table 3, in the composition with PCOS 65 used technical latex Mowilith DM 21. This paint is stabilized by surface-active substances and GMGEC Natrosol Plus low molecular weight.

Example 20

Paint with PCOS 80, based on the vinyl acetate-butyl acrylate latex stabilized by surfactants and GMGEC low molecular weight

In the paint with PCOS 80 used latex according to example 9, as shown in table 3.

Example 21

Paint with PCOS 80, prepared on the basis of styrene-acrylate latex stabilized by surfactants and low molecular weight CMC

As shown in table 3, the functions of the latex paint with PCOS 80 performed latex described in example 4, except that the protective colloid used 33 g of the solution Ambergum3021 (instead of 16.6 g).

Comparative example TO

Paint with PCOS, prepared on the basis of technical styrene-acrylate latex (Acronal 290 D)

Also in accordance with the presented in the table 3 data in combination with GST 80 used technical latex (Acronal 290 D).

Example 22

Paint with PCOS 15, cooked to asnom with PCOS 15 used as shown in table 3, the latex described in example 1.

Comparative example L

Paint with PCOS 15, prepared on the basis of technical acrylic latex (Primal AC 507)

The composition of the GST 15, as shown in table 3, used technical latex Primal AC 507.

The properties of the inks according to examples 19 to 21 and comparative examples K and L are given in tables 4 and 5.

Relatively thickeners, are shown in tables 4 and 5, it should be noted that Natrosol MBR and Natrosol HBR is used as associative thickeners, and Natrosol Plus and Primal RMB is used as associative thickeners. Natrosol MBR and Natrosol HBR, as well as Natrosol Plus, are supplied to the market by the company Hercules Incorporated, Wilmington, pieces of Delaware; Primal RMB marketed by the company Rohm & Haas, Philadelphia, pieces Pennsylvania.

Example 23

Does not contain solvents latex paint for Matt coatings were prepared using the following components, including, as mentioned, the latex according to example 13.

Component Amount (grams)

Water - 197

Calgon N - 1,0

Pigment dispersant 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 and according to example 23 are presented in table 6.

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

1. The method of preparation of the latex system, which is characterized by improved mechanical stability, includes water emulsion (co)polymerization of at least one ethyleneamines monomer in the presence of effective to stabilize the latex system number of water-soluble protective colloid selected from the group consisting of carboxymethyl cellulose and its derivatives, the lower limit of the degree of carboxyl substitution which is approximately 0.7, hydroxyethyl cellulose, metilgidroxiatilzelllozu, methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, hydrophobically modified ethers of cellulose, polyacrylic acid and its alkali metal salts, ethoxylated starch derivatives, polyacrylates, sodium and other alkali metals, water-soluble starch glue, gelatin, of a water-soluble alginates, casein, agar, natural and synthetic Kameda is alimera metilfenidato ether and maleic anhydride, as well as the polymerization initiator, characterized in that as ethylenevinylacetate monomer using a monomer selected from the group consisting of acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, acrylic esters, styrene, vinyl ethers, vinyl, vinylidenechloride, N-vinylpyrrolidone, ethylene, C3-C24alpha-olefins, allylamine, allyl esters of saturated monocarboxylic acids, their amides, propylene, 1-butene, 1-pentene, 1-hexene, 1-mission ZIOC scientists arylpropionate, allylacetate, their amides and their mixtures, and used water-soluble protective colloid has a mass-average molecular mass of less than approximately 75,000.

2. The method according to p. 1, characterized in that use is also from about 0.1 to about 5.0 wt.% surfactants of the total content ethyleneamines monomer.

3. The method according to p. 2, characterized in that the surfactant is chosen from the group consisting of anionic, cationic, nonionic and amphoteric surfactants and mixtures thereof.

4. The method according to p. 3, characterized in that the surfactant is chosen from the group consisting of simple floors fatty acids, esters of sulfuric acid and fatty alcohols, ethoxylated C4-C50ALKYLPHENOLS and their products of sulfonation, ethoxylated C4-C50alkanols and their products of sulfonation, esters sulfonterol acid and mixtures thereof.

