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WO2025163070A1 - Water-redispersible powder polymer, process to prepare them, and the use thereof in cementitious compositions - Google Patents

Water-redispersible powder polymer, process to prepare them, and the use thereof in cementitious compositions

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Publication number
WO2025163070A1
WO2025163070A1 PCT/EP2025/052400 EP2025052400W WO2025163070A1 WO 2025163070 A1 WO2025163070 A1 WO 2025163070A1 EP 2025052400 W EP2025052400 W EP 2025052400W WO 2025163070 A1 WO2025163070 A1 WO 2025163070A1
Authority
WO
WIPO (PCT)
Prior art keywords
monomer unit
water
polymer
weight
redispersible powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/052400
Other languages
French (fr)
Inventor
Miray SEVER
Jean-Yves Petit
Yeşim INAN AYAS
Gamze CETIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Organik Kimya Sanayi ve Ticaret AS
Original Assignee
Organik Kimya Sanayi ve Ticaret AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Organik Kimya Sanayi ve Ticaret AS filed Critical Organik Kimya Sanayi ve Ticaret AS
Publication of WO2025163070A1 publication Critical patent/WO2025163070A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2623—Polyvinylalcohols; Polyvinylacetates
    • C04B24/2629—Polyvinylalcohols; Polyvinylacetates containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688—Copolymers containing at least three different monomers
    • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0057—Polymers chosen for their physico-chemical characteristics added as redispersable powders
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0065—Polymers characterised by their glass transition temperature (Tg)
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00637—Uses not provided for elsewhere in C04B2111/00 as glue or binder for uniting building or structural materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
    • C04B2111/00801—Membranes; Diaphragms
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures

Definitions

  • the present invention relates to a water-redispersible powder polymer comprising specific monomer units, a process for producing said polymer, and the use of said polymer in construction and building applications.
  • the water-redispersible powder polymer of the invention may be advantageously used to improve both adhesion after water immersion and flexibility of cementitious compositions.
  • Water-redispersible polymer powders are commonly used as additives in construction and building applications to improve the performance of the materials such as adhesion, strength, impact and abrasion resistance, self-levelling property, water resistance, flexibility.
  • water-redispersible polymer powders are prepared by spray drying the appropriate polymer dispersion or emulsion. Generally, water-redispersible polymer powders are dry blended with cement and other component mixtures, followed by mixing with water. During wet mixing, the redispersible polymer powders are redispersed. After redispersion, these redispersed particles fill the pores between the cement crystals and make polymer bridges between these crystals, resulting in enhanced binder properties of cement.
  • the water-redispersible powder polymer of the invention offers a great opportunity to improve the quality of the materials and by way of consequence to increase the durability of the resulting construction materials and building made with said polymers.
  • the present invention relates to a water-redispersible powder polymer comprising specific monomer units, a process for producing said polymer, a cementitious composition comprising said polymer.
  • the present invention also relates to the use of the water redispersible powder polymer construction and building applications, especially in cementitious composition such as tile adhesive, water proofing membrane, thermal insulation adhesive, and topcoat.
  • the water-redispersible powder polymer surprisingly offers improved performances, especially both adhesion after water immersion and flexibility of cementitious compositions.
  • This new water-redispersible powder polymer offers a significant advantage in terms of polymer performances, and in terms of green impact.
  • the Applicant has discovered that the polymers of the invention can surprisingly improve the quality and the durability of the construction materials for example by decreasing the frequency of reparability.
  • the present invention relates to a water-redispersible powder polymer comprising:
  • polymer is used in the present description and refers to the “water- redispersible powder polymer”.
  • the expression “monomer unit” refers to the monomer present in the polymer chain, that has reacted, and which participate to the creation of the polymer chain.
  • the expression “monomer” refers to the monomer before its polymerization. The difference relates to the Carbon-Carbon double bond which is unsaturated and unopen in the “monomer”, and which has reacted and be opened in the case of the “monomer unit” in polymer chain.
  • the water redispersible polymer powder of the present invention has the desired flow property for easy application.
  • the water redispersible polymer powder of the present invention can be redispersed in water when agitated to obtain a paste.
  • the polymer of the invention preferably comprises between 0.1 and 15% by weight of at least one propoxylated hydroxyalkylvinylether monomer unit, more preferably from 1 to 10 % by weight, more preferably from 2 to 8% by weight.
  • the polymer of the invention preferably comprises between 1 and 40% by weight of at least one vinylester of monocarboxylic acid monomer unit, more preferably from 5 to 40%, even more preferably from 10 to 30%, even more preferably from 15 to 25% by weight.
  • the propoxylated hydroxyalkylvinylether monomer is preferably such that its homopolymer have a glass transition temperature Tg lower than - 25°C, preferably lower than - 30°C, even more preferably lower than - 40°C, even more preferably lower than - 50°C, even more preferably lower than - 65°C.
