WATER-DISPERB POWDER POLYMER, PROCESS FOR THEIR PREPARATION AND THEIR USE IN CEMENT-BASED COMPOSITIONS

Abstract

The invention relates to a water-dispersible powder polymer containing specific monomer units, a process for the production of said polymer, and the use of said polymer in construction and building applications.

Description

WATER-DISPERB POWDER POLYMER, THESE ARE PROCESS FOR PREPARING AND THEIR CEMENT-BASED ONES USAGE IN COMPOUNDS TECHNICAL FIELD OF THE INVENTION The present invention is a water-dispersible powder containing specific monomer units. polymer, a process for producing that polymer, and the construction of that polymer. and its use in construction applications. The subject of the invention is a water-dispersible material. Powder polymer improves both the adhesion of cement-based compounds after immersion in water and It can also be used advantageously to improve its flexibility. STATE OF THE ART Water-dispersible polymer powders improve the adhesion, strength, impact, and other properties of materials. properties such as abrasion resistance, self-leveling, water resistance, and flexibility. as additives in construction and building applications to improve performance It is widely used. These water-dispersible polymer powders require a suitable polymer dispersion or It is prepared by spray drying the emulsion. Generally, it is reused in water. Dispersible polymer powders are dry-blended with cement and other component mixtures, and then mixed with water. During wet mixing, redispersible polymer powders are formed. It redistributes. After redistribution, these redistributed particles form cement. It fills the spaces between the crystals and forms polymer bridges between these crystals. This creates a bonding effect that improves the binding properties of the cement. Major technical improvements have been made to water-dispersible polymer powders. 1 828.18 8828.18 However, cement-based compositions have both adhesion after immersion in water and There is still a need to improve its flexibility. The applicant proposed a water-redispersible solution composed of specific monomer units. They determined that this goal could be achieved using polymer powder. Summary of the Invention The invention's water-dispersible powder polymer aims to improve the quality of materials and Consequently, the resulting construction materials and those made with the polymers in question It presents a great opportunity to increase the structural integrity of the building. The present invention is a water-dispersible powder containing specific monomer units. polymer, a process for producing that polymer, and the material containing that polymer. It relates to a cement-based composition. The present invention also involves a composition that is redispersible in water. Polymer powder is used in construction and building applications, especially as tile adhesive and water-based products. cement-based materials such as insulation membranes, thermal insulation adhesives, and topcoats. It relates to its use in compositions. Detailed Description of the Invention The invention involves at least two different and specific monomers in the polymer chain. Thanks to the selection of its unit, the water-dispersible polymer powder is cement-based. especially in terms of adhesion and flexibility after immersion in water for the compositions. It delivers improved performance and produces unexpectedly superior results. This new water-dispersible powder polymer improves polymer performance and environmental impact. This offers a significant advantage. Contrary to all expectations, the applicant, The invention concerns polymers that improve the quality and durability of building materials, for example They found that it could surprisingly increase efficiency while reducing the frequency of repair needs. 2 828.18 8828.18 Water-dispersible powder polymer The present invention relates to a water-dispersible powder polymer and includes the following: It includes: - at least one propoxylated hydroxyalkylvinyl ether monomer unit, - at least one monocarboxylic acid vinyl ester monomer unit - optionally at least one vinyl acetate monomer unit. The term "polymer" is used in the current specification and refers to "water-dispersible powder". It refers to "polymer". The term "monomer unit" refers to a reactive component found in the polymer chain that reacts with the polymer. It refers to the monomer that contributes to the formation of the chain. The term "monomer" means... It refers to the monomer before polymerization. The difference is that "monomer" is unsaturated and unopened and reacting in the "monomer unit" state in the polymer chain It is related to the carbon-carbon double bond that has been inserted and is about to be opened. The present invention provides a water-dispersible polymer powder, desired for easy application. It has flow properties. The present invention is a water-dispersible polymer powder, a When mixed to form a paste, it can be redistributed in water. 