MXPA97003243A - Eteres de cellulosa in dispersions depolimerizacion by emuls - Google Patents

Abstract

The present invention relates to a process for the preparation of a latex system having a tendency to flocculation due to grafting, the improvement comprising the aqueous emulsion polymerization of at least one ethylenically unsaturated monomer selected from the group consisting of acrylic acid , methacrylic acid, butyl acrylate, butyl methacrylate, acrylic esters

Description

CELLULOSE ETERS IN EMULSION POLYMERIZATION DISPERSIONS BACKGROUND OF THE INVENTION 1. APPLICATION CONTINUATION DATA This application is a partial conformance to US Application Serial No. 08 / 542,269, filed on October 20, 1995 (No. attorney registration P14184), which is a continuation in part of US Application Serial No. 08 / 333,697, filed on November 3, 1994 and currently abandoned. These applications are incorporated herein in their entirety by reference. 2. FIELD OF THE INVENTION This invention relates to aqueous polymer dispersions derived from ethylenically unsaturated monomers in the presence of a water-soluble protective colloid and to processes for their preparation. 2. DESCRIPTION OF THE BACKGROUND AND ADDITIONAL INFORMATION In industrial processes of emulsion polymerization, surfactants are usually used either alone or in combination with polymeric protective colloids. A disadvantage in these processes is that surfactants must be used to obtain stable crosslinking to the shear that is not economical and that may have negative side effects. For example, the presence of surfactants in the presence of laser? < It can have negative effects on the sensitivity to water and can cause the formation of foam in the final products. In addition, at conventional levels of use, surfers do not provide sufficient mechanical stability to the final products. It is known in the prior art that the presence of protective colloids as co-stabilizers, such as, for example, hydroxyethylcellulase < HEC) and polyvinyl alcohol (PVOH), in emulsion polymerization of ethylenically unsaturated polymers, including vinyl monomers, vinyl monomers with an acrylic monomer with, for example, acrylic esters, methacrylic esters or mixtures thereof, provides crosslinked of particle size lower than mine with rheological characteristics, improved stability and performance. These aqueous polymer dispersions are useful in the manufacture of latex paints, binders for non-woven materials, water-based inks, paper coatings as well as water-borne adhesives such as pressure sensitive adhesives. In emulsion polymerization processes of monomers comprising acrylics or styrene either alone or in combination with other monomers, it is not always possible to employ protective colloids such as cellulosics or PVOH, co-ca-sta 1 i zadores. When protective colloids of the prior art are used in latex systems based on acrylic or based on styrene, a high degree of flocculation occurs which manifests itself in a lack of mechanical stability. This flocculation results from the remarkable tendency of the protective colloid to be incorporated directly into the polymer chain in reaction. This phenomenon is known as grafting. It should be understood that the graft itself should not be totally eliminated. Does a lower amount of graft not cause flocculation? furthermore, it improves the stability of latex systems, as has been known for a long time for vinyl acetate copolymer crosslinkers. It is the combination of an excessive graft with the possibility of establishing bridges between particles that causes coagulation. The formation of bridges between particles is not only determined by the amount of grafted material or the particle size alone, but also depends on the amount of water-soluble polymer present in the aqueous phase, the molecular weight of the protective colloid, the solid content, etc. In any case, according to the particular latex system, the lack of mechanical stability can be overcome by using high levels of surfactant alone or in combination with protective colloid. For example, in systems based on vinyl acetate, high levels of protective colloid are used in combination with surfactant, while in the case of systems based on acrylic >3, elevated levels of surfactant alone were removed. However, cross-links prepared with such high levels of surfactants have the performance problems described above. Accordingly, there is a need in the industry to overcome the drawbacks inherent in latex systems in the prior art in connection with the high use of surfactant or protective colloids of the prior art. An approach in accordance with CRAIG '704, U.S. Patent No. 4,684,704, is the use of approximately 0.0114 to about 1.7%, by weight based on the total monomer content, of a hydrophobically modified amount of hydroxyethylcellulose (HMHEC). ) which is easily and successfully incorporated into the dispersions or crosslinked by means of emulsion polymerization of monomers having a low protective potential of protective colloid. The resulting crosslinks have a particle size of less than one millimeter and excellent mechanical stability. Another approach for polymerizing acrylic monomer systems, presented in LO, North American Patent Na. No. 4,845,175, is to employ 0.02 to 2.14 by weight of a hydrophobically modified hydroxyethylcellulose as a rotatable colloid. Another approach for the polymerization of acrylic monomer systems, presented in CRAIG '771, US Pat. No. 4,659,771, is to employ, in addition to a protective colloid, from about 0.114 to 514 by weight of an unsaturated monomer conjugated substantially completely soluble in water from furoic acid, steric acid, and metal salts, amine salts, ammonium salts and quaternary salts of rosin and acids having from 4 to 36 carbon atoms. SUMMARY OF THE INVENTION The present invention is directed to a process for preparing a latex having improved mechanical stability comprising the emulsion polymerization of at least one ethylenically unsaturated monomer in the presence of, by weight based on the total ethylenic anomer content unsaturated, of an effective amount of a polymer which is a protective colloid with a molecular weight less than about 75,000 selected from the group consisting of polysaccharides, polyacrylyl acid and salts thereof, partial psvyl alcohol and fully hydrolyzed, polyacrylamide, polyvinylpyrrolidone , pallets, ivins, gelatin, casein and derivatives and mixtures of the group. The present invention is further focused on a latex system comprising an aqueous emulsion of a polymer of at least one ethylenically unsaturated monomer, and further including the indicated protective colloid. DESCRIPTION OF THE INVENTION It has been unexpectedly found that the use of low molecular weight protective colloid in emulsion polymerization of ethylenically unsaturated monomers produces excellent stability of the resulting polymer. The upper limit of the molecular weight of the protective colloid is about 75,000, preferably about 50,000 and with optimum preference about 20,000. The lower limit of the molecular weight of the protective colloid is about 5,000, preferably about 10,000, and with optimum degree of preference approximately 15,000. The present invention is especially useful for acrylic or styrene latex systems. As indicated above, with respect to the acrylic or styrene-based latex systems of the prior art, the use of commercially desirable levels of protective colloid is not practical due to the high levels of flocculation observed. The use of high levels of surfactants to overcome this problem can have a negative effect on the sensitivity to water and causes foaming of final products. In addition, at conventional levels of use, surfactants do not provide sufficient mechanical stability to the final products. It has been unexpectedly found that the use of low molecular weight protective colloid, in latex systems based on acrylic or styrene, allows the reduction of the level - or even the omission - of the surfactant. It has generally been found that the final products have a lower sensitivity to water, less foaming, and greater mechanical stability compared to prior art systems. Mechanical stability can be manifested in a longer shelf life. Additionally, in paint applications there is a reduced tendency to bleed, and a better equalization. The preferred polysaccharide protective colloid is a water-soluble cellulose ether which has been derivatized with ethylene oxide, methyl chloride, propylene oxide, onocloroacetic acid, etc., or mixtures thereof. Especially preferred are carboxymethylcellulose (CMC) and derivatives thereof, with a degree of substitution (DS) of carboxyl from approximately 0.7 to approximately 2.9, more preferably from approximately 0.7 to approximately 1.5, and with an even higher level. elevated preferably from about 1.0 to about 1.4. Suitable derivatives of carboxymethylcellulose include methyl carboxymethylcellulose, ethyl carboxymethylcellulose, hydroxyethyl carboethylmethylcellulose, hydroxypropyl carboxymethylcellulose, methoxyethyl cellolate, ethoxyethyl carboethylethylcellulose, and diethyloxycarboxymethylcellulose. Hydrocellulose can also be used <(HEC), the preferred molar hydroxyethyl (MS) substitution is from about 1.6 to about 4.0, with a greater degree of preference from about 1.8 to about 3.5, with even more preferably between 1.8 and about 2.9. Additionally, hydrophobically modified cellulose ethers can be employed. Suitable hydrophobically modified cellulose ethers are cellulose ethers further substituted with a hydrocarbon having from 4 to 25 carbon atoms, in a weight amount of the hydrophobically modified cellulose ether from about 0.114 to about 3.014, with a higher degree of preference of Approximately 0.114 to approximately 2.0%. A preferred hydrophobically modified cellulose ether is hydrophobically modified hydroxyethylcellulose (HMHEC). The hydrophobically modified hydraxyl cellulose useful in the practice of this invention is a hydroxyethyl cellulose additionally substituted with a hydrocarbon having from 4 to 25 carbon atoms, in a weight amount of hydrophobically modified hydroethyl cellulose from about 0.114 to about 3.014, with highest preference of approximately 0.114 per year immately 2,014. The hydroxyethyl MS of the HMHEC is preferably within the range of from about 2.9 to about 4.0, more preferably from about 2.9 to about 3.5. Other cellulose ethers, for example, which can be employed in this