  • the vinylester of monocarboxylic acid monomer is preferably such that its homopolymer have a glass transition temperature Tg lower than - 15°C, preferably lower than - 25°C, preferably lower than - 30°C.
  • the vinylester of monocarboxylic acid is different from vinyl acetate.
  • the glass transition temperature mentioned for a monomer corresponds to the glass transition of its homopolymer.
  • the method for determining transition temperature is Differential Scanning Calorimetry (DSC) with a temperature’s rate of 10°C per minute.
  • the at least one propoxylated hydroxyalkylvinylether monomer is preferably the monomer of formula (1).
  • the at least one vinylester of monocarboxylic acid monomer unit is preferably the vinylester of 2-ethyl hexanoic acid.
  • the polymer of the invention may also advantageously further comprise at least one vinylacetate monomer unit.
  • the polymer of the invention comprises from 30 to 95% by weight of vinyl acetate monomer unit, preferably from 40 to 90% by weight, more preferably from 45 to 75% by weight.
  • the polymer of the invention may also advantageously further comprise at least one vinylester of an alpha-branched monocarboxylic acid monomer unit.
  • the polymer of the invention comprises from 0.1 to 30% by weight, preferably from 1 to 20% by weight of at least one vinylester of an alpha-branched monocarboxylic acid monomer unit.
  • Said vinylester have preferably between 7 to 17 carbon atoms and is more preferably the vinylester of versatic acid 10.
  • the polymer of the invention comprises:
  • the polymer of the invention comprises:
  • the total weight of monomer unit being 100% by weight based on the total weight of monomer unit in the polymer.
  • the polymer of the invention comprises:
  • the polymer of the invention comprises:
  • vinylester of an alpha-branched monocarboxylic acid having preferably between 7 to 17 carbon atoms wherein said vinylester is preferably vinylester of versatic acid 10.
  • the total weight of monomer unit being 100% by weight based on the total weight of monomer unit in the polymer.
  • the polymer of the invention may also advantageously further comprise at least one additional ethylenically unsaturated monomers preferably selected from the list comprising alkyl acrylates or alkyl methacrylates such as linear, branched or cycloaliphatic Ci-C22-alkyl(meth)acrylates, methyl(meth)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, te
  • the polymer according to the invention may be linear, branched, crosslinked or have a starshaped structure.
  • At least one crosslinker may be used to obtain the polymer of the invention.
  • Said crosslinkers are preferably chosen from the list comprising N-methylol acrylamide, N- methylolmethacrylamide, N-(alkoxymethyl)acrylamides or N-(alkoxymethyl)methacrylamides containing a Cl-C6-alkyl radical, e.g.
  • ethylene glycol diacrylate 1,3- butylene glycol di(meth)acrylate, 1,4
  • a chain transfer agent may be used to obtain the polymer of the invention.
  • Suitable chain-transfer agents could be isopropanol, mercaptoethanol, 3 -mercaptopropanol, 3- mercaptopropionic acid, 1 -butanethiol, 1 -propanethiol, 1-prentanethiol, 2-methyl-2- propaneethiol, 1 -hexanethiol, 1 -octanethiol, tert-nonyl mercaptane, n-dodecyl mercaptane, tert-dodecyl mercaptane, 3 -mercapto-3 -methyl butanol, l-mercapto-2-phenyl-2-ethanol, thioglycolic acid, methyl thioglycolate, n-butyl thioglycolate, 2-ethylhexyl thioglycolate, i- octyl thioglycolate, dodecy
  • the glass transition temperature mentioned for the polymer is Differential Scanning Calorimetry (DSC).
  • the present invention also relates to a process to prepare a water redispersible powder polymer comprising:
  • aqueous emulsion or suspension by polymerizing at least one propoxylated hydroxyalkylvinylether monomer and at least one vinylester of monocarboxylic acid monomer, in the presence of a free radical initiator and optionally in the presence of a surfactant and/or a stabilizer,
  • the aqueous emulsion or suspension is obtained by emulsion polymerization or suspension polymerization or dispersion polymerization.
  • the polymerization reaction is preferably carried out in a temperature range of from 25°C to 100°C.
  • the polymerization is preferably a seeded polymerization.
  • a seeded polymerization is a specific mode of polymerization that comprises the use of seed polymer in the polymerization process.
  • a seeded polymerization comprises the use of finely divided polymer particles during the emulsion polymerization. These finely divided polymer particles are called “seed polymer” because they act like a seed or a nuclei, on which the polymerization of the reactive monomers can start.
  • the seed polymers are generally, and preferably added at the early stage of the polymerization.
  • a seeded polymerization is a polymerization made in the presence of seed polymers, preferably added at the beginning of the polymerization, and comprising a nucleation stage at the start of the reaction and a stabilization stage of the nuclei during the growth stage.