3 828.18 The polymer subject to the invention shall preferably contain between 0.1% and 15% by weight, more preferably by weight. Between 1% and 10%, or even better, between 2% and 8% by weight, at least one It contains a propoxyylated hydroxyalkylvinyl ether monomer unit. The polymer subject to the invention may preferably contain between 1% and 40% by weight, and preferably between 5% and 40%. between, more preferably, 10% to 30%, or even more preferably, 15% to 25% It contains at least one vinyl ester monomer unit of a monocarboxylic acid. Propoxylated hydroxyalkylvinyl ether monomer, its homopolymer, from -25°C low, preferably below -30°C, even more preferably below -40°C, even more preferably - Having a glass transition temperature (Tg) lower than 50°C, preferably lower than -65°C. It is preferred in such a way as to be. The vinyl ester monomer of monocarboxylic acid, and its homopolymer, can withstand temperatures below -15°C. preferably having a glass transition temperature (Tg) lower than -25°C, preferably lower than -30°C It is preferred in such a way as to be. According to one configuration of the invention, the vinylester of monocarboxylic acid is derived from vinyl acetate. They are different. The specified glass transition temperature for a monomer is the glass transition temperature of its homopolymer. It corresponds to the transition. In the present invention, the method for determining the transition temperature is: Differential Scanning Calorimetry (DSC) with a temperature increase rate of 10°C per minute. It is the method. The expression "-30°C" means minus 30 degrees Celsius. "-50°C" The same is meant for [the other option], which is minus 50 degrees Celsius. At least one propoxylated hydroxyalkylvinyl ether monomer preferably with the following formula (1) It is a monomer. 4 828.18 The vinyl ester monomer unit of at least one monocarboxylic acid should preferably be 2-ethylhexanoic. It is the vinylester of acid. The polymer subject to the invention advantageously contains at least one vinyl acetate monomer unit. may include. In a preferred application, the polymer subject to the invention may contain between 30% and 95% by weight. preferably 40% to 90%, or even more preferably 45% to 75% vinyl acetate monomer It includes the unit. The polymer subject to the invention also advantageously contains at least one alpha-branched monocarboxylic acid. The acid's vinyl ester may also contain a monomer unit. In a preferred configuration, The polymer of the invention shall contain 0.1% to 30% by weight, preferably 1% to 20% by weight, at It contains a small amount of alpha-branched monocarboxylic acid vinyl ester monomer unit. The vinylester in question preferably contains 7 to 17 carbon atoms, and even more preferably... It is the vinylester of versatic acid 10. In a preferred configuration, the polymer subject to the invention includes the following: - at least one propoxylated hydroxyalkylvinyl ether monomer unit, - at least one monocarboxylic acid vinyl ester monomer unit - at least one vinyl acetate monomer unit. In a preferred configuration, the polymer subject to the invention includes the following: - at least one propoxylated compound between 0.1% and 15% by weight hydroxyalkylvinyl ether monomer unit, 828.18 - vinyl of at least one monocarboxylic acid, between 1% and 40% by weight. ester monomer unit - at least one vinyl acetate monomer unit, between 30% and 95% by weight. The total weight of a monomer unit is the total weight of a monomer unit in the polymer. It is 100% by weight, depending on its weight. In another preferred configuration, the polymer subject to the invention can be used as follows: It includes: - at least one propoxylated hydroxyalkylvinyl ether monomer unit, - at least one vinyl ester monomer unit of a monocarboxylic acid, - at least one vinyl acetate monomer unit, - at least one alpha-branched molecule, preferably with 7 to 17 carbon atoms. The monomer unit of the vinyl ester of monocarboxylic acid is the vinyl in question. The ester is preferably the vinyl ester of Versatik Acid 10. In another preferred configuration, the polymer subject to the invention may be the following: It includes: - at least one propoxylated compound between 0.1% and 15% by weight hydroxyalkylvinyl ether monomer unit, - vinyl ester of at least one monocarboxylic acid, in a ratio of 1% to 40% by weight monomer unit, - at least one vinyl acetate monomer unit, between 30% and 95% by weight, - between 0.1% and 30% by weight, preferably with 7 to 17 carbon atoms. a small alpha-branched monocarboxylic acid vinyl ester monomer unit It contains; the vinyl ester in question is preferably the vinyl ester of Versatik Acid 10. The total weight of a monomer unit is the total weight of a monomer unit in the polymer. 6 828.18 Depending on the weight, it is 100%. The polymer subject to the invention shall have at least one additional ethinizer, preferably selected from the list below. It may also contain unsaturated monomers: alkyl acrylates or alkyl methacrylates; for example Linear, branched, or cycloaliphatic C1-C22-alkyl(methyl)acrylates, methyl(methyl)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl-(meth)acrylate, lauryl(meth)acrylate, 2- ethylhexyl(meth)acrylate, stearyl-(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, 2-octyl-(meth)acrylate and tert-butyl(meth)acrylate, aryl(meth)acrylates, benzyl(meth)acrylate and phenyl(meth)-acrylate, tetrahydrofurfuryl(meth)acrylate, methoxyethoxyethyl(meth)acrylate, 1-butoxypropyl(meth)acrylate, cyclohexyloxymethyl(meth)acrylate, methoxymethoxyethyl(meth)acrylate, benzyloxymethyl(meth)acrylate, furfuryl-(meth)acrylate, 2-butoxyethyl(meth)acrylate, 2- ethoxyethyl(meth)acrylate, allyloxymethyl(meth)acrylate, 1-ethoxybutyl(meth)acrylate, 