invention as a protective colloid are ethyl hydroxyethylcellulose (EHEC), methylcellulose (MC), methyl hydroxypropylcellulose (MHPC), and hydroxypropylcellulose (HPC). Other polysaccharides and materials that can be employed as protective colloids in the present invention are ethoxylated starch derivatives, partially and fully hydrolyzed polyvinyl alcohol, polyacryl acid, alkali metal polyacrylates (potassium, sodium, etc.), polyacrylamides, poly (ether) metilvin 1-maleic anhydride), polyvinylpyrrolidone, water-soluble starch glue, gelatin, water-soluble alginates, casein, agar, and natural and synthetic gums. The protective colloid is preferably used in an amount effective to stabilize the latex system of the invention. In this context, an effective amount is the amount that serves to stabilize the latex system during polymerization by aqueous emulsion and "after completion of polymerization. Especially, the concentration of protective colloid in the emulsion polymerization process of the present invention can vary within a wide range, the upper limit being determined only by economic and practical considerations based on the desired properties in the final product. Preferably, the upper limit is about 5.0%, with a higher degree of preference 3.5%, and with an optimum degree of preference about 2.5%, by weight, based on the total content of ethylenically unsaturated monomer in the mass of the reaction. The preferred lower limit is about 0.005%. A more preferred lower limit is about 0.05%, and the lower limit with optimum preference preferably in the total weight of the ethylenically unsaturated monomer content is 0.1% by weight. The protective colloid of the present invention can be used either alone or in combination with other protective colloids or surfactants. For example, the CMC derivative can be used as a single stabilizer or in combination with one or more surfactants. CMC as used in this invention is available under the trademark "Ambergum", water soluble polymers, types 1221 and 3021, marketed by Aqualon Company, Wilmington, Delaware. A hydrophobically suitable hydroxyethyl cellulose is available under the trademark "Natrosol Plus" marketed by Hercules Incorporated, Wilmingts, Delaware. Also, in accordance with the present invention, the monomers used in this invention are at least one ethylenically unsaturated monomer, such as vinyl esters or ethers, styrenes, and others. The acrylates used in this invention are acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, and other acrylate or methacrylate esters. In general terms, all ethylenically unsaturated monomers that can optionally be cyclic, which can be polymerized by free radical initiation can be employed in the practice of this invention. Preferred ethylenically unsaturated monomers include those having up to 23 carbon atoms. Examples of suitable monomers include vinyl steines, vinyl ethers, vinyl and vinylidene halides, N-vini lpyrrole idone, ethylene, C3 or greater alpha-alefins, allyl amines, allyl esters of saturated monocarboxylic acids, and amides of the so bed dienos and derivatives thereof. Suitable vinyl esters include aliphatic vinyl esters with, for example, methyl formate, vinyl acetate, vinyl propyanate, methyl butyrate, vinyl isobutene, vinyl valerate, vinyl caproate and methyl versatate. Typical vinyl ethers include ethyl ether, vinyl ether, ethyl ether, and 1-ytter ether and n-butyl ether. Suitable C3 alpha or olefins or higher include propylene, 1-butene, 1-pentene, cyclopenene, 1-hexen, cyclohexene and 1-decene. Allyl amines and allyl amines with N-substitution are examples of typical allyl amines. Suitable dienes are butadiene, cyclopentadiene, and diclopentadiene. Suitable allyl esters of saturated monocarboxylic acids may include allyl acetate, allyl propionate, and allyl lactate, and their amides, among others. The polymers of the present invention can be prepared from one or more of the monomers and il nically unsaturated. Regarding this aspect, it is observed that the term "polymer" also requires ho spolimers, and copolymers polymerized with 2 or more different monomers. In the case of the acrylic and styrene based crosslinkers, low molecular weight CMC is preferred. In the case of the lacetate-acrylate systems, HMHEC of low molecular weight is preferably used, but also low molecular weight HEC and low molecular weight CMC can be used. When acrylic acid or methacrylic acid is used in the polymerization, the level employed is preferably from 0.005% to approximately 2% - with a greater degree of preference from approximately 0.05% to approximately 1% - by weight based on the total content of ethylenically unsaturated monomer. The polymers of the present invention with relatively high glass transition temperatures - for example, approximately 50 ° C to approximately 150 ° C - can be characterized as "hard".; The polymers of the present invention with relatively low glass transition temperatures - for example about -100 ° C to about -3 ° C - can be characterized as "soft". One factor that affects the degree of hardness and softness is the identity of the ethylenically unsaturated monomers used. Different ethylenically unsaturated monomers contribute to hardness or softness in different degrees, and are therefore known as "hard" and "soft" monomers. The hardness and relative softness of different monomers is known in the art. The degree of hardness or softness of a polymer is therefore affected by the hardness or softness of the monomers that make up the polymer, and by the relative proportions of t monomers. When a copolymer latex system is made, the "hard" and "soft" monomer ratios are chosen in such a way that a continuous latex film is formed at the temperature of use. Acrylics within the range of approximately 0.005% to approximately 70% by weight of styrene in the formed copolymer can be made vini lo-acrylates within the ratio range from about 1: 1 to about 10: 1 , preferably from about 7: 3 to about 9: 1, by weight of vinyl acetate / acrylate monomer The resulting dispersions prepared in accordance with the present invention provide a significant improvement to the float resistance of the latex formulations with them Latex paints include glossy and matte paints - bright latex paints with a pigment concentration in less than 50 ppm, and latex matte paint. on a pigment volume of approximately 50 or more. Anionic, cationic, non-ionic and amphoteric surfactants and mixtures thereof known in the art can be employed in the practice of this invention. Suitable surfactants include pal II esters, sulfonated paraffin hydrocarbons, higher alkyl sulfates such as for example lauryl sulfate, alkali metal salts of fatty acids such as for example sodium stearate and sodium oleate, sulfuric acid esters of fatty alcohols , C4-50 alkyl phenols and their sulphonation products, such as, for example, nonylphenol ethoxylate with 4-50 - more preferably 10-20 - ethylene oxide units, ethoxylated C4-50 alkanols and their sulphonation products , as well as sulphosuccinic acid esters such as, for example, sodium dioxysulfasuccinat; t surfactants or emulsifiers are optional and not always required, but when used, they are present in amounts generally from 0.1 to 5.0%, preferably from 0.1 to 2.0%, by weight, based on the total amount of ethylenically manomeric saturated present in the process. Any known method of emulsion polymerization can be employed, including batch, semi-batch, or continuous techniques and thermal techniques or desaturation-or oxidation. The addition of monomer in blended or batchwise or continuous addition of the initiator or catalyst is the preferred form. The polymerization can also be carried out under high shear stress, which means that, for example, a loop reactor can be used to carry out the reaction. Preferably, an amount of from about 0% to about 40% is added - with a greater degree of preference of approximately 1% to about 15%, and with an optimum degree of preference of about 5% to about 15% - of monomer or ethylenically unsaturated monomers (s) in the initial charge to the reactor. Also, preferably, an amount of from about 0% to about 60% is added - with a higher degree of preference, of approximately 50% to approximately 60% by weight of the initiator in the initial charge to the reactor. The continuous addition of any ingredient or ingredients of the reaction is generally carried out for a period from about 2 to about 5 hours. The addition of catalyst or initiator in batch or in a delayed manner can be used, even though these variants are not necessary for the success of this invention. In general terms, the monomers are polymerized by means of aqueous emulsion techniques at a temperature level from about 20 * C to about 120 ° C, preferably from about 45 ° C to about 95 ° C, in the presence of a free radical polymerization initiator, especially a water-soluble peroxide, for example, hydrogen peroxide, persulfates such as, for example, potassium, sodium and ammonium persulfate, or in some cases, perborates. Other methods known in the art may also be used to convert monomers, such as, for example, by reduction-oxidation polymerization catalyst systems, for example potassium persulfate and sodium disulfite. The initiator is used in a concentration of 0.2 - 2.0% by weight based on the weight of the monomer (s); s), preferably in an amount of 0.3 - 1.0%. The resulting product of the present invention is a latex system, including particles of the polymer prepared in this way dispersed as a discontinuous phase in an aqueous continuous phase, and also includes protective coloring. The particles indicated preferably have a particle size less than approximately 500 nanometers - with a greater degree of preference of less than about 300 panomers, and with an even greater degree of preference less than approximately 200 nanometers. The latex system of the present invention has excellent shear stability. Consistent with the above comments, it can be used in latex paint compositions. These paint compositions preferably also include at least one of the following: pigment and extender pigment; however, conventional additional components may be employed for latex paint formulations, including thickeners. In addition, the latex system of the present invention can be employed in water-based bath compositions, paper coating compositions, binders for nonwovens, and adhesive compositions-especially dextrin-free adhesive compositions.