  • the polymerization reaction is preferably initiated by means of water-soluble free-radical initiators.
  • the polymerization initiators may be selected from the group consisting of thermal polymerization initiators, redox polymerization initiators and combinations thereof, particularly inorganic and/or organic persulfates such as ammonium, potassium persulfate, sodium persulfates and the like, peroxides such as cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, hydrogen peroxide, and the like and also perbenzoates, peralkanoates or azoinitiators such as azobis- isobutyronitrile (AIBN) and combinations thereof for the production of sustainable binder composition.
  • thermal polymerization initiators redox polymerization initiators and combinations thereof
  • inorganic and/or organic persulfates such as ammonium, potassium persulfate, sodium persulfates and the like
  • peroxides such as cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, hydrogen peroxid
  • Suitable reducing agents of a redox initiator system may include compounds, such as sulphur compounds, such as alkali metal bisulfites, hydrogen sulfites, ketone adducts of bisulfites, such as acetone bisulfite, alkali metal disulfites, metabisulfites and its salts, formaldehyde sulfoxylates and its salts, thiosulfates, reducing nitrogen compounds, such as hydroxylamine hydrosulfate , hydroxylamines and hydroxylammonium salts, polyamines and reducing sugars, such as sorbose, fructose, glucose, lactose and derivatives thereof, enediols, such as and isoascorbic acid, ascorbic acid sulfinic acids, hydroxy alkyl sulfinic acids, such as hydroxy methyl sulfinic acid and 2-hydroxy-2-sulfinactic acid and its salts.
  • Suitable surfactant can be all commercially available ionic and non-ionic surfactant.
  • fatty alcohol ether sulphates ethoxylated alcohol polyethylene glycol ethers, ethoxylated fatty alcohols and also alkali metal and ammonium salts of long-chain alkyl sulfates (C8-C12-alkyl radical), of sulfuric monoesters of ethoxylated alkanols and ethoxylated alkylphenols of alkyl acids and of alkylaryl sulfonic acids.
  • the stabilizer is preferably polyvinyl alcohols, hydroxy ethyl cellulose, polyethylene glycol, polyvinylpyrrolidone, carboxymethylcellulose, starch and cellulose derivatives.
  • the stabilizer is colloidal stabilizer. It may be a polymeric stabilizer.
  • polymeric stabilizer refers to a type of stabilizer which have generally both hydrophobic moieties and carboxylic acid functional groups.
  • the polymeric stabilizer has preferably a weight average molecular weight within the range of 1.000 to 120.000 Daltons, preferably within the range of 5.000 to 60.000, more preferably within the range of 10.000 to 50.000, even more preferably within the range of 10.000 to 30.000 Daltons.
  • the polymer aqueous emulsion or dispersion obtained after the polymerization has a polymer content generally comprised between 20 and 70% by weight.
  • the process of the invention comprises an additional step in which the polymer emulsion or dispersion is dried to obtain a polymer powder.
  • the polymer emulsion or dispersion is dried, for example by means of fluidized-bed drying, freeze-drying or spray-drying, preferably spray-drying.
  • the spray-drying is carried out in conventional spray-drying plants by hot air steam known from the prior art. It is possible to effect the atomization by means of airless nozzles, binary nozzles or multiple nozzles or with a rotating disk.
  • the inlet temperature of the spray dryer is usually from 80 to 150°C, preferably from 120 to 145°C.
  • the outlet temperature of the spray dryer is usually from 40 to 100°C, preferably from 50 to 80°C.
  • anticaking agents such as finely divided silica, kaolin, calcium carbonate, magnesium carbonate, talc, aluminium silicates, combinations of dolomite or other mineral auxiliaries can be added to the water-redispersible powder polymer, in a known manner.
  • the present invention also relates to a cementitious composition
  • a cementitious composition comprising at least one water redispersible powder polymer according to the present invention or obtained according to the process of the invention.
  • the amount of said polymer in said cementitious composition is preferably comprised between 0,1 to 30 % by weight.
  • the present invention also relates to the use of the water redispersible powder polymer according to the invention or obtained according to the process of the invention in cementitious composition, preferably tile adhesive, water proofing membrane, thermal insulation adhesive, and topcoat.
  • the present invention also relates to the use of the redispersible powder polymer according to the invention or obtained according to the process of the invention to improve the adhesion after water immersion and the flexibility of cementitious composition.
  • the polymer of the invention may be used to produce coating, paint, primer, ink, adhesives such as pressure sensitive adhesive, textile and leather additive, paper additive, constructions additive.