1-ethoxyethyl- (meth)acrylate, ethoxymethyl(meth)acrylate, poly(ethyleneglycol)methyl-ether(meth)acrylate and poly(propylene glycol)methyl ether(meth)acrylate or N,N-dimethyl aminoethyl(meth)acrylate, 2- such as trimethylammonium methyl(meth)acrylate chloride and N,N-dimethylaminopropyl(meth)acrylate aminoalkyl(meth)acrylates, 2,3-epoxy-butyl(meth)acrylate, 3,4-epoxy-butyl(meth)acrylate and Oxiranyl(meth)acrylates such as glycidyl(meth)acrylate, styrenes, α-methylstyrenes, 4- methylstyrenes, substituted 4-vinylbenzoic acid and sodium-4-vinylbenzene sulfonate Styrenes are vinylesters of carboxylic acids containing 1 to 20 carbon atoms, especially vinylacetate, vinylesters of versatic acids, (meth)acrylamides, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, n-butylacrylic acid, iso-butylacrylic acid, laurylacrylic acid, 2-ethylhexylacrylic acid, stearylacrylic acid, cyclohexylacrylic acid, Acid functional monomers such as isobornylacrylic acid and tert-butylacrylic acid. The polymer subject to the invention has a linear, branched, cross-linked or stellate structure. it could be. The polymer subject to the invention has a branched, cross-linked or star-shaped structure. 7 828.18 when this is the case, at least one crosslinking agent is required to obtain the polymer that is the subject of the invention. available. The crosslinking agents in question are preferably N-methylol acrylamide, N-methylolmethacrylamide, N-(alkoxymethyl)acrylamides or N-containing C1-C6-alkyl radicals (alkoxymethyl)methacrylamides, for example N-isobutoxymethyl)acrylamide (IBMA), N- (isobutoxymethyl)methacrylamide (IBMMA), N-(n-butoxymethyl)acrylamide (NBMA), N- (n-butoxymethyl)methacrylamide (NBMMA), diacetone acrylamide (DIAAM); ethylene glycol diacrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, propylene glycol diacrylate, divinyl adipate, divinyl benzene, vinyl methacrylate, vinyl acrylate, allyl (meth)acrylate, diallyl maleate, diallyl phthalate, diallyl fumarate, methylenebisacrylamide, as multiple ethylenes such as cyclopentadienyl acrylate or triallyl cyanide It is selected from the list containing the unsaturated comonomer. A chain transfer agent can be used to obtain the polymer that is the subject of this invention. Suitable chain transfer agents include isopropanol, mercaptoethanol, 3-mercaptopropanol, 3- mercaptopropionic acid, 1-butanetiol, 1-propanethiol, 1-prentanetiol, 2-methyl-2- propanethiol, 1-hexanethiol, 1-octanethiol, tert-nonyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, 3-mercapto-3-methyl butanol, 1-mercapto-2-phenyl-2-ethanol, thioglycolic acid, methyl thioglycolate, n-butyl thioglycolate, 2-ethylhexyl thioglycolate, i-octyl thioglycolate, dodecyl thioglycolate, octadecyl thioglycolate, methyl-3-mercaptopropionate, butyl-3-mercaptopropionate, isooctyl-3-mercaptopropionate, isodecyl-3- mercaptopropionate, dodecyl-3-mercaptopropionate, octadecyl-3-mercaptopropionate, 4-methylbenzene thiol, benzenethiol, 4,4'-thiobisbenzenethiol, azelaic alkyl mercaptan, These could be tetrabromomethane and carbon tetrachloride. In a preferred application, the polymer subject to the invention may preferably be used between -30°C and +80°C. It preferably has a glass transition temperature (Tg) between -15°C and +30°C. 8 828.18 The present invention describes a method for determining the specified glass transition temperature for a polymer. It is defined as Differential Scanning Calorimetry (DSC). Process The present invention also allows for the preparation of a powder polymer that is dispersible in water. It relates to a process that includes the following steps: - At least one propoxylated hydroxyalkylvinyl ether monomer and at least one vinylester monomer of monocarboxylic acid, free radical initiator and optionally in the presence of a surfactant and / or stabilizer Preparation of an aqueous emulsion or suspension by polymerization, - Aqueous polymer emulsion or dispersion resulting from obtaining powder drying. In the invention process, the choices described in the "polymer" section above apply to each including the quality and quantity of the monomer, for the process in question as well. It is valid. Aqueous emulsion or suspension, emulsion polymerization or suspension It is obtained by polymerization or dispersion polymerization. Polymerization The reaction is preferably carried out within a temperature range of 25°C to 100°C. The polymerization is preferably a nucleated polymerization. Nucleated polymerization, a special polymerization process involving the use of a core polymer It is a polymerization method. A nucleated polymerization results in finely divided particles during emulsion polymerization. It involves the use of polymer particles. These are finely divided polymer particles. 