5. The method according to p. 4, characterized in that the surfactant is chosen from the group consisting of nonylphenolethoxylate 4 - 50 ethylenoxide links of dioctylsulfosuccinate sodium lauryl sulphate, sodium stearate, sodium oleate, and mixtures thereof.

6. The method according to p. 1, characterized in that the protective colloid selected from the group consisting of hydroxyethyl cellulose, metilgidroxiatilzelllozu, carboxymethylcellulose, the lower limit of the degree of carboxyl substitution which is approximately 0.7, methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, ethoxylated starch derivatives, partially and fully hydrolyzed polyvinyl alcohol, polyacrylic acid, polyacrylate sodium and other alkali metals, polyacrylamide, copolymer metilfenidato ether and maleic anhydride, polyvinylpyrrolidone, water-soluble starch glue, gelatin, of a water-soluble alginates, casein, anemoscope molecular weight protective colloid is approximately 50,000.

8. The method according to p. 1, wherein the protective colloid is a simple cellulose ether selected from the group consisting of hydroxyethyl cellulose, metilgidroxiatilzelllozu, carboxymethylcellulose, the lower limit of the degree of carboxyl substitution which is approximately 0.7, methylcellulose, methylhydroxypropylcellulose and hydroxypropylcellulose.

9. The method according to p. 1, characterized in that the upper limit on the mass-average molecular weight protective colloid is about 20000.

10. The method according to p. 1, characterized in that the degree of carboxyl substitution of carboxymethyl cellulose is approximately 0.7 and 2.9.

11. The method according to p. 1, characterized in that the upper limit hydroxyethylene molar substitution of hydroxyethyl cellulose is 4.0.

12. The method according to p. 11, characterized in that the lower limit hydroxyethylene molar substitution of hydroxyethyl cellulose approximately 1.6.

13. The method according to p. 1, characterized in that the hydrophobic modified ethers of cellulose are cellulose ethers, which are optionally substituted hydrocarbon containing 4 to 25 carbon atoms, and the mass is modified simple cellulose ether.

14. The method according to p. 13, characterized in that the hydrophobic modified simple cellulose ether is a hydrophobically modified hydroxyethyl cellulose.

15. The method according to p. 14, where the upper limit hydroxyethylene molar substitution hydrophobically modified hydroxyethyl cellulose is approximately 4,0.

16. The method according to p. 15, where the lower limit hydroxyethylene molar substitution hydrophobically modified hydroxyethyl cellulose is around 2.9.

17. The method according to p. 1, characterized in that the initiator is chosen from the group consisting of water-soluble peroxides, persulfates and perborates.

18. The method according to p. 17, characterized in that the initiator is chosen from the group consisting of hydrogen peroxide, persulfate potassium, sodium and ammonium and sodium perborate.

19. The method according to p. 1, characterized in that the (co)polymerization is conducted semi-continuous with the introduction at the beginning of the reaction is from about 0 to about 60% of the total amount of initiator and from about 0 to about 40% of the total number of at least one ethyleneamines monomer.

20. The method according to p. 1, characterized in that the (co)polymerization is conducted continuously.

manual preparation of the latex system, characterized by superior mechanical stability, includes water emulsion (co)polymerization of at least one ethyleneamines monomer in the presence of effective to stabilize the latex system number of water-soluble protective colloid selected from the group consisting of hydroxyethyl cellulose, metilgidroxiatilzelllozu, methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, hydrophobically modified ethers of cellulose, ethoxylated starch derivatives, partially and fully hydrolyzed polyvinyl alcohol, polyacrylic acid, polyacrylate sodium and other alkali metals, polyacrylamide, copolymer metilfenidato ether and maleic anhydride, polyvinylpyrrolidone, water-soluble starch glue, gelatin, of a water-soluble alginates, casein, agar, natural and synthetic gums and derivatives thereof, and the polymerization initiator, characterized in that the use of protective colloid with mass-average molecular mass of less than approximately 75,000.