  • the polymer of the invention may be advantageously used in coating formulations such as interior or exterior paints, primers, plasters, trowel applied decorative coatings for architectural applications, also for industrial wood and metal coatings, coatings for plastic & composite surfaces, road marking paints, roof coatings, roof tile paints, printings inks, agricultural coatings, dust and sol stabilization coatings, and overprint varnishes, pressure sensitive adhesives such as paper label adhesive, packaging tape adhesive, protective film adhesive, lamination adhesive, contact adhesive, paper tape adhesive, masking tape adhesive, film label adhesive, cold seal-heatseal adhesive, flooring, adhesive, flexible packaging adhesive, tapes, protective films, packaging lamination, specialty paper, paper coating, paper impregnation binder, release binder, paper saturation binder etc., textile and leather applications such as finishing, coating, flocking, nonwoven, printing, wet end, finishing and construction applications such as construction adhesives and coatings as waterproofing and sealing, cement modifiers, sealants, tile adhesives and grouts, mortar and repair mortar, external thermal insulation composite system, self
  • the polymer of the invention offers a significant advantage in terms of polymer performances, and in terms of green impact.
  • the polymer of the invention can improve the quality and the durability of the construction materials, for example by decreasing the frequency of reparability.
  • the invention relates to a water-redispersible powder polymer comprising:
  • the at least propoxylated hydroxyalkylvinylether monomer unit is replaced by at least one monomer unit of the monomer of formula (2).
  • the “n” value is preferably comprised between 1 and 20, more preferably between 2 and 15, more preferably between 5 and 12.
  • the monomer unit of the monomer of formula (2) is Rhodasurf AAE10.
  • the polymer of this aspect preferably comprises between 0.1 and 15% by weight of at least one monomer unit of the monomer of formula (2), more preferably from 1 to 10 % by weight, more preferably from 2 to 8% by weight.
  • the at least one monomer unit of the monomer of formula (2) has “m” propoxylation and not “n” ethoxylation in its structure.
  • the “m” value has the same preferences as the “n” value.
  • Another alternative is that the at least one monomer unit of the monomer of formula (2) has both propoxylation and ethoxylation in its structure.
  • the invention relates to a water-redispersible powder polymer comprising:
  • the at least propoxylated hydroxyalkylvinylether monomer unit is replaced by at least one vinyl ether monomer unit.
  • the vinyl ether monomer unit has preferably at least C3, more preferably at least C5, more preferably at least C7, more preferably at least CIO side chain.
  • the vinyl ether monomer unit has preferably at least one OH termination.
  • the vinyl ether monomer unit has preferably at least one propoxylated unit and/or at least ethoxylated unit. The propoxylated versions are preferred.
  • the polymer of this aspect preferably comprises between 0.1 and 15% by weight of at least one vinyl ether monomer unit, more preferably from 1 to 10 % by weight, more preferably from 2 to 8% by weight.
  • the invention relates to a water-redispersible powder polymer comprising:
  • the at least propoxylated hydroxyalkylvinylether monomer unit is replaced by at least one vinyl ether monomer unit (i).
  • the vinyl ether monomer unit (i) has preferably at least C3, more preferably at least C5, more preferably at least C7, more preferably at least CIO side chain.
  • the vinyl ether monomer unit (i) has preferably at least one OH termination.
  • the vinyl ether monomer unit (i) has preferably at least one propoxylated unit and/or at least ethoxylated unit.
  • the propoxylated versions are preferred.
  • the polymer of this aspect preferably comprises between 0.1 and 15% by weight of at least one vinyl ester monomer unit, more preferably from 1 to 10 % by weight, more preferably from 2 to 8% by weight.
  • the invention relates to a water-redispersible powder polymer comprising:
  • the water redispersible powder polymers are obtained by dispersion polymerization and spraydrying of the resulting polymer dispersion.
  • Monomers are polymerized in seeded polymerization in the presence of a polymeric stabilizer (a hydrolyzed polyvinyl alcohol). Hydrogen peroxide, sodium sulphoxylate and sodium bicarbonate are added in the monomer mixture. The polymerization is conducted at 75°C for 3 hours, and the resulting polymer dispersion is heated at reaction temperature for additional 30 minutes. The temperature is then decreased to 70°C and tert-butyl hydroperoxide dissolved in deionized water is added. A polymer dispersion is obtained. The resulting polymer dispersion is then spray dried to obtain a polymer powder. The resulting polymer dispersion is first heated at 70°C and spray dried in a Niro spray dryer system using an inlet temperature of 140°C. The drying gas is air.
  • a polymeric stabilizer a hydrolyzed polyvinyl alcohol
  • Example 1 to 4 Four water-redispersible powder polymers according to the invention have been prepared (Example 1 to 4), and six water-redispersible powder polymers not according to the invention have been prepared (Counterexample 1 to 6).
  • the water-redispersible powder polymers have the following monomer composition.
  • Table 1 - Polymer compositions Exl to Ex4 are examples corresponding to polymers of the invention.