9 828.18 It is called a "core polymer" because of the reactive monomers They act as a nucleus in which polymerization can begin. Core polymers It is usually and preferably added in the early stages of polymerization. Core polymerization, preferably with a core added at the beginning of the polymerization process. nucleation occurs in the presence of polymers at the beginning of the reaction. a phase that includes the stabilization phase of the kernels during the growth phase It is polymerization. The polymerization reaction is preferably carried out with water-soluble free radical initiators. is initiated. Preferably, polymerization initiators, thermal polymerization initiators, from the group consisting of redox polymerization initiators and combinations thereof, especially inorganic substances such as ammonium, potassium persulfate, sodium persulfate and the like. and / or organic persulfates; cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl Peroxides such as hydrogen peroxide and the like; also perbenzoates, per- azo initiators such as alkanoates or azobis-isobutyronitrile (AIBN) and their combinations can be selected and for the production of a sustainable binder composition. available. Suitable reducing agents for redox initiator systems include alkali metal bisulfides, Hydrogen sulfides, ketone adducts of bisulfides such as acetone bisulfite, alkali metals disulfides, metabisulfites and their salts, formaldehyde sulfoxylates and their salts, thiosulfates Sulfur compounds such as hydroxylamine hydrosulfate, hydroxylamines, and Reducing nitrogen compounds such as hydroxylammonium salts; polyamines and sorbose, Reducing sugars such as fructose, glucose, lactose and their derivatives; isoascorbic acid, ascorbic acid sulfinic acids, hydroxymethylsulfinic acid and 2-hydroxy-2-sulfinactic acid and their salts Enediols, for example, may be present. Additionally, the metal may be in various oxidation states. The use of metal compounds in which it can be found, for example iron(II) sulfate 828.18 It is possible. If at least one surfactant is to be used during the polymerization phase, a suitable surfactant must be selected. all ionic and non-ionic surfactants available on the market as active ingredients The following materials can be used. Particularly preferred examples include fatty alcohol ether sulfates and ethoxylated alcohols. polyethylene glycol ethers, ethoxylated fatty alcohols, and also long-chain alkyls sulfates (C8-C12-alkyl radical), sulfuric monoesters of ethoxylated alkanols and alkaline ethoxylated alkyl phenols of alkyl acids and alkylarylsulfonic acids These include metals and ammonium salts. When at least one stabilizer is used, the stabilizer should preferably be polyvinyl alcohols, hydroxyethyl cellulose, polyethylene glycol, polyvinylpyrrolidone, carboxymethylcellulose, starch It is recommended that it be cellulose derivatives. The stabilizer is a colloidal stabilizer. Polymeric It could be a stabilizer. The term "polymeric stabilizer (PS)" as used here and throughout the specification, generally both hydrophobic moieties and carboxylic acid functional groups It refers to a type of stabilizer that it possesses. The weight-average molecular weight of the polymeric stabilizer should preferably be between 1,000 and 120,000. In the Dalton range, preferably between 5,000 and 60,000, or even more preferably between 10,000 and It should be in the range of 50,000, or even better, between 10,000 and 30,000 Daltons. The polymer obtained after polymerization is usually an aqueous emulsion or dispersion. It has a polymer content of between 20% and 70% by weight. 11 828.18 In the process described in the invention, polymer emulsion or dispersion is dried to form polymer powder. An additional step is involved in obtaining it. For example, polymer emulsion or dispersion. Fluidized bed drying, freeze-drying, or spray drying, preferably spray drying. It is dried by drying. Generally, spray drying, traditional spray drying. Atomization is carried out in the facilities using the known hot air vapor technique. via airless nozzles, dual nozzles, multiple nozzles, or a rotating disc. This is feasible. The inlet temperature of the spray dryer is generally between 80 and 150°C. The temperature is preferably between 120 and 145°C. The outlet temperature of the spray dryer is usually 40°C. between 50 and 80°C, preferably between 50 and 100°C. To prevent the polymer powder from clumping, finely ground silica, kaolin, and calcium are added. combinations of carbonate, magnesium carbonate, talc, aluminum silicates, and dolomite or other mineral additives, such as anti-caking agents, known It can be added to a powder polymer that is dispersible in water by a certain method. Use of polymer This invention also includes at least one invention which is the subject of this invention or which is derived in accordance with the process of this invention. It also relates to a cement-based composition containing a water-dispersible powder polymer. The amount of the polymer in question in the cement-based composition should preferably be by weight. It ranges from 0.1% to 30%. The present invention also involves the reuse of water obtained according to the invention or the process of the invention. Dispersible powder polymer in cement-based compositions, preferably in tile adhesive, Used in waterproofing membranes, thermal insulation adhesives, and topcoat applications. It is also related. The present invention also describes the adhesion of the cement-based composition after immersion in water and to improve its flexibility, the product of the invention or the process derived from the invention 12 828.18 This also relates to the use of the redispersible powder polymer produced. In another context of the invention, the subject matter of the invention is a polymer, coating, paint, primer, ink, an adhesive such as pressure-sensitive adhesive, textile and leather additive, paper additive This material can be used to produce construction