All parts of percentages used in this specification are by weight unless otherwise indicated. The invention is illustrated by means of the following examples which are provided for the purpose of representation, and are not to be construed as limiting the scope of the present invention. EXAMPLES Molecular weight was determined by the high performance size exclusion chromatography (SEC) method in accordance with the following: APPARATUS - A Varian 5010 LC equipped with a Waters Assocates R401 differential refractometer and a Kepp and Zonen recorder, model BD 40, were used for SEC analyzes. A 3-way articulated valve, Rheodyne, model 5302 was installed between the sample and reference entry lines to allow periodic cleaning of the reference side of the cell. However, by analysis, the reference side of the refractometer contained stationary mobile phase. Injections were performed using a Rheodyne model 7010 valve equipped with a 50μl sample loop. CHROMATOGRAPHY COLUMNS - SEC columns were purchased from SynChrom, Inc. (Linken, Indiana) and contained a phase chemically linked with glycerol on silica. The «column set used consisted of a guard column GPC 100 ngstrom (pore size) (5 cm x 4.1 mm ID Lot No. 227904), two analytical columns of 100 angstram GPC (25 cm ¡<4.6 mm ID, lots numbers 222033, 49201), and an analytical GPC 1000 angstrom column (25 cm x 4.6 mm I. D,, lot No. 48205). The columns were connected in series in accordance with the list. PREPARATION OF THE MOBILE PHASE - The mobile phase used in the analyzes was an acetate regulator solution with an ionic strength of 0.7 M with a pH of 3.7. The mobile phase with a pH of 3.7 was prepared by first adding 60 ml of undernourned sodium acetate and 440 ml of 4-acetic acid to a one-liter volumetric flask and filling by volume with distilled, deionized water . This provided a regulator with an ionic strength of 0.24 Jü at a pH of 3.7. The ionic strength of this solution was then increased to 1.44 M by the addition of 0.4 moles of sodium sulfate to 1 liter of the 0.24 J¿ acetate solution. The solution with an ionic strength of 1.44 was used during the sample preparations to minimize the difference between the mobile phase. The final mobile phase was prepared by diluting the double strength solution 1.44 J3. 1: 1 with distilled deionized water and by filtration through a Millipore membrane of 0.22 μm of ipo GS.

SPECIMEN PREPARATION - All samples were separated by dissolving 0.150 g of polymer (base to solids - corrected for moisture content) in distilled, deionized water, to a total volume of 25 ml providing an initial concentration of 6 mg / ml. These aqueous solutions can be diluted 1: 1 with a solution of acetate regulation are a double force of 1.4 M at a concentration of 3 mg / ml, corresponding to the composition of the mobile phase. All sample solutions were filtered through a 0.45 μm Millex-HV disposable filter unit (from Millipore) before injections. Analysis Conditions Column set: GPC 100 & guard, 100 ft, 100 ft, 1000 ft (Synchropa-) Mobile phase: acetate regulator 0.7 M, pH 3.7 Flow rate: 0.5 ml / min (measured 0.51 ml / min) Pressure: approximately 135-140 ATM Chart speed: 1 cm / min Sample concentration: 1.5-2.0 mg / ml DRI attenuation: 2X Multiple injections of each sample were made using the above conditions. The sheet tracings on laying of the resulting SEC chromatograms were prepared for comparison of standard molecular weights.

CALIBRATION - A series of molecular weight dextran standards from the American Paly er Standards Corporation (DXTl'IT) were analyzed using the previous volume (distance). The lowest molecular weight standard (DXT180 Muí), which is essentially eluted in the total permeation limit, was also used as an internal standard. Method of determining the average molecular weight (Mw) Example 1 All acrylic stabilized with low molecular weight CMC This example illustrates an embodiment of the aqueous dispersions of this invention and how to prepare it. The polymerizations were carried out in a 2 liter glass reaction vessel equipped with a thermocouple, a reflux condenser, a monomer inlet, an initiator inlet and a crescent shaped stirrer. 16.6 grams of the protective colloid were dissolved. { carboxymethylcellulose (CMC), marketed under the tradename Ambergum 3021, with an average molecular weight (Mw) of about 7,000 to 11,000 and a carbidoxyl substitute of approximately 1.2, available from Aqualon Company, with a concentration in solution of 29.6% with a Brook field viscosity of 630 mPa.s at 25 ° C), together with 1.6 grams of sodium bicarbonate in 461 grams of demineralized water. After complete dissolution, 13. temperature was raised to 85 ° C by means of a sea bath. Then, 40% of the initiator solution (1.5 potassium persulfate granules in 50 grams of deminerized water) was added regularly in 30 seconds. One minute later, the addition of the monomer was started. The mixture of manomeres (248.6 grams of butyl acrylate, 248.6 grams of methyl methacrylate and 2.8 grams of methyl methacrylate acid and 2.8 grams of methacrylic acid) was introduced with an addition rate of 54.5 grams per hour initially and this speed was increased gradually up to 163.5 grams per hour in the first hour of the reaction. When the temperature returned to 85 ° C, 95% of the rest of the initiator solution was introduced, with the remaining 5% of the initiator solution kept and added after the introduction of all the monomer. The addition of the indicated 95% of the rest of the initiator was carried out during the same period of time as the manomer, with the rate of initiator addition being adjusted to the monomer addition rate in such a way that the monomer addition and the 95% indicated in the rest of the initiator they came to an end simultaneously. Both the monomer and the initiator were added over a period of 3.5 to 4 hours, with a plunger pump and a peristaltic pump, respectively. The reaction temperature was maintained at 85 ° C. The polymerization was terminated by maintaining the temperature at 85 ° C for 1 hour after the addition of the initiator and monomer. Afterwards, the cross-linked resins were cooled before at room temperature. The stirring speed was 200 rpm during the functions. Comparative Example A All acrylic stabilized with high molecular weight CMC This comparative example illustrates the need for the low molecular weight of the protective colloid. The formulation and the procedure were used in accordance with that described in Example 1, except for the following changes: 16.6 grams of Ambergum (r) 3021 product are used, 10 grams of CMC 12M8P (viscosity of Broo field 430) were used. mPa.s (2% solution at 25ßC.) >; with a molecular weight of approximately 300,000. The amount of demineralized water had to be adjusted in this case to 473 grams to reach the same solid content of the resulting latex. Comparative Example B All Acrylic Stabilized with Nonionic Surfactant This comparison example illustrates the significant amount of nonionic surfactant necessary to obtain shear stable crosslinkers and serves as a comparison for the invention. The formulation and procedure of Example 1 were used except that instead of using 16.6 grams of protective colloid, 20 grams of nonionic surfactant (noni lphenyletoxylate with IO units of ethylene oxide: Intrasol NP10, 100% active material, were dissolved. of St «D« -: Jthausen) in 433 grams of ineral water. Example compares i or C All acrylic stabilized with ammonium and nonionic surfactant This comparison example illustrates the need for a high amount of surfactant in all acrylic crosslinks without the use of a protective colloid to obtain shear stable crosslinks. The formulation and procedure of Example 1 were employed except that instead of using 16.6 grams of protective colloid, 10 grams of nonionic surfactant (standard lignoletoxy lato with 10 units of ethylene oxide: Intrasol NP10, 100% active) together with 10 grams of an ammonium surfactant (dioctyl sulfosuccinate: Aerosol OT-75, 75% active material, from Cyanamid) in 472 grams of demineralized water. E n g u p e r 2 Static-surfactant free ion stabilized with low molecular weight CMC This example illustrates another embodiment of the invention. The polymerizations were carried out in a 2 liter glass reaction vessel equipped with a thermocouple, a reflux condenser, a monomer inlet, an initiator inlet and a crescent shaped stirrer. 