  • CExl to CEx6 are counterexamples corresponding to polymers out of the invention.
  • VAM Vinylacetate
  • PHAV Propoxylated hydroxyalkylvinylether monomer having the formula (1).
  • Veova EH Vinyl ester of 2-ethyl hexanoic acid
  • Veova 10 Vinyl ester of versatic acid 10
  • the water-redispersible powder polymers previously prepared are formulated and tested in plaster and tile adhesive applications.
  • Water-redispersible powder polymer of Example 1 and of Counter Examples 1 to 4 are formulated and tested in plaster application according to ETAG 004 Standard.
  • Water-redispersible powder polymer of Example 1 is compared to water-redispersible powder polymer of Counter Examples 1 to 4.
  • “Plaster Exl” corresponds to the plaster formulation made with the water-redispersible powder polymer of Example 1.
  • “Plaster CExl” corresponds to the plaster formulation made with the water-redispersible powder polymer of Counterexample 1, etc...
  • the water-redispersible powder polymer according to the invention offers a significant advantage in terms quality and durability of the plaster materials.
  • the green impact is significantly improved thanks to the decrease of the reparability frequency.
  • the water-redispersible powder polymer according to the invention allows a far better compromise between adhesion after immersion and flexibility.
  • Water-redispersible powder polymer of Example 2 to 4 and of Counter Examples 1, 2, 3, 5 and 6 are formulated and tested in tile adhesive application according to EN 12004 Standard.
  • Water-redispersible powder polymer of Example 2 to 4 are compared to water-redispersible powder polymer of Counter Examples 1, 2, 3, 5 and 6.
  • “Tile adhesive Ex2” corresponds to the tile adhesive formulation made with the water-redispersible powder polymer of Example 2.
  • “Tile adhesive CExl” corresponds to the tile adhesive formulation made with the water- redispersible powder polymer of Counterexample 1, etc. . .
  • TAS Tensile Adhesion Strength (N/mm 2 )
  • TAS after heat aging Adhere tile after 5min waiting on cementitious tile adhesive and condition: 2 weeks climatic room (23°C and 50% Humidity) and 2 weeks at 70°C oven. TAS after water immersion: 1-week climatic room (23°C and 50% Humidity) and 3 weeks in water pool.
  • TAS open time Adhere tile after 30min waiting on cementitious tile adhesive and condition: 4 weeks in climatic room (23°C and 50% Humidity).
  • Tile adhesive formulated with the water-redispersible powder polymers according to the invention (Ex2 to 7) give significant better results compared to tile adhesive formulated with the water-redispersible powder polymers of counterexamples 1, 2, 3, 5 and 6.
  • the tensile adhesion strengths are improved in all conditions: initial, after heat aging, after water immersion and open time.
  • the transverse deformation is also improved which corresponds to a better flexibility.
  • the water-redispersible powder polymers according to the invention offer a significant advantage in terms quality and durability of the tile adhesive materials.
  • the green impact is significantly improved thanks to the decrease of the reparability frequency.
  • the water-redispersible powder polymers according to the invention allows a far better compromise between adhesion after immersion and flexibility.

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Abstract

The present invention relates to a water-redispersible powder polymer comprising specific monomer units, a process for producing said polymer, and the use of said polymer in construction and building applications.

Description

Title: « Water-redispersible powder polymer, process to prepare them, and the use thereof in cementitious compositions”
Technical domain of the invention
The present invention relates to a water-redispersible powder polymer comprising specific monomer units, a process for producing said polymer, and the use of said polymer in construction and building applications. The water-redispersible powder polymer of the invention may be advantageously used to improve both adhesion after water immersion and flexibility of cementitious compositions.
Background of the invention
Water-redispersible polymer powders are commonly used as additives in construction and building applications to improve the performance of the materials such as adhesion, strength, impact and abrasion resistance, self-levelling property, water resistance, flexibility.
These water-redispersible polymer powders are prepared by spray drying the appropriate polymer dispersion or emulsion. Generally, water-redispersible polymer powders are dry blended with cement and other component mixtures, followed by mixing with water. During wet mixing, the redispersible polymer powders are redispersed. After redispersion, these redispersed particles fill the pores between the cement crystals and make polymer bridges between these crystals, resulting in enhanced binder properties of cement.
Despite great technical improvements of the water-redispersible polymer powders, there is still a need to improve both adhesion after water immersion and flexibility of cementitious compositions.
The Applicant has discovered that it is possible to reach this goal with a water-redispersible powder polymer comprising specific monomer units.
Summary of the invention
The water-redispersible powder polymer of the invention offers a great opportunity to improve the quality of the materials and by way of consequence to increase the durability of the resulting construction materials and building made with said polymers. The present invention relates to a water-redispersible powder polymer comprising specific monomer units, a process for producing said polymer, a cementitious composition comprising said polymer. The present invention also relates to the use of the water redispersible powder polymer construction and building applications, especially in cementitious composition such as tile adhesive, water proofing membrane, thermal insulation adhesive, and topcoat.