additives. The polymer subject to this invention is advantageously used in interior and exterior paints, primers, plasters, and architectural applications. Decorative coatings applied with a trowel for various applications, including industrial wood and metal coatings, coatings for plastic and composite surfaces, road markings. paints, roofing coatings, roof tile paints, printing inks, agricultural coatings, such as dust and ground stabilization coatings and overprint varnishes. in their formulations, paper label adhesive, packaging tape adhesive, preservative film adhesive, lamination adhesive, contact adhesive, paper tape adhesive, masking tape adhesive, film label adhesive, cold bonding and heat bonding. adhesive bonding, floor covering adhesive, flexible packaging adhesive, tapes, protective films, packaging lamination, specialty paper, paper coating, paper pressure-sensitive binders such as impregnation binders, separation binders, paper saturation binders, etc. in sensitive adhesives, finishing, coating, flocking, nonwoven surfaces, printing, wet end In textile and leather applications, such as in the production and finishing stages, and in construction applications; For example, construction adhesives and coatings for waterproofing and sealing, cement. Modifiers, sealants, tile adhesives and grout, mortar and repair mortar, exterior thermal insulation composite system, self-leveling It can be used in applications such as compounds and dispersible powders. The polymer that is the subject of the invention has significant advantages in terms of polymer performance and environmental impact. It offers an advantage. The polymer that is the subject of the invention can, for example, reduce the frequency of repairs in construction materials. It can improve its quality and durability. 13 828.18 Other Purposes of the Invention In another case, the invention relates to a powder polymer that is redispersible in water, This includes the following: - at least one monomer unit of the formula (2) monomer, - at least one monocarboxylic acid vinyl ester monomer unit - optionally at least one vinyl acetate monomer unit. In this invention, at least the propoxyylated hydroxyalkylvinyl ether monomer unit, formula (2) is replaced with at least one monomer unit of monomer. The value of "n" is preferably 1 between 2 and 20, even more preferably between 2 and 15, even more preferably between 5 and 12 should be. Preferably, the monomer unit of the formula (2) monomer is Rhodasurf AAE10. The polymer in this case preferably contains at least one monomer unit of the monomer of formula (2). between 0.1% and 15% by weight, more preferably between 1% and 10%, even more preferably It contains between 2% and 8%. In this case, please refer to the detailed description section regarding the water-dispersible powder polymer. All the preferences mentioned also apply to the polymer in this case; this is the monomers its nature, monomer concentrations, Tg, polymer structures, crosslinkers, 14 828.18 chain transfer agents, processes, polymerizations, initiators, surfactants ingredients, stabilizers, polymer forms (emulsion powder) and their areas of application It includes without any limitations. An alternative to this situation is that at least one monomer unit of the formula (2) monomer in its structure "n" indicates the presence of propoxytion, not ethoxylation. The value of "m" is related to the value of "n". They have the same preferences. Another alternative is that at least one of the monomers of formula (2) This refers to the presence of both propoxylation and ethoxylation in the structure of the monomer unit. In another case, the invention is a water-dispersible powder polymer containing the following: It is related to: - at least one vinyl ether monomer unit, - at least one vinyl ester monomer unit of a monocarboxylic acid, - optionally at least one vinyl acetate monomer unit. In this invention, at least the propoxyylated hydroxyalkylvinyl ether monomer unit, It is replaced with at least one vinyl ether monomer unit. In this case, the vinyl ether monomer unit should preferably be at least C3, and even more preferably the least... at least C5, even better at least C7, even better at least C10 It has a chain. The vinyl ether monomer unit preferably has at least one OH termination. It has. The vinyl ether monomer unit preferably contains at least one propoxylated unit and / or It contains at least one ethoxylated unit. Propoxylated versions are preferred. In this case, this polymer should preferably be between 0.1% and 15% by weight, and even more preferably 1%. between 10% and, more preferably, between 2% and 8% of at least one vinyl ether monomer. It is expected to include the unit. 828.18 In this case, please refer to the detailed description section regarding the water-dispersible powder polymer. All the preferences mentioned also apply to the polymer in this case; this is the monomers its nature, monomer concentrations, Tg, polymer structures, crosslinkers, chain transfer agents, processes, polymerizations, initiators, surfactants ingredients, stabilizers, polymer forms (emulsion powder) and their areas of application It includes without any limitations. In another case, the invention relates to a powder polymer that is redispersible in water, The polymer includes the following: - at least one vinyl ester monomer unit (i), - at least