33 grams of protective colloid (Ambergum (r) 3021, CMC, was dissolved with a solution concentration of 29.6% with a viscosity of a solution of 630 mPa.s at 25 ° C.) And 1.6 grams of sodium bicarbonate. in 450 grams of water (Generalized water) After a complete dissolution, the temperature was raised to 85 ° C by means of a bath, then 40% of the initiator solution was added regularly (1.5 grams of potassium persulfate). in 50 grams of demineralised water) for 30 seconds, the addition of the monomer was started a few minutes later, the monomer mixture (245 grams of butyl acrylic, 245 grams of styrene and 10 grams of methacrylic acid) was initially added. at a speed of 54.5 grams per hour, this speed was gradually increased to 163.5 grams per hour in the first hour of the reaction.The rest of the polymerization procedure was the same as that described in example 1. Example of comparison D Urethane-acrylic stabilized with anionic and non-ionic surfactant This comparison example illustrates the need for low molecular weight CMC as a stabilizer at low concentrations of surfactant to obtain stable cross-links. The formulation and procedure described in Example 2 were employed except that instead of 33 grams of the protective colloid, 15 grams of an ammonium surfactant (at which q = 11 ether sulfate: Dispom) AES 60 was used; 33% active material, from Henkel GmbH, Dusseldorf, Germany) together with 5 grams of non-ionic surfactant < no 1 phenolate with 10 units of ethylene oxide: Intrasol NP10, 100% active material) in 463 grams of water. The monomer mixture was in this case 248.6 grams of butyl acrylic, 248.6 grams of styrene and 2.8 grams of methacrylic acid. EXAMPLE 3 Urethane-acrylated ionic stabilized with both surfactants and with low molecular weight CMC The formulation and procedure described in example 2 were employed except that in addition to the solution of A bergum (mr), 15 grams of an ionic surfactant (alquilei létersul fato: Disponil AES 60; 33% active material) and 5 grams of a nonionic surfactant (nonylphenol ethoxylate with 10 units of ethylene oxide: Intrasol NP10, 100% active material) in 400 grams of water for stabilization. EXAMPLE 4 Styrene-acrylated 1 ico stabilized with both surfactants and with low molecular weight CMC The formulation and procedure described in example 2 were employed except that instead of using 33 grams, 16.6 grams of Ambergum (mr) 3021 was used in combination with 5.1? «Grams of ammonium surfactanfce < Sodium diollohexoducuccinate (aerosol A196, active material 85%), 5 grams of nonionic surfactant (Nitlfepol ethalate with 4 units of full oxide: Surfonic N40 '100% active material) were used in 463 grams of water The monomer mixture was in this case 248.6 grams of butyl acrylate, 248.6 grams of styrene and 2.8 grams of methylacrylic acid. The amount of initiator was increased to improve monomer conversion, but was still at a low level. The initiator solution contained 3 grams of potassium persulfate in 100 grams of water. EXAMPLE 5 Low Alkyl Acrylate with Low Molecular Weight CMC This example illustrates the possibility of making a surfactant free and aqueous dispersion with a relatively high amount of butyl acrylate in the manomer composition. The polymerizations were carried out in a 2 liter glass reaction vessel equipped with a thermocouple, a reflux condenser, a monomer inlet, an initiator inlet, and a crescent shaped stirrer. 33 grams of the protective colloid (solution of CMC Amberg? M (mr) 3021) were dissolved, with a solution concentration of 29.6% with a visasid-id of Brao! <F? Eld of 630 mPa.s at 25 ° C. 2.0 grams of sodium bicarbonate in 397 grams of water in water 1 izad After complete dissolution, the temperature was raised to 80 ° C by means of a water bath, then 40% of the initiator solution was added regularly. (1.5 grams of potassium persulfate in 50 grams of desalinated water) in 30 seconds.After one minute, the addition of monomers began.The monomer mixture (350 grams of vinyl acetate and 150 grams of butyl acrylate) It was initially added at a rate of 54.5 grams per hour and this speed was gradually increased to 163.5 grams per hour in the first hour of the reaction.When the temperature reached 80 ° C again, the introduction of 95% of the rest of the Initiator solution The remaining 5% of the solution The initiator was saved and added after the introduction of all the monomer. The initiator was added during the same period of time as the manomer and the rate of addition of the initiator was adjusted to the rate of addition of the monomer. Both the monomer and the initiator were added over a period of 3.5 to 4 hours, with a piston pump and a peristaltic pump, respectively. The reaction temperature was maintained at 80 ° C. The polymerizations were terminated by maintaining the temperature at 80 ° C for 1 hour after the addition of the initiator and monomer. Then, the crosslinkers were cooled to room temperature. The stirring speed was 200 rpm «during the reaction.

E em lo 6 Vini acetate. ls-acrylic 1 ico with surfactant and low molecular weight CMC In this example, the same formulation and the same procedure as described in example 5 was used with the following changes: instead of using 33 grams of Ambergum (mr) 3021 CMC , 67 grams of the product Ambergum (mr) 1521 (concentration of the solution at 14.7%, Brookfield visual at 25 ° C: 1540 mPa.s with a molecular weight of about 35,000 to 50,000 and a degree of carbon dioxide substitution) were dissolved. Approximately 1.2) together with 17 grams of anionic surfactant (sulphonated nonylphenol ethoxylate with 30 units of ethylene oxide: Fenopon EP 120, 30% active material) and 7.1 grams of the nonionic. { nonylphenol ethoxylate, Antarox C0 897, 70% active material) in 363 grams of demineralized water. The remainder of the formulation was the same as in Example 4. EXAMPLE 7 Alkyl Acetate 1 ico with Surfactant and Low Molecular Weight CMC In this example, the same formulation and the same procedure as that used in Example 5 was used. except that in this case also surfactaptes were added: the protective colloid and the regulator were dissolved in 397 grams of water together with 5 grams of non-ionic surfactant. { Nonylphenol ethoxylate with 20 units of?:, ethyl acetate in «D: Tergitol NP40; 100% active material) and 17 grams of ammonium surfactant (sulphonated nonyl phenol ethoxylate with 30 ethylene oxide units: Fenopon EP 120: 30% active material) EXAMPLE 8 VSNILO-ACRIL ICO ACETATE WITH SURFACTANT AND HEC UNDER MOLECULAR WEIGHT In this example the same formulation and the same procedure as described in example 1 were used except for the following changes: 12.5 grams were dissolved > of a mixed anionic surfactant (Disponil MGS 156, active material: 40%), together with 7.1 grams of a non-ionic (nonylphenol etaxylate, Antarox C0 897, 70% active material), 33 grams of low molecular weight HEC (solution concentration 29.1%, Brookfield viscosity of 260 mPa.s at 25 ° C) with a molecular weight of approximately 7,000 Approximately 11,000 and 2.8 grams of sodium bicarbonate in 397 grams of demineralized water. The reaction temperature was 80 ° C and the monomer mixture comprised 350 grams of vinylacetate and 150 grams of butyl acrylate. EXAMPLE 9 VINI LO - ACRI IC0 ACETATE WITH MOLECULAR LOW WEIGHT SUPPLANT AND HMHEC (INVENTION) The same formulation and the same procedure as described in example 8 were used, except that low molecular weight CMC was not used but 47.4 grams of HMHEC Ma roso1 Plus of low molecular weight (concentration of solution: 21.1% with a Brookfield viscosity of 28.5 mPa.s at 25 ° C). The average molecular weight of this protective colloid is about 25,000. The amount of water, therefore, had to be adjusted to reach the same solids content as latex. Surfactants, regulator (in this case 2.0 grams) and protective colloid were dissolved in 383 grams of demineralized water. EXAMPLE 10 VINYL ACETATE - ACRYLIC WITH SURFACTANT AND HMHEC OF LOW MOLECULAR WEIGHT The formulation and procedure used were the same as described in Example 8, except that low molecular weight CMC was not used, but 10 grams of HMHEC Natrosol Plus of low molecular weight (2% solution, viscosity of 4 mPa.s at 25"C with a molecular weight of approximately 25,000) .Therefore the water quantity had to be adjusted.Surfactants, 2.0 grams of regulator, and protective colloid were dissolved in 383 grams of izad demineral water COMPARATIVE EXAMPLE VINYL ACRYLIC-STABILIZED ACRYLIC WITH SURFACTANT In this example, exactly the same formulation and the same pro-led were used as in e3 example 9, except that the protective colloid was not present, the surfactant mixture and regula.d «3r were therefore dissolved in 420 grams of water., the conversion of monomers is worse when only surfactants are used and the latex has a very low viscosity. EXAMPLE 11 STABILIZED VINYL-ETHYLENE ACETATE WITH SURFACTANT AND MOLECULAR LOW WEIGHT CMC The polymerization was carried out in a 2 liter stainless steel reaction vessel equipped with a thermocouple, a monomer inlet, an initiator inlet, and a stirrer . 