Detailed description of the invention
According to the invention, thanks to the selection of at least two different and specific monomer units present in the polymer chain, the water-redispersible powder polymer surprisingly offers improved performances, especially both adhesion after water immersion and flexibility of cementitious compositions.
This new water-redispersible powder polymer offers a significant advantage in terms of polymer performances, and in terms of green impact. Against all expectations, the Applicant has discovered that the polymers of the invention can surprisingly improve the quality and the durability of the construction materials for example by decreasing the frequency of reparability.
The water-redispersible powder polymer
The present invention relates to a water-redispersible powder polymer comprising:
- at least one propoxylated hydroxyalkylvinylether monomer unit,
- at least one vinylester of monocarboxylic acid monomer unit,
- optionally at least one vinylacetate monomer unit.
The expression “polymer” is used in the present description and refers to the “water- redispersible powder polymer”.
The expression “monomer unit” refers to the monomer present in the polymer chain, that has reacted, and which participate to the creation of the polymer chain. The expression “monomer” refers to the monomer before its polymerization. The difference relates to the Carbon-Carbon double bond which is unsaturated and unopen in the “monomer”, and which has reacted and be opened in the case of the “monomer unit” in polymer chain. The water redispersible polymer powder of the present invention has the desired flow property for easy application. The water redispersible polymer powder of the present invention can be redispersed in water when agitated to obtain a paste.
The polymer of the invention preferably comprises between 0.1 and 15% by weight of at least one propoxylated hydroxyalkylvinylether monomer unit, more preferably from 1 to 10 % by weight, more preferably from 2 to 8% by weight.
The polymer of the invention preferably comprises between 1 and 40% by weight of at least one vinylester of monocarboxylic acid monomer unit, more preferably from 5 to 40%, even more preferably from 10 to 30%, even more preferably from 15 to 25% by weight.
The propoxylated hydroxyalkylvinylether monomer is preferably such that its homopolymer have a glass transition temperature Tg lower than - 25°C, preferably lower than - 30°C, even more preferably lower than - 40°C, even more preferably lower than - 50°C, even more preferably lower than - 65°C.
The vinylester of monocarboxylic acid monomer is preferably such that its homopolymer have a glass transition temperature Tg lower than - 15°C, preferably lower than - 25°C, preferably lower than - 30°C.
According to a particular embodiment, the vinylester of monocarboxylic acid is different from vinyl acetate.
The glass transition temperature mentioned for a monomer, corresponds to the glass transition of its homopolymer. In the present invention, the method for determining transition temperature is Differential Scanning Calorimetry (DSC) with a temperature’s rate of 10°C per minute.
The use of the expression 30°C” means minus 30 degrees Celsius. Same for 50°C”, that means minus 50 degrees Celsius.
The at least one propoxylated hydroxyalkylvinylether monomer is preferably the monomer of formula (1). The at least one vinylester of monocarboxylic acid monomer unit is preferably the vinylester of 2-ethyl hexanoic acid.
The polymer of the invention may also advantageously further comprise at least one vinylacetate monomer unit. In a preferred embodiment the polymer of the invention comprises from 30 to 95% by weight of vinyl acetate monomer unit, preferably from 40 to 90% by weight, more preferably from 45 to 75% by weight.
The polymer of the invention may also advantageously further comprise at least one vinylester of an alpha-branched monocarboxylic acid monomer unit. In a preferred embodiment the polymer of the invention comprises from 0.1 to 30% by weight, preferably from 1 to 20% by weight of at least one vinylester of an alpha-branched monocarboxylic acid monomer unit. Said vinylester have preferably between 7 to 17 carbon atoms and is more preferably the vinylester of versatic acid 10.
In a preferred embodiment, the polymer of the invention comprises:
- at least one propoxylated hydroxyalkylvinylether monomer unit,
- at least one vinylester of monocarboxylic acid monomer unit,
- at least one vinylacetate monomer unit
In a preferred embodiment, the polymer of the invention comprises:
- from 0.1 and 15% by weight of at least one propoxylated hydroxyalkylvinylether monomer unit,
- from 1 to 40% by weight of at least one vinylester of monocarboxylic acid monomer unit,
- from 30 to 95% by weight of at least one vinylacetate monomer unit,
The total weight of monomer unit being 100% by weight based on the total weight of monomer unit in the polymer.
In another preferred embodiment, the polymer of the invention comprises:
- at least one propoxylated hydroxyalkylvinylether monomer unit,
- at least one vinylester of monocarboxylic acid monomer unit,
- at least one vinylacetate monomer unit, - at least one vinylester of an alpha-branched monocarboxylic acid having preferably between 7 to 17 carbon atoms, wherein said vinylester is preferably vinylester of versatic acid 10.