one vinyl ester monomer unit of a monocarboxylic acid, - optionally at least one vinyl acetate monomer unit. In this invention, at least the propoxyylated hydroxyalkylvinyl ether monomer unit, at least one vinyl ether monomer unit (i) is replaced. In this case, the vinyl ether monomer unit (preferably at least C3, even more preferably the most at least C5, even better at least C7, even better at least C10 It has a chain. The vinyl ether monomer unit (i) preferably has at least one OH termination. It has. The vinyl ether monomer unit (i) preferably contains at least one propoxylated unit and / or It contains at least one ethoxylated unit. Propoxylated versions are preferred. In this case, the polymer should preferably be between 0.1% and 15% by weight, more preferably 1%. between 10% and, more preferably, between 2% and 8% of at least one vinyl ester monomer It is expected to include the unit. In this case, please refer to the detailed description section regarding the water-dispersible powder polymer. All the preferences mentioned also apply to the polymer in this case; this is the monomers 16 828.18 its nature, monomer concentrations, Tg, polymer structures, crosslinkers, chain transfer agents, processes, polymerizations, initiators, surfactants ingredients, stabilizers, polymer forms (emulsion powder) and their areas of application It includes without any limitations. The invention is explained in more detail with the following examples, but is not limited to them. This is not the case. The ratios and percentages given in the examples are weighted, unless otherwise stated. It has been given. In another case, the invention relates to a powder polymer that is redispersible in water, The polymer includes the following: - at least one propoxylated compound between 0.1% and 15% by weight hydroxyalkylvinyl ether monomer unit or one of the formula (2) monomers monomer unit - vinyl ester of at least one monocarboxylic acid, in a ratio of 1% to 40% by weight monomer unit; vinyl ester monomer of the monocarboxylic acid in question. the unit will have a glass transition temperature (Tg) lower than -15°C for its homopolymer. It is as follows: - at least one vinyl acetate monomer unit, between 30% and 95% by weight, where the total weight of a monomer unit, the total weight of a monomer unit in the polymer It is 100% by weight, according to its weight. Examples 17 828.18 Water-dispersible powder polymer Water-redispersible powder polymers, dispersion polymerization and is obtained by spray drying the resulting polymer dispersion. Monomers in the presence of a polymeric stabilizer (a hydrolyzed polyvinyl alcohol) It is polymerized in core polymerization. Hydrogen peroxide is added to the monomer mixture. Sodium sulfoxylate and sodium bicarbonate are added. Polymerization is carried out for 3 hours at 75°. This is carried out at C, and the resulting polymer dispersion is observed at the reaction temperature for 30 minutes. It is heated further. The temperature is then reduced to 70°C and tert- dissolved in deionized water is added. Butyl hydroperoxide is added. A polymer dispersion is obtained. The resulting polymer dispersion is then spray-dried to obtain polymer powder. The resulting polymer dispersion is first heated to 70°C and then to an inlet temperature of 140°C. It is dried using a Niro spray dryer system. The drying gas is air. To prevent clumping, kaolin is added through other nozzles. The resulting polymer... The powder mixes easily with water to provide a free-flowing, blockage-resistant and stable dispersion. miscible. The invention consists of four water-dispersible powder polymers (Samples 1 to 4) and the invention Six water-dispersible powder polymers that are not compatible with other materials (Corresponding Examples 1 to 6) It has been prepared. Water-dispersible powder polymers have the following monomer composition. VAM PHAV Veova Veova 10 2-HEA BA AAE EH Ex1 80 10 10 Ex2 65 10 10 15 18 828.18 Ex3 65 10 20 5 Ex4 75 5 20 Ex5 65 10 15 10 Ex6 65 20 5 10 Ex7 75 20 5 CEx1 80 20 CEx2 80 20 CEx3 80 20 CEx4 80 20 CEx5 65 15 20 CEx6 65 5 20 Table 1 - Polymer compositions Ex1 to Ex4 are examples corresponding to the polymers of the invention. CEx1 to CEx6 are examples of the invention. These are counter-examples corresponding to polymers that fall outside the scope. VAM: Vinyl acetate PHAV: Propoxylated hydroxyalkylvinyl ether having the formula (1). monomer. Veova EH: vinyl ester of 2-ethyl hexanoic acid. Veova 10: Vinyl ester of versatic acid 10 2-HEA: 2-Hydroxyethyl acrylate BA: Butyl acrylate AAE: Allyl Alcohol Ethoxylate (CAS 27274-31-3) Application Tests Previously prepared water-redispersible powder polymers for plaster and tiles. It is formulated and tested in adhesive applications. Application Tests for Plasters Water-dispersible powder polymer in Example 1 and Counterexamples 1 to 4, ETAG 004 19 828.18 Formulated and tested according to standards for plaster applications. The following plaster formulation is detailed in Table 2. Ingredients Quantity (by weight %) CEM I 42.5 cement 23 60-70 AFS sand 67 Cellulose Ether 0 Water-dispersible powder polymer 2 Ca(OH)2 3 Calcite 5 Water content (%) 22.0 Table 2 - Plaster formulation The water-dispersible powder polymer in Example 1 is similar to the water-dispersible polymers in Counter Examples 1 through 4. It was compared with redispersible powder polymer. "Plaster