33 grams of the protective colai (Ambergum (MR) 3021 CMC, with a solution concentration of 29.6% with a solution viscosity of 630 mPa.s at 25ßC) and 1.25 grams of sodium bicarbonate in 337 grams of demineralized water were dissolved. . After this, 21.5 grams of 100% active HESS (sodium bis (ethylheyl) sulfocuc salt) and 3.6 grams of Ant ro material were added. C0 897 indolenyl phenol 40E0). After complete dissolution, the temperature was raised to 80 ° C. Then, 15% of the solution (2.5 grams of potassium persulfate in 100 grams of desalinated water) was added regularly in 30 seconds. One minute later, the addition of the monomer and the rest of the initiator solution was initiated. 445 grams of i acetate were gradually added or read over a period of 120 minutes, maintaining the ethylene pressure in the reaction vessel at 21 bars. The initiator was added during the same period of time as the monomer. The reaction temperature was maintained at 80 ° C. The polymerization was terminated by maintaining the temperature at 80 ° C for one hour after the complete addition of the initiator and monomer. Thereafter, the crosslinks were cooled to room temperature. EXAMPLE 12 VINYL ACETATE-BUTYL ACRYLATE STABILIZED WITH SURFACTANTS AND CMC OF LOW MOLECULAR WEIGHT; POLYMERIZATION WITH THE TO CUTTING EFFORT This example illustrates the possibility of using high shear in the reaction when a low molecular weight protective colloid is stirred. In this example, the same formulation and process as described in example 5 were used, except that in this example a mixture of 12.5 grams of an anionic surfactant (Disponil MGS 156, active material: 40%), 7.1 grams of an nonionic surfactant (nonylphenol ethoxylate, Anta ax CO 897, 70% active material), 33 grams of protective colloid (Ambergum (MR) 3021 CMC, with a solution concentration of 29.6% having a Braokfield viscosity of 630 mPa .sa 25 ° C), and 2.0 grams of sodium bicarbonate in 397 grams of demineralized water 1 raised. The vel «; > Agitation rate in this example was 400 rpm (tip speed 2.72 m / s). EXAMPLE F VINYL-APETATE ACETATE STABILIZED BUTYLLOAT WITH SUPPLIERS, POLYMERIZATION WITH HIGH CUTTING ESFUERZD This comparative example illustrates the need for a protective colloid in the polymerization when a high shear stress is applied. In this example, the same formulation and the same procedure as those described in Example 5 were used, except that in this example a mixture of 12.5 grams of an ammonium surfactant (Deisponil MGS 156, active material 40%), 7.1 grams was dissolved. of a non-ionic surfactant (nom 1 phenol ethoxylate, Antarox CO 897, 70% active material), and 2.0 grams of sodium bicarbonate in 420 grams of demineralised water 1. The stirring speed in this example was 400 rpm (tip speed 2.72 m / s). EXAMPLE 13 ALL ACRYLIC LATEX WITH A MINIMUM LOW FILM TEMPERATURE TEMPERATURE AND STABILIZED WITH CMC The polymerization was rationed according to that described in example 1, except for the following changes. Instead of 16.6 grams Ambergum (MR) 3021 CMC, 33 grams of A bergum íMP) 3 1 CMC were dissolved together with 6.25 grams of dihexyl sulfosuccinate (Dispoml SUS IC 680, 80% active material), 5 grams of ethoxylate of nonilfepol with 4 units of ox? d «: J of ethylene (Surfonic N40, 100% active material), and 1.6 grams of sodium dicarbonate in 450 grams of demineralized water 11. the monomer mixture used comprised 200 grams of methyl methacrylate, 300 grams of butyl acrylate, and 2.8 grams of methacrylic acid. EXAMPLE GL TEX ALL ACRI IC0 WITH A TEMPERATURE OF MINIMUM LOW FILM FORMATION AND STABILIZED WITH SURFACTANTS The polymerization of this comparison example was carried out in accordance with that described in example 13, except that the polymer Ambergum (MR) was not used for stabilizes ion. The surfactants and the regulator were then dissolved in 473 grams of water. EXAMPLE 14 LATEX OF VINYL ACETATE-ACRYL ICO WITH A MINIMUM LOW FILM FORMATION TEMPERATURE AND STABILIZED WITH A ULTRA LOW MOLECULAR WEIGHT HMHEC The pol i er i z c in was performed in accordance with that described in example 10, except for the following changes. 12.7 grams of mixed anionic surfactants (Disponil MGS 156, active material 40%), 7.7 grams of an ethoxylated fatty alcohol (Disponil APE 257, active material: 65%), 1.6 grams of sodium bicarbonate, and 10 grams were dissolved. or of HMHEC Natrosol Plus of low molecular weight in 422 grams of demyelinated water. The monomer mixture contained 200 grams of vinyl acetate and 300 grams of acrylate-butyl.1.-3. EXAMPLE 15 LATEX OF VINYL ACETATE / VeoVa-10 WITH A TEMPERATURE OF MINIMUM MOVIE TRAINING MIXED AND STABILIZED WITH CMC The polymerization was carried out in a 2 liter glass reaction vessel equipped with a thermocouple, a reflux condenser, a monomer inlet, an initiator inlet, and a half moon shaped ajitator. 40 grams of the protective colloid (Ambergum (MR) 3021 CMC, with a solution concentration of 29.6% with a Brookfield viscosity of 630 mPa.s at 25 * C) were dissolved together with 1.6 grams of sodium bicarbonate, 7.5 grams of diethyl sulfosuccinate (Disponil SUS IC 680, 80% active material), and 6 grams of a nonionic surfactant (ATP0L E 5720) in 432 grams of demineralized water. After complete dissolution of this mixture, the temperature was raised to 80 ° C in a water bath. Then, 5 of the tatal amount of the monomer was added for one minute. After 2 minutes, 25% of the initiator solution (1.8 grams of potassium persulfate in 60 grams of demineralized water) was added. When the temperature reached 72 ° C again, the monomer addition was started. The mixture of monomers (300 grams of vinyl acetate, 300 grams of VeoVa-10 monomer) was introduced at an addition rate of 1 R0 grams per day. VeoVa is the commercial brand under which such vi versatate products are sold by the Shell Chemical Company. After 5 minutes, the temperature was raised to 80 ° C and maintained at this temperature. The flow of the initiator solution was stirred to the monomer flow. The agitation speed of the agitator was 200 rpm during the reaction. Polymerization was terminated by maintaining it at 80 ° C for one hour after the addition of the initiator and the monomer. Thereafter, the polyexed mass was cooled to room temperature. EXAMPLE H LATEX OF VINYL ACETATE / VeoVa-10 WITH A TEMPERATURE OF FORMATION DF MINIMUM MEDIUM FILM AND STABILIZED WITH SURFACTANT The polymerization of this comparison example was carried out according to example 15 with the exception that no protective colloid was used. Therefore, the quantity of water had to be adjusted to 460 grams. EXAMPLE 16 LATEX OF METHYL METHACRYLATE / VeoVa-9 / ACPI BUTYL BUTYL STABILIZED WITH CMC AND SURFACTANT The polymerization was carried out in accordance with Example 13 with the exception that the monomer mixture contained 100 grams of methyl methacrylate, 100 grams. - of VeoVa-9 monomers, 300 grams of butyl acrylate, and 2.8 grams of methacrylic acid. EXAMPLE 17 LATEX OF METHYL METACRYLATE / VeoVa-9 / STYLILED BUTYL BUTYL ACRYLATE WITH CMC WITHOUT SURFACTANTS The polymerization was carried out in accordance with Example 16, except that the surfactants were omitted. EXAMPLE 18 LATEX OF METHYL METHACRYLATE / ACPI BUTYL LATO STABILIZED WITH H IDROX IPROP I CELLULOSE OF MOLECULAR WEIGHT ULTRA LOW The polymerization was carried out in accordance with the procedure described in example 1. As a protective colloid, 16.5 grams of a 30% solution of hydraxipropycellulose of ultra low molecular weight (molecular weight 6500) with a cloudy point were used. higher than 90 ° C instead of 16.6 grams of CMC Ambergum (MR) 3021. The properties of the cross-links of the above examples and of the comparative points are presented below in Tables 1 and 2. TABLE 1 Solids particle pH PS < 1) Stability { % by weight) pm (nm) to shear stress (2) (in) 1 48.8 200 6.4 310 > 5 A coagulated B 46.2 70 6.3 n.d. > 5 C 48.0 80 6.5 < 1 0 1 2 46.9 9900 5.8 220 1 D coagulated 3 47.0 100 5 5..77 7 74400 > 5 4 48.0 130 5 5..44 2 23300 > 5 5 49.9 11000 4 4..88 8 83300 > 5 6 49.9 380 5 5..11 2 24400 > 5 7 48.9 670 5 5..11 2 23300 > 5 8 49.7 406 4.9 200 9 50.8 130 4.7 220 10 50.6 610 3 3..77 3 35500 4 E 49.1 170 5 5..00 1 17700 1 11 52.2 190 4 4..99 3 32200 5 12 50.0 20 5 5..55 5 59900 > 5 F 45.4 400 5.4 210 13 45.1 80 5 5..99 2 23300 N.D, G sedimentation 14 49.7 180 4.7 280 N.D. 52.3 70 4.8 480 N.D. Coagulated H 16 44.9 60 6.4 215 N.D. 17 44.3 40 6.2 170 N.D. 18 46.2 90 6.0 345 N.D. 1. Average particle size number, determined with a Joyce Loebl disc centrifuge. 2. The shear stability is determined with a Waring mixer for 5 minutes at high speed, the figures indicate when the coagulation occurred. 3. N.D. it is the abbreviation for not determined. TABLE 2 Ejieemmppl1oo V Viissccoossiiddaadd ((11)) Film Brightness (%) mPa. s FDT 20ßC - 45 ßC 1 200 78 82 A coagulated B 20 25 61 C 480 63 65 2 1 50 76 90 D coagulated 3 3000 79 84 4 940 49 89 5 40 73 79 6 2625 79 82 7 680 78 80 8 365 79 81 9 485 80 81 10 960 81 81 E 5 80 81 11 90 77 82 12 50 79 82 F 30 76 82 13 600 83 83 Sediment G 14 2325 81 82 15 420 77 83 Coagulated H 1 166 2 2110000 82 tJ * - - 17 1200 81 81 18 20 30 33 Example Film a point (2) MFT (3) FDT 20 * C - 45 ßC (ßC) 1 8 9 N.D. A B 9 9 N.D.