In another preferred embodiment, the polymer of the invention comprises:
- from 0.1 and 15% by weight of at least one propoxylated hydroxyalkylvinylether monomer unit,
- from 1 to 40% by weight of at least one vinylester of monocarboxylic acid monomer unit,
- from 30 to 95% by weight of at least one vinylacetate monomer unit,
- from 0.1 to 30% by weight of at least one vinylester of an alpha-branched monocarboxylic acid having preferably between 7 to 17 carbon atoms, wherein said vinylester is preferably vinylester of versatic acid 10.
The total weight of monomer unit being 100% by weight based on the total weight of monomer unit in the polymer.
The polymer of the invention may also advantageously further comprise at least one additional ethylenically unsaturated monomers preferably selected from the list comprising alkyl acrylates or alkyl methacrylates such as linear, branched or cycloaliphatic Ci-C22-alkyl(meth)acrylates, methyl(meth)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, methoxymethoxy ethyl(meth )acrylate, benzyloxymethyl(meth)acrylate, furfuryl-(meth)acrylate, 2-butoxy ethyl (meth)acrylate, 2-ethoxyethyl(meth)acrylate, allyloxymethyl(meth)acrylate, 1 ethoxybutyl(meth)acrylate, 1 -ethoxy ethyl- (meth)acrylate,ethoxymethyl(meth)acrylate, poly(ethyleneglycol)methyl-ether(meth)acrylate, and poly(propyleneglycol) methylether (meth)acrylate or aminoalkyl(meth)acrylates such as N,N-dimethyl aminoethyl
(meth)acrylate, 2- trimethylammoniumethyl(meth)acrylatchloride and N,N-dimethyl mino- propyl(meth)acrylate, oxiranyl(meth)acrylates such as 2,3-epoxy butyl(meth)acrylate, 3,4- epoxy- butyl(meth)acrylate and glycidyl(meth)acrylate, styrenes, substituted styrenes such as a-m ethyl styrenes, 4-m ethyl styrenes, 4-vinylbenzoic acid and sodium -4-vinylbenzene sulfonate, vinylesters of carboxylic acids comprising 1 to 20 carbon atoms, especially vinylacetate, vinylesters of versatic acids, (meth)acrylamides, acid functional monomers such as 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, isobomylacrylic acid and tert-butylacrylic acid.
The polymer according to the invention may be linear, branched, crosslinked or have a starshaped structure.
When the polymer of the invention is branched, crosslinked or have a star-shaped structure at least one crosslinker may be used to obtain the polymer of the invention.
Said crosslinkers are preferably chosen from the list comprising N-methylol acrylamide, N- methylolmethacrylamide, N-(alkoxymethyl)acrylamides or N-(alkoxymethyl)methacrylamides containing a Cl-C6-alkyl radical, e.g. N-isobuthoxymethyl)acrylamide (IB MA), N- (isobutoxymethyl)methacrylamide (IBMMA), N-(n-butoxymethyl)acrylamide (NBMA), N-(n- butoxymethyl)methacrylamide (NBMMA), diacetone acrylamide (DIAAM); multiple ethylenically unsaturated comonomers such as 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, cyclopentadienyl acrylate or triallyl cyanurate.
A chain transfer agent may be used to obtain the polymer of the invention.
Suitable chain-transfer agents could be isopropanol, mercaptoethanol, 3 -mercaptopropanol, 3- mercaptopropionic acid, 1 -butanethiol, 1 -propanethiol, 1-prentanethiol, 2-methyl-2- propaneethiol, 1 -hexanethiol, 1 -octanethiol, tert-nonyl mercaptane, n-dodecyl mercaptane, tert-dodecyl mercaptane, 3 -mercapto-3 -methyl butanol, l-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 mercaptane, tetrabromomethane and carbon tetrachloride. In a preferred embodiment, the polymer of the invention has preferably a glass transition temperature Tg between - 30°C and +80°C, more preferably between - 15°C and +30°.
In the present invention the glass transition temperature mentioned for the polymer, the method for determining transition temperature is Differential Scanning Calorimetry (DSC).
The process
The present invention also relates to a process to prepare a water redispersible powder polymer comprising:
- Preparing an aqueous emulsion or suspension by polymerizing at least one propoxylated hydroxyalkylvinylether monomer and at least one vinylester of monocarboxylic acid monomer, in the presence of a free radical initiator and optionally in the presence of a surfactant and/or a stabilizer,
- Drying the resulting aqueous polymer emulsion or dispersion to obtain a powder.
In the process of the invention, the same preference as described in the above “polymer” part applies to said process, including the nature and the quantity of each monomer.