23. The method according to p. 22, characterized in that it additionally used as surfactant in an amount of from about 0 about on p. 23, characterized in that the surfactant is chosen from the group consisting of anionic, cationic, nonionic and amphoteric surfactants and mixtures thereof.

25. The method according to p. 23, characterized in that the surfactant is chosen from the group consisting of simple polyglycolic esters, sulfonated paraffin hydrocarbons, higher alkyl sulphates, alkali metal salts of fatty acids, esters of sulfuric acid and fatty alcohols, ethoxylated C4-C50ALKYLPHENOLS and their products of sulfonation, ethoxylated C4-C50alkanols and their products of sulfonation, esters sulfonterol acid and mixtures thereof.

26. The method according to p. 25, characterized in that the surfactant is chosen from the group consisting of nonylphenolethoxylate 4 - 50 ethylenoxide links of dioctylsulfosuccinate sodium lauryl sulphate, sodium stearate, sodium oleate, and mixtures thereof.

27. The method according to p. 22, characterized in that at least one ethanobotany monomer selected from the group consisting of acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, acrylic esters, styrene and mixtures thereof.

28. The way the th of vinyl esters, vinyl ethers, vinyl, vinylidenechloride, N-vinylpyrrolidone, ethylene, C3-C24alpha-olefins, allylamine, allyl esters of saturated monocarboxylic acids, their amides and mixtures thereof.

29. The method according to p. 22, characterized in that the upper limit on the mass-average molecular weight protective colloid is approximately 50,000.

30. The method according to p. 22, characterized in that the upper limit on the mass-average molecular weight protective colloid is about 20000.

31. The method according to p. 22, wherein the protective colloid is a simple cellulose ether selected from the group consisting of hydroxyethyl cellulose, metilgidroxiatilzelllozu, methylcellulose, methylhydroxypropylcellulose and hydroxypropylcellulose.

32. The method according to p. 22, characterized in that the upper limit hydroxyethylene molar substitution of hydroxyethyl cellulose is 4.0.

33. The method according to p. 32, characterized in that the lower limit hydroxyethylene molar substitution of hydroxyethyl cellulose approximately 1.6.

34. The method according to p. 22, characterized in that the hydrophobic modified ethers of cellulose are the way the native atoms, and the massive amount of hydrocarbon is from about 0.1 to about 3 wt.% of the total number of hydrophobic modified simple cellulose ether.

35. The method according to p. 34, characterized in that the hydrophobic modified simple cellulose ether is a hydrophobically modified hydroxyethyl cellulose.

36. The method according to p. 35, characterized in that the upper limit hydroxyethylene molar substitution hydrophobically modified hydroxyethyl cellulose is approximately 4,0.

37. The method according to p. 36, characterized in that the lower limit hydroxyethylene molar substitution hydrophobically modified hydroxyethyl cellulose is around 2.9.

38. The method according to p. 22, characterized in that the initiator is chosen from the group consisting of water-soluble peroxides, persulfates and perborates.

39. The method according to p. 38, characterized in that the initiator is chosen from the group consisting of hydrogen peroxide, persulfate potassium, sodium and ammonium and sodium perborate.

40. The method according to p. 22, characterized in that the (co)polymerization is conducted semi-continuous with the introduction at the beginning of the reaction is from about 0 to about 60% of the total kalisher.

41. The method according to p. 22, characterized in that the (co)polymerization is conducted continuously.

42. The method according to p. 22, characterized in that the (co)polymerization is carried out in a reactor with circulation.