C 1100 1100 N.D. 8 9 N.D. D 3 8 9 N.D. 4 9 9 N.D. 4 4 N.D. 6 9 9 N.D. 7 9 9 N.D. 8 99 99 N.D. 9 9 9 9 9 N.D. 10 1 100 1 100 N.D. E 1 100 9 9 N.D. 11 66 88 N.D. 12 88 99 N.D. F 1100 ÍÍO N.D. 13 99 99 < 0 G 14 9 9 < 0 15 8 9 11 H 16 9 9 12 17 9 9 N.D. 18 9 9 N.D. 1. Viscosity of Brookfield at 25'C, 20 rpm. 2. FDT refers to the film drying temperature. 3. MFT is the minimum temperature of film formation. 4. N.D. it is the abbreviation for not determined. The solids content was determined gravimetrically by weighing a quantity of latex, drying this amount to 120 ° C, the weight again of the dried amount, and then dividing the dry weight by the wet weight. The particulate content was determined as the fraction greater than the number 200 by sieving a heavy amount of latex on a 200-number sieve. The film properties were measured on latex film with a humerous thickness of 200 micrometers (μ) in idia substrate for the water point tests and the sheets of Leneta for the determination of the brightness of the film. The latex films were dried at 20 ° C and at 45 ° C. The film brightness was measured with a Byk glass head at a 60 ° angleThe resistance to water was measured by placing a few drops of water on the films. After 5 minutes, the appearance of the films was rated. The evaluation was the following. 10 light 8 slightly cloudy 6 cloudy 4 milky 2 white 0 the film is emulsified again The distribution of particle sizes was determined with a Joyce Loebl disc centrifuge. EXAMPLE 19 PAINTING 65 OF CONCENTRATION OF PIGMENT VOLUME (PVC) MADE WITH A LATEX OF VINYL ACETATE-BUTYL ACRYLATE ESTABLI7 D0 WITH SURFACTANT AND HMHEC OF LOW MOLECULAR WEIGHT This example illustrates that a latex stabilized with a protective colloid with the discontinuous polymer part characterized by a small particle size - in this case, approximately 200 nanometers. F, resen * to excellent properties in this painting due to the good capacity of film formation. Having such a fine particle size, the paints can be formulated into higher filled systems. The latex of Example 9 was used in a PVC paint 65 as shown in Table 3. COMPARATIVE EXAMPLE I PAINTING 65 OF PVC MADE OF COMMERCIAL LATEXES OF VINYL ACETATE-VeoVa (Mowilith DM 21) A commercial latex (Mowilith DM 21) was used in a PVC 65 formulation, as also shown in Table 3. The paint was sterilized with surfactants and a low molecular weight HMHEC Natrosol Plus. EXAMPLE 20 PVC PAINT 80 PREPARED WITH LATEX OF VINYL ACETATE-BUTYL ACRYLATEL, STABILIZED WITH SUPPLIERS AND MOLECULAR LOW WEIGHT HMHEC The latex of Example 9 was used in a PVC paint 80 as shown in Table 3. EXAMPLE 21 PAINTING 80 OF PVC PREPARED FROM A LATEX OF ESTIPEN-STERILIZED ACRYLATE WITH SURFACTANTS AND CMC IS LOW MOLECULAR WEIGHT The latex according to that described in example 4 -except that 36 grams (instead of 16.6 grams) of a solution were used of Ambergum MR) 3021 as a protective colloid - it worked like the latex in a paint 80 PVC, which is also shown in Table 3. COMPARATIVE EXAMPLE J PAINTING 80 OF PVC MADE OF A LATEX OF STYRENE-COMMERCIAL ACRYLATE (Acroñal 290 D) A commercial latex (Acranal 290 D) was prepared in a PVC formulation, which is also shown in Table 3. EXAMPLE 22 PVC PAINT 15 PREPARED FROM AN ACRYLIC LATEX STABILIZED WITH LOW MOLECULAR WEIGHT CMC The whip was used ex in accordance with that described in example 1 in a high gloss paint 15 of PVC, as shown in Table 3. COMPARATIVE EXAMPLE PVC PAINT 15 PREPARED FROM A COMMERCIAL ACRYLIC LATEX (Primal AC 507) A commercial latex was used (Primal AC 705) in a PVC formulation 15, as also shown in Table 3. Properties of the paints of examples 19-21 and of the comparative examples to J and K are presented in Tables 4 and 5 .

As regards the thickeners shown in Tables 4 and 5, Natrosol MBR and Na trasoi HBR serve as non-associative thickeners, and Natrosol Plus and Primal PM8 «... D. > 3 espe ad > Dres asac? At? V «-JS. N t ros) 1 MBR and Natrosol HBR, co or Natrosol Plus, are marketed by Hercules Incorpora ted, Wilmin tan, Delaware; Primal PMS is a product that is served by Rohm? Haas of Philadelphia, Pnnsylvama. TABLE 3 PAINTING FORMULATIONS Ingredient PVC 65 PVC 80 PVC 15 (grams) (grass) (grams) water 197.0 230.0 49.7 Calgon N 1.0 1.5 2.02 Pi gmento 2.0 3.0 Verteiler A Tamol 731 0.69 CA 24 2.0 3.0 0.51 Agitan 280 1.0 5.0 1.0 Thickener according to demand according to demand Ammonia (25%) 0.4 Kranos RN57 159.0 198.0 210.9 O yite 90 114.0 140.0 Durcal 5 159.0 198.0 alcu AT 200 23.0 28.0 Latex 167.0 93.0 671.9 But i 1g 1 i.col 15.0 20.0 Texanol 4.0 5.0 12.0 Agitan 280 0.6 WATER 150 71.5 52.1 TOTAL 1000 1000 1000 TABLE 4 PAINTING PROPERTIES OF PAINTS PREPARED FROM STABILIZED RETICULATES WITH LOW WEIGHT CELLULOSE ETHER MOLECULAR Example Thickener Weight% viscosity thickener Stor er (KU) 19 Natrosol Plus 0 0. .5522 19 Natrosol. MBR 0 0 .. .5511 102 IIN Naattrroossooll P Pl1uuss 0 0 0 .., .555000 100 I Natrosol MBR 0 0. .5500 104 20 Natrosol Plus 0 0., .3333 120 20 Natrosol HBR 0 0., .3311 112 21 Natrosol Plus 0 0 .., 4400 128 2 211 N Nattrroossooll H HBBRR 0 0 0 ..., 333222 112 JN trosol Plus 0 0., .4433 109 J Natrosol HBR 0 0 .., 3366 104 22 N trasoí Plus 0 0 .. .1111 96 22 Natrosol. HBR 0 0..2 233 96 K K P Prriimmall RR-.MM88 0 0 0 ... 00 0333 94 Natrosol HBR. 0.24 94 Use V isosity ICI Equalization (mPa. S) (lenet (1)) 19 110 19 110 7 I 110 5 I 110 5 20 90 20 1 0 21 9 900 21 120 J 110 J 120 22 100 5 2222 112200 4 K 100 5 K 98 2 1. Qualification 1-10, 10 = better. TABLE 5 Example Thickener Resistance to Splash Resistance (l) rubbing (2) (cycles) 19 N t bear1 Plus 6 > 10000 19 Natrosol MBR 2 > 10000 I Natrosol. Plus July 2300 I 2000 20 Na trasoí MBP Nat roso1 P Natrosol HBR 1us 940 20 850 21 1010 21 Natrosol Plus Natrosol HBR 640 J Natrosol Plus 7 JN troso1 HBR Natrosol Plus Natrosol HBR Primal RM8 KN K t rose HBR Ejempl'D Bril the 19 19 II 20 20 21 21 JJ 59 5 63 71 1. Score 1-10, 10 = better. 2. DIN 53778. EXAMPLE 23 A solvent-free latex paint was prepared from the following ingredients, including - as indicated - the latex of example 13. Ingredients Quantities (grams) water 197 Calgort N 1.0 Vertex pigment A 2.0 CA 24 2.0 Agitan 280 1.6 Natrosol 250 NBR 5.0 Ammonia (25%) 0.4 rones RN 57 159 Omya lite 90 114 Durcal 5 159 Talc? M AT200 23 Latex (from example 13) 167 Water 150 The properties of the paint in example 23 are presented in Table 6. TABLE 6 EVALUATION OF PAINTING IN SOLVENT-FREE PAINT Efficiency of Natrosol Thickener 250 MBR 0.57% Viscosity ñtor er < U) 103 Viscosity JCl 90 Finally, even though the invention has been described with reference to particular means, materials and odalities, it will be noted that the invention is not limited to the details presented and that it encompasses all equivalents within the scope of the claims. .