Ex1", in water as in Sample 1. This corresponds to a plaster formulation made with redispersible powder polymer. "Plaster CEx1" is a plaster made with water-redispersible powder polymer as shown in Counterexample 1. It corresponds to the formulation. The expressions continue similarly. Test results are detailed in Table 3. Plaster Plaster Plaster Plaster Ex1 CEx1 CEx2 CEx3 CEx4 828.18 Adhesion in EPS after 28 days (kPa) - 81.34 74.01 75.38 58.65 63.56 Beginner (no submersion) Adhesion of EPS to water after 28 days (kPa) 47.41 31.52 26.98 15.74 12.84 after immersion (28 days at room temperature, 2 immersion in water throughout the day, (2 hours at room temperature) Adhesion of EPS to water after 28 days (kPa) 87.41 73.45 74.82 60.46 59.73 after immersion (28 days at room temperature, 2 immersion in water throughout the day, 7 hours at room temperature) Effect after 14 days (3 Joules) 0 1 2 2 2 0: Good, 5: Weak Effect after 14 days (10 Joules) 0 2 2 3 3 0: Good, 5: Weak Table 3 - Test Results of Plaster Performance In adhesion tests, the higher the value, the better the adhesion. Regarding flexibility... In the impact test, the lower the value, the better the result. The subject of the invention is "Plaster Ex1", formulated with a water-dispersible powder polymer, 1 to Formulated with water-redispersible powder polymers in countersample #4 It gives significantly better results compared to plasters. The initial adhesion on expanded polystyrene occurs after immersion in water. And flexibility (resistance to impact) has been significantly improved. 21 828.18 The subject of the invention is a water-dispersible powder polymer, aimed at improving the quality of plaster materials and It offers a significant advantage in terms of durability. Reduced frequency of repairs. Thanks to this, the environmental impact has been significantly improved. The subject of the invention is a water-dispersible powder polymer with post-immersion adhesion and It allows for a much better balance between flexibility and other factors. Application Tests for Tile Adhesive Examples 2 through 4 and Counterexamples 1, 2, 3, 5, and 6 are water-dispersible powders. Polymers formulated according to EN 12004 Standard for tile adhesive application. It has been done and tested. The following tile adhesive formulations are detailed in Table 4. Ingredients Quantity (by weight %) CEM I 42.5 R Grey Cement 35 50-55 AFS Silica Sand 53.965 Cellulose Ether 0.435 Powder Polymer 5 Calcium Formate 0.1 Calcium carbonate (20 microns) 5 Ca(OH)2 0.5 Total 100 22 828.18 Water content (%w) 23.5 Table 4 - Tile adhesive formulation The water-dispersible powder polymer in Examples 2 through 4, vs. Examples 1, 2, 3, 5 and Compared to water-redispersible powder polymer in section 6. "Tile adhesive" Ex2", tile adhesive made with water-redispersible powder polymer as in Example 2. It corresponds to the formulation "Tile adhesive CEx1", in water as shown in Counter Sample 1. in contrast to tile adhesive formulations made with redispersible powder polymer. income. The statements continue in a similar vein. Test results are detailed in Table 5. Initially, the heat transfer to the water transversely. aging, immersion, waiting, deformation After that, the duration of the CYD (mm) CYD Tile making. Ex2 1.65 1.77 1 0.92 2.79 Tile making. Ex3 1.63 1.78 1.07 0.90 2.77 Tile making. Ex4 1.61 1.73 1.03 0.81 2.67 Tile making. Ex5 1.62 1.74 1.02 0.79 2.69 Tile making. Ex6 1.58 1.70 1.01 0.77 2.65 Tile making. Ex7 1.55 1.66 1.01 0.78 2.61 Tile making. CEx1 1.63 1.70 0.98 0.63 2.13 Tile making. CEx2 1.51 1.45 0.91 0.55 1.85 Tile making. CEx3 1.50 1.45 0.78 0.46 1.63 Tile making. CEx5 1.58 1.71 1.01 0.78 2.21 Tile making. CEx6 1.54 1.58 0.92 0.72 2.09 23 828.18 Table 5 - Test results of tile adhesive performance: Tensile Adhesion 2 Strength (N / mm³) After heat aging: 5 days after cement-based tile adhesive is applied After a few minutes, the tiles are glued and left to dry under the following conditions: climate for 2 weeks. Controlled storage (23°C and 50% humidity) and in an oven at 70°C for 2 weeks. Post-immersion EID: 1 week in a climate-controlled room (23°C and 50%). humidity) and 3 weeks in the pool Waiting time for CFD: After waiting 30 minutes in cement-based tile adhesive. Then the tiles are glued and left to dry under the following conditions: 4 weeks in a climate-controlled room (23°C) and 50% humidity). The invention concerns a tile adhesive formulated with a water-dispersible powder polymer. (Examples 2 through 7) with water-redispersible powder polymers in contrast to examples 1, 2, 3, 5, and 6. Significantly better results compared to formulated tile adhesives. It provides. Tensile adhesion strength is maintained under all conditions, i.e., initially and after heat aging. It showed improvement after immersion in water and after the waiting period. Transversely Deformation has also shown improvement, which corresponds to better flexibility. The invention concerns water-dispersible powder polymers used in tile adhesive materials. It offers a significant advantage in terms of quality and durability. The frequency of repairs... Thanks to the reduction, the environmental impact has been significantly improved. The invention concerns water-dispersible powder polymers and adhesion after immersion in water. It allows for a much better balance between flexibility and reliability. 24