43. Latex system, which is characterized by improved mechanical stability, includes water emulsion containing (a) a (co)polymer of at least one ethyleneamines monomer and (b) effective for stabilization of the latex system the amount of water-soluble protective colloid selected from the group consisting of carboxymethyl cellulose and its derivatives, the lower limit of the degree of carboxyl substitution which is approximately 0.7, hydroxyethyl cellulose, metilgidroxiatilzelllozu, methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, polyacrylic acid and its alkali metal salts, ethoxylated starch derivatives, polyacrylates, sodium and other alkali metals, water-soluble starch glue, gelatin, of a water-soluble alginates, casein, agar, natural and synthetic gums, partially and fully hydrolyzed polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone and copolymers metilfenidato ether and maleinos the howling acid, methacrylic acid, butyl acrylate, methyl methacrylate, acrylic esters, styrene, vinyl ethers, vinyl, vinylidenechloride, N-vinylpyrrolidone, ethylene, C3-C24alpha-olefins, allylamine, allyl esters of saturated monocarboxylic acids, their amides, propylene, 1-butene, 1-pentene, 1-hexene, 1-mission ZIOC scientists arylpropionate, allylacetate, their amides and mixtures thereof, and water-soluble protective colloid has a mass-average molecular mass of less than approximately 75,000.

44. Latex system on p. 43, characterized in that the (co)polymer obtained aqueous emulsion (co)polymerization in the presence of water-soluble protective colloid.

45. Latex system on p. 43, characterized in that it further comprises from about 0.1 to about 5.0 wt.% surfactants of the total number ethyleneamines Monomeric component.

46. Latex system on p. 43, characterized in that the upper limit on the mass-average molecular weight protective colloid is approximately 50,000.

47. Latex system on p. 43, characterized in that the (co)polymer is a dispersed phase, characterized by an average size across one product, selected from the group consisting of pigment and filler, and the latex system, characterized in that it contains the latex system on p. 43.

49. The composition is a latex paint on p. 48, characterized in that the latex does not contain solvent.

50 Composition of latex paint on p. 48, characterized in that the (co)polymer comprises particles of average size less than about 500 nanometers.

51. The composition is a latex paint on p. 48, wherein the paint is a paint for a glossy coating, the volume concentration of the pigment is less than about 50.

52. The composition is a latex paint on p. 48, wherein the paint is a matte paint for coating, the volume concentration of the pigment in which approximately 50 or more.

53. Composition printing of water-based paints, including latex system and at least another component of printing ink, characterized in that the latex system contains latex system on p. 43.

54. Composition for coating paper, comprising the latex system and at least another component of the composition for melove is 5. Not containing dextrin adhesive composition comprising a latex system and at least another does not contain dextrin component adhesive, characterized in that the latex system contains latex system on p. 43.

56. The binder for non-woven textile materials, including latex system and at least another component of the binder, characterized in that the latex system contains latex system on p. 43.

57. Latex system, which is characterized by improved mechanical stability, includes water emulsion containing (a) a (co)polymer of at least one ethyleneamines monomer and (b) effective for stabilization of the latex system the amount of water-soluble protective colloid selected from the group consisting of hydroxyethyl cellulose, metilgidroxiatilzelllozu, methylcellulose, methylhydroxypropylcellulose, hydroxypropylcellulose, ethoxylated starch derivatives, partially and fully hydrolyzed polyvinyl alcohol, polyacrylic acid, polyacrylate sodium and other alkali metals, polyacrylamide, copolymer metilfenidato ether and maleic anhydride, the floor is, prirodnykh and synthetic gums and their derivatives, characterized in that the water-soluble protective colloid has a mass-average molecular mass of less than approximately 75,000.

58. Latex system on p. 57, characterized in that the (co)polymer obtained aqueous emulsion (co)polymerization in the presence of water-soluble protective colloid.

59. Latex system on p. 57, characterized in that it further comprises from about 0.01 to about 4.0 wt.% surfactants of the total number ethyleneamines Monomeric component.

60. Latex system on p. 57, characterized in that the upper limit on the mass-average molecular weight protective colloid is approximately 50,000.

61. Latex system on p. 57, characterized in that at least one ethanobotany monomer selected from the group consisting of acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, acrylic esters, styrene and mixtures thereof.

62. Latex system on p. 57, characterized in that at least one ethanobotany monomer selected from the group consisting of vinyl esters, vinyl ethers, vinyl, is IRow saturated monocarboxylic acids, their amides and mixtures thereof.

63. Latex system on p. 57, characterized in that the upper limit on the mass-average molecular weight protective colloid is approximately 20,000.

 

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