Claims (63)

1. CLAIMS 1. In a process > _ > for the preparation of a latex system which has a tendency to flocculate due to grafting, the improvement comprises the aqueous emulsion poly erization of at least one lymically unsaturated monomer selected from the group consisting of acrylic acid, ethacrylate i 1 co, butyl acrylate, butyl metaplatter, acrylic esters, styrene, vinyl ethers, vinyl, vimlidene halides, N-in 1 pi rrol idona, ethylene, f-olef inas C3 or greater, at i lamí , esters of saturated monacarboxylic acid esters and amides thereof, propylene, 1-butene, 1-pentene, 1-hexene, 1-decene, allylamines, acetal acetate, iron propionate, iron lactate, amides, and mixtures thereof, in the presence of an effective amount to stabilize the latex system of a water-soluble protective colloid with a molecular weight of less than about 75,000, selected from the group consisting of carboether and cellulose and ivados of the same that has a lower limit of degree of substitution of carbóxilo of approximately 0,7, h droxieti lcelulosa, hydraxiet i lcelulosa of ethyl, met i lcelulosa, hidr-nxipropí lcelulosa of methyl, hidrox ipropícelulos, acid poli lacríico, and you come out of me. the alkalines of them, derived from starch eto! Blended, polyacrylates of sodium and other alkali metals, water soluble starch glue, gelatin, water soluble alginates, casein, agar, natural and synthetic gums, partial and fully hydrolyzed polyanthi alcohol, polyamide lick , pol ivi nor lpirral idona, poly (ether 11 v íní 1 ico-anhedid maleic), gelatin, and casein.
2. 2. The process of the rei indicates ion 1, where it is also present from approximately 0.01 to about 4.0%, by weight on the basis of the monomer content and not total unsaturated, of a surfactant.
3. 3. The process of re-indication 2, wherein the surfactant comprises a member selected from the group consisting of ammonium, cationic, non-ionic and amphotepic surfactants, and mixtures thereof.
4. 4. The process of claim 3, wherein the surfactant comprises a member selected from the group consisting of polyol ethers, sulfonated paraffin hydrocarbons, higher alkyl sulfates, alkali metal salts of fatty acids, esters of sulfuric acid from fatty alcohols, phenols of C4-C12 alkylated ethoxy sides and their sulfonation products, ethoxylated C4-C12 alkanols and their sulfating products, and esters of sulfosuccinic acid and mixtures thereof.
5. The process of claim 4, wherein the surfactant comprises a member selected from the group consisting of "non-phenol efcaxylate" with 4-50 ethylene oxide units, dioctyl sodium phosphate, sodium sulfate, stearate of sodium, sodium oleate, and mixtures thereof.
6. 6. The rei-indication process 1, wherein the protective colloid comprises a member selected from the group consisting of hydroxyethylcellulose, ethylhydroxyl ethylcellulose, carboxylcellulose and cellulose with a lower limit of carbon dioxide substitution degree. Approximately 0.7, mecellulose, methylpropylcellulose, hydropropylcellulose, ethoxylated starch derivatives, partial and fully hydrolyzed polyvinyl alcohol, polyacrylic acid, sodium and other alkali metals , pol iacp lick, poly (ether et 11 v 1 1 alic acid anhydride), pol iv iru lpi rrol idona, glue of starch soluble in aej? , gelatin, water-soluble alginates, casein, agar as well as natural and synthetic gums.
7. 7. The process of claim 1, wherein the protective colloid has an upper molecular weight limit of approximately 50,000.
8. 8. The process of claim 1, wherein the protective colloid has an upper limit of molecular weight of approximately 20,000.
9. 9. The process of claim 1where the protective colloid comprises a cellulose ether selected from the group consisting of hydroxyethylcellulose, hydroxyethylcellulose, carboxyethylcellulose with a lower limit of substitution degree. carbóxil of approximately 0.7, met i Ice! Methyl hydroxypropyl cellulose, and hydrophilic cell.
10. 10. The process of reivi tion 9, wherein the cellulose ether comprises carboxymethyl cellulose with a degree of carbon dioxide substitution of approximately 0.7-2.9.
11. 11. The process of claim 10, wherein the cellulose ether comprises hydroxyl ether 11 l with a molar upper limit of hydroxyethyl substitution of 4.0.
12. 12. The process of claim 11, wherein the hydroxyethyl cellulose has a lower molar limit of substitution of hydroxyl of about 1.6 imadamerite.
13. 13. The process of claim 1, wherein the protective colloid comprises an idrophically modified cellulose ether, the hydrophobe being a hydrocarbon having 4-25 carbon atoms in a weight amount of the hydrophobic cellulose ether being modified. from approximately 0.1% to approximately 3%.
14. 14. The process of claim 13, wherein the modified dramatically modified cellulose ether comprises a hydrophobically modified hydroxyethyl cellulose.
15. 15. The process of claim 14, wherein the hydroxyl and hydrolyzed hydrophilic hydrocarbon has a molar upper limit of hydroxyl substitution.;: > Appropriately 4.0.
16. 16. The process of claim 15 wherein the modified hydrocarbyl hydrocarbyl substitution has a lower molar limit of hydroxyethyl substitution of 2.9.
17. 17. The process of claim 1, wherein an initiator is present and comprising a member selected from the group consisting of water-soluble persulfates, perborates, and peroxides.
18. 18. The process of claim 17, wherein the initiator comprises a member selected from the group consisting of hydrogen peroxide, potassium, sodium and ammonium persulfates, and sodium perborate.
19. 19. The process of the reagent 1, wherein the polymerization is carried out semi-continuously with from about 0% to about 60% of the total amount of an initiator and from about 0% to approximately 40%. % of the total amount of at least one non-saturated le monomer added at the beginning of the reaction.
20. 20. The process of claim 1, wherein the polymerization is carried out continuously.
21. 21. The process of claim 1, wherein the polymerization is carried out in a "loop" reactor.
22. 22. In a process for preparing a latex system which improves flocculation due to grafting, the improvement comprises the aqueous emulsion polymerization of at least one monomer and 11 only unsaturated, in the presence of an effective amount. to stabilize the latent system, of a water-soluble protective colloid with a molecular weight of less than about 75, OO, selected from the group consisting of hydroxyethylcellulose, hydro? leti Icelulosa of ethyl, met i elulosa, h i drox i prop i lulululosa of methyl, hi droxipropí Ice! What are the starch products? I wastes, partial and fully hydrolyzed polyvinyl alcohol, pyrimidic acid, sodium and other alkali metals, polyacrylate, etc. ~ p 1 amide, poly (methyl ether 11 vi or 11 male-male co-anhydride), ideal polyol, water-soluble starch glue, gelatin, water-soluble algae, casein, agar and natural and synthetic gums thus with or derivatives thereof, polyacrylic acid and alkali metal salts thereof, partially and fully hydrolyzed polyvinyl alcohol, pol lacp lamide, idioral polyvinyl alcohol, poly (methyl ether 11 vy 1 ico-anhydride maleic), gelatin and casein.
23. 23. The process of claim 22, wherein 0.01 is also present to approximately 4% by weight based on the total unsaturated monomer content of a surfactant.
24. 24. The process of claim 23, wherein the surfactant comprises a member selected from the group q-j? It consists of ammonium, cationic, nonionic and aphatic surfactants, and mixtures thereof.
25. 25. The process of the inductive cycle 26, where the surfactant comprises a member selected from the group consisting of polyol ether, paraffin sulphide hydrocarbons, higher alkyl sulfates, salts of alkaline metals of fatty acids, sulfuric acid esters of fatty alcohols, ethoxylated C4-C12 alkyl phenols and their sulphonation products, C4-C12 alkanols and their sulphonation products, and sulfosuccinic acid esters and mixtures thereof. same.
26. 26. The process of the indication 25, wherein the surfactant comprises a member selected from the group consisting of nonyl phenol ethoxylate with 4-50 units of ethylene, dioctyl, sodium fasuccinate, sulphate of lauryl, stearate sodium, sodium oleate, and mixtures thereof.