Claims

1. It is a water-dispersible powder polymer whose characteristic is that it contains the following: - at least one propoxylated compound between 0.1% and 15% by weight hydroxyalkylvinyl ether monomer unit or monomer of the following formula (2) a monomer unit (2) - vinyl ester of at least one monocarboxylic acid, in a ratio of 1% to 40% by weight monomer unit; vinyl ester monomer of the monocarboxylic acid in question. the unit will have a glass transition temperature (Tg) lower than -15°C for its homopolymer. It is as follows: - at least one vinyl acetate monomer unit, between 30% and 95% by weight, where Total weight of monomer unit, total monomer unit in the polymer It is 100% by weight, according to its weight.

2. According to claim 1, it is a water-dispersible powder polymer with the following properties: It includes: - at least one propoxylated compound between 0.1% and 15% by weight hydroxyalkylvinyl ether monomer unit, - vinyl ester of at least one monocarboxylic acid, in a ratio of 1% to 40% by weight monomer unit; vinyl ester monomer of the monocarboxylic acid in question. the unit will have a glass transition temperature (Tg) lower than -15°C for its homopolymer. It is as follows: 828.18 - at least one vinyl acetate monomer unit, between 30% and 95% by weight, where The total weight of a monomer unit is the total weight of monomer units in the polymer. It is 100% by weight, according to its weight.

3. It is a water-dispersible powder polymer according to any of the previous requirements, The characteristic feature is that at least one propoxylated hydroxyalkylvinyl ether monomer is present here. the glass transition temperature (Tg) of the homopolymer is lower than -25°C 4. It is a water-dispersible powder polymer according to any of the previous requirements, The characteristic feature is that at least one propoxylated hydroxyalkylvinyl ether monomer is present here. The glass transition temperature (Tg) of the homopolymer is lower than -50°C.

5. It is a water-dispersible powder polymer according to any of the previous requirements, The characteristic feature is that at least one propoxylated hydroxyalkylvinyl ether monomer is present here. The formula (1) is its monomer:

6. It is a water-dispersible powder polymer according to any of the previous requirements, The characteristic is that at least one monocarboxylic acid vinyl ester monomer unit is present here, 2- It is a vinyl ester of ethylhexanoic acid.

7. It is a water-dispersible powder polymer according to any of the previous requirements, Its characteristic feature is that the polymer contains the following: - at least one propoxylated compound between 0.1% and 15% by weight 26 828.18 hydroxyalkylvinyl ether monomer unit, - vinyl ester of at least one monocarboxylic acid, in a ratio of 1% to 40% by weight monomer unit; vinyl ester monomer of the monocarboxylic acid in question. the unit will have a glass transition temperature (Tg) lower than -15°C for its homopolymer. It is as follows: - at least one vinyl acetate monomer unit, between 30% and 95% by weight, between 0.1% and 30% by weight, preferably having 7 to 17 carbon atoms. - a vinyl ester of a small alpha-branched monocarboxylic acid, Here, the total weight of the monomer unit represents the total monomer in the polymer. It is 100% by weight, according to the weight of the unit.

8. Water-redispersible powder polymer according to any of claims 1 to 7. The process for preparing it involves the following steps: - at least one propoxylated hydroxyalkylvinyl ether monomer and at least one vinyl ester of monocarboxylic acid monomer unit free radical initiator and optionally a surfactant and / or stabilizer an aqueous emulsion or suspension formed by polymerization in the presence of preparation, - the resulting aqueous polymer emulsion or dispersion is dried into powder. to be transformed into.

9. At least one that is in accordance with claims 1 to 7 or obtained according to the process in claim 8. It is a cement-based composition containing water-dispersible powder polymer, the characteristic of which is; here refers to the water-redispersible powder polymer in the cement-based composition in question. The amount should be between 0.1% and 30% by weight.

10. Water obtained according to claims 1 to 7 or according to the process in claim 8. Redispersible powder polymer in cement-based composition, preferably for tiles. 27 828.18 in adhesives, waterproofing membranes, thermal insulation adhesives, and topcoats. Its use is in coating.

11. Water obtained according to claims 1 to 7 or according to the process in claim 8. redispersible powder polymer, cement-based composition after immersion in water Its use is to improve adhesion and flexibility. 28