27. The process of claim 22, wherein the at least one ethically unsaturated monomer comprises a member selected from the group consisting of acrylic acid, methacrylic acid, butyl acrylate, methyl metaplastic, acrylic steres and styrene, as well as mixtures thereof.
28. 28. The process of claim 22, wherein the at least one ionically unsaturated monomer comprises a member selected from the group consisting of vinyl esters, vinyl ethers, vinyl, vimlidene halides, Nv im Ip i rrol suitable, ethylene, C3 alpha olefms or greater, to the lamellar, saturated esters of saturated monocarboxylic acids as well as amides, and of the same, and mez >; :: 1a s of 1os i smo.
29. 29. The pruceso of the rei ation 22, where the protective colloid has an upper limit of molecular weight of approximately 50,000.
30. 30. The process of claim 22, wherein the protective colloid has an upper molecular weight limit of approximately 20 OO.
31. 31. The process of claim 22, wherein the protective colloid comprises a cellulose ether selected from the group consisting of hydroxytricelulase, ethylhydroxyethylcellulose, methylcellulose, methylhydropropylcellulose, and hydroxypropylcellulose.
32. 32. The process of claim 31, wherein the cellulose ether comprises hydroxyethylcellulose with a molar upper limit of substitution of hydraxyethyl of 4.0.
33. 33. The process of claim 32, wherein the cellulose has a lower molar limit of hydroxyethyl substitution of an appropriate 1.6.
34. 34. The process of claim 22, wherein the protective colloid comprises a modified hydrophobic cellulose ether, the hydrophobe is a hydrochloride having from 4 to 25 carbon atoms in a quantity by weight of the cellulose ether. - Hydrophobically modified form of apro? immately 0.1% to about 3%.
35. 35. The process of claim 34, wherein the hydrophobically modified cellulose ether comprises a hydrophobically modified hydroxyethyl cellulose.
36. 36. The process of the reagent 35, where hydrophobic modified hydrophilic cellulose has a molar upper limit of hydroxyethyl substitution of about 4.0.
37. 37. The process of claim 36, wherein the hydrophobic modified hydraxyl hydrate has a lower molar hydroxyethyl substitution limit of about 2.9.
38. 38. The process of claim 22, wherein an initiator is present and comprises a member selected from the group consisting of water-soluble persulfates, perborates and peroxides.
39. 39. The process of claim 38, wherein the initiator comprises a member selected from the group consisting of hydrogen peroxide, potassium persulfate, sodium and ammonium, and sodium perborate,
40. 40. The process of claim 22, in where the polymerization is effected in a manner with approximately 0% to 60% of the total amount of an initiator and from about 0% to about 40% of the total amount of the at least one monomer et i licamente not saturated adding to the beginning of the
41. 41. The process of claim 22, wherein the polymerization is carried out continuously.
42. 42. The process of claim 22, wherein the polymerization is carried out in a "loop" reactor.
43. 43. In a latex system having a tendency to flocculate due to grafting, the improvement comprising: - an acuplus emulsion comprising: (a) a polymer of at least one ethnically unsaturated comonomer selected from the group consisting of acrylic, acrylic or methacrylic acid, butyl acrylate, methyl methacrylate, acrylic esters, styrene, vinyl ethers, vinyl, vinylidene halides, N-vini lpi rol idona, ethylene, C3-olefins or higher, allylamines, esters of allyl of acids onoca rbox í 1 i cos saturated and amides > thereof, prapi ene, 1-benthene, 1-pentene, 1-hexens, 1-decene, allylamines, allyl acetate, propionate of allyl, allyl lactate, their amides, and mixtures of 1 os; and (b) an effective amount to stabilize the latex system of a soluble, protective colloid with a molecular weight less than about 75,000, is "zielded into the group consisting of carboxymethylcellulose and derivatives thereof having a lower limit «of carbidoxyl substitution degree of approximately 0.7, hydroxyethylcellulose, hydrophilic ethylcellulose, methylcellulose, methylpropylcellulose, hydrocarbons, polyacrylic acid and alkali metal salts thereof, ethoxylated starch derivatives, sodium and other alkali metals pallets, water soluble starch glue, gelatin, water-soluble alginates, casein, agar, natural and synthetic gums, partial and fully hydrolyzed polyvinyl alcohol, polyacrylamide , poly inylpyrrolidone, methylene polyvinyl 1-maleic anhydride), gelatin, and casein.
44. 44. The latex system of re-ionization 43, the polymer having been polymerized by aqueous emulsion polymerization in the presence of the water-soluble protective colloid.
45. 45. The latex system of claim 43, further comprising from about 0.1 to about 4.0%, by weight based on the total content of ethically unsaturated monomer, of a surfactant.
46. 46. The latex system of the indication 43, where if protective col'Dide has an upper limit of molecular weight of approximately 5 (5,000.
47. 47. The latex system of claim 43, wherein the polymer comprises a discontinuous phase characterized by an average particle size of less than about 300 nanometers.
48. 48. A latex paint composition comprising: (a) at least one member selected from the group consisting of a pigment and an extender pigment; Y (b) the latex system of claim 43.
49. 49. The latex paint composition of claim 48, wherein the latex is free of solvent.
50. 50. The latex paint composition of the claim 48, wherein the polymer comprises particles having a mean size of less than about 500 nanometers.
51. 51. The latex paint composition of the re vindi drops to 48, where the paint is a bright paint with a pigment concentration in volume less than about 50.
52. 52. The latex paint composition of claim 48, wherein The paint is a matte paint with a concentration of pigment in volume of approximately 50 or more.
53. 53. A water-based ink composition comprising the latex system of claim 43 and at least one other ink ingredient.
54. 54. A paper coating composition comprising the latex system of claim 43 and at least one other ingredient of coating composition of paper.
55. 55. A dextrin-free adhesive composition comprising the latex of the indication 43 and at least one other adhesive ingredient that does not contain dextpna.
56. 56. A binder for undesired material comprising the latex of claim 43 and at least one other binder ingredient.
57. 57. In a latex system having a tendency to flocculation due to grafting, the improvement comprises: an aqueous emulsion comprising: (a) a polymer of at least one monomer ethically unsaturated; and ib) an effective amount for stabilizing the latex system, of a water-soluble protective colloid with a molecular weight less than about 75,000, selected from the group consisting of hydroxyethylcellulose, ethylhydroxyethylcellulose, methylcellulose, hydroxy methyl methylcellulose, hydroxypropylcellulose, ethoxylated starch derivatives, partially and fully hydrolyzed polyvinyl alcohol, pol lacrylic acid, sodium and other alkali metals, pol lacp lick, poly (ether met ii vi ni 1 Ica-anhydrous bad ico), pol i vim Ipirral idona, glue of water-soluble starch, gelatin, water-soluble alginates, casein, agar and natural and synthetic gums and derivatives thereof, ác? d «: > pallets and salts of alkali metals thereof, polyvinyl alcohol partially and wholly hydrolyzed, polyamide, polyvinyl, polyhydric, poly (ether 5 meth, 11 ammonium hydroxide) , gelatin, and casein.
58. 58. The latex system of claim 57, the polymer having been polymerized by aqueous emulsion polymerization, in the presence of the water-soluble protective colloid.
59. S1 ?.
60. The latex system of claim 57, which also comprises from about 0.01 to about 4.0%, by weight based on the total content of the ethically unsaturated monomer, of surfactant. 'of re-indication 57, where the protective colloid has an upper limit of molecular weight Approximately 50,000.
61. 61. The latex system of claim 57, wherein the at least one ethylenically unsaturated monomer comprises a member selected from the group consisting of acrylic acid, methacrylic acid, 0-butyl acrylate, methyl metaclasm, acrylic esters, I am reindeer, and mix the same.
62. 62. The lítex system of claim 57, wherein the at least one ethylenically unsaturated monomer comprises a member selected from the group consisting of vinyl esters, vinyl ethers, vimlo, vipilidene halides, N- vinylpyrrolidone, ethylene, C3 alpha olefins or greater, to the sheets, allyl esters of saturated monocarboxylic acids and amides thereof, and mixtures thereof.
63. 63. The latex system of claim 57, wherein the protective colloid has an upper molecular weight limit of about 20,000. RFSUMFN OF THE INVENTION 8e provides a process for the preparation of an acrylic copal line which has a stiffness > l to the improved mechanical and shear stress comprising the emulsion polymerization of at least one ethically unsaturated monomer having up to 23 carbon atoms in the presence of, by weight based on the total content of munomers, a) of about 0.05% to 5.0% of a protective colloid with a molecular weight less than 75,000, and b) from about 0.01% to about 1.5% of at least one water-soluble free radical polymerization initiator. This latex provides coating manufacturers with the flexibility to either completely remove the surfactants from the coating or to use small-sized materials. same.