The aqueous emulsion or suspension is obtained by emulsion polymerization or suspension polymerization or dispersion polymerization. The polymerization reaction is preferably carried out in a temperature range of from 25°C to 100°C.
The polymerization is preferably a seeded polymerization. A seeded polymerization is a specific mode of polymerization that comprises the use of seed polymer in the polymerization process. A seeded polymerization comprises the use of finely divided polymer particles during the emulsion polymerization. These finely divided polymer particles are called “seed polymer” because they act like a seed or a nuclei, on which the polymerization of the reactive monomers can start. The seed polymers are generally, and preferably added at the early stage of the polymerization.
A seeded polymerization is a polymerization made in the presence of seed polymers, preferably added at the beginning of the polymerization, and comprising a nucleation stage at the start of the reaction and a stabilization stage of the nuclei during the growth stage. The polymerization reaction is preferably initiated by means of water-soluble free-radical initiators. Preferably the polymerization initiators, may be selected from the group consisting of thermal polymerization initiators, redox polymerization initiators and combinations thereof, particularly inorganic and/or organic persulfates such as ammonium, potassium persulfate, sodium persulfates and the like, peroxides such as cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, hydrogen peroxide, and the like and also perbenzoates, peralkanoates or azoinitiators such as azobis- isobutyronitrile (AIBN) and combinations thereof for the production of sustainable binder composition.
Suitable reducing agents of a redox initiator system may include compounds, such as sulphur compounds, such as alkali metal bisulfites, hydrogen sulfites, ketone adducts of bisulfites, such as acetone bisulfite, alkali metal disulfites, metabisulfites and its salts, formaldehyde sulfoxylates and its salts, thiosulfates, reducing nitrogen compounds, such as hydroxylamine hydrosulfate , hydroxylamines and hydroxylammonium salts, polyamines and reducing sugars, such as sorbose, fructose, glucose, lactose and derivatives thereof, enediols, such as and isoascorbic acid, ascorbic acid sulfinic acids, hydroxy alkyl sulfinic acids, such as hydroxy methyl sulfinic acid and 2-hydroxy-2-sulfinactic acid and its salts. In addition, it is possible to use metal compounds in which the metal can be present in various oxidation states, e.g. iron (Il)sulfate.
When at least one surfactant is be used for the polymerization step. Suitable surfactant can be all commercially available ionic and non-ionic surfactant. Particularly, preferred examples are fatty alcohol ether sulphates, ethoxylated alcohol polyethylene glycol ethers, ethoxylated fatty alcohols and also alkali metal and ammonium salts of long-chain alkyl sulfates (C8-C12-alkyl radical), of sulfuric monoesters of ethoxylated alkanols and ethoxylated alkylphenols of alkyl acids and of alkylaryl sulfonic acids.
When at least one stabilizer is used the stabilizer is preferably polyvinyl alcohols, hydroxy ethyl cellulose, polyethylene glycol, polyvinylpyrrolidone, carboxymethylcellulose, starch and cellulose derivatives. The stabilizer is colloidal stabilizer. It may be a polymeric stabilizer.
The term “polymeric stabilizer (PS)” as used herein and throughout the specification refers to a type of stabilizer which have generally both hydrophobic moieties and carboxylic acid functional groups.
The polymeric stabilizer has preferably a weight average molecular weight within the range of 1.000 to 120.000 Daltons, preferably within the range of 5.000 to 60.000, more preferably within the range of 10.000 to 50.000, even more preferably within the range of 10.000 to 30.000 Daltons.
The polymer aqueous emulsion or dispersion obtained after the polymerization has a polymer content generally comprised between 20 and 70% by weight.
The process of the invention comprises an additional step in which the polymer emulsion or dispersion is dried to obtain a polymer powder.
The polymer emulsion or dispersion is dried, for example by means of fluidized-bed drying, freeze-drying or spray-drying, preferably spray-drying. In general, the spray-drying is carried out in conventional spray-drying plants by hot air steam known from the prior art. It is possible to effect the atomization by means of airless nozzles, binary nozzles or multiple nozzles or with a rotating disk. The inlet temperature of the spray dryer is usually from 80 to 150°C, preferably from 120 to 145°C. The outlet temperature of the spray dryer is usually from 40 to 100°C, preferably from 50 to 80°C.
To avoid caking of the polymer powder, anticaking agents such as finely divided silica, kaolin, calcium carbonate, magnesium carbonate, talc, aluminium silicates, combinations of dolomite or other mineral auxiliaries can be added to the water-redispersible powder polymer, in a known manner.
The use of the polymer
The present invention also relates to a cementitious composition comprising at least one water redispersible powder polymer according to the present invention or obtained according to the process of the invention. The amount of said polymer in said cementitious composition is preferably comprised between 0,1 to 30 % by weight.
The present invention also relates to the use of the water redispersible powder polymer according to the invention or obtained according to the process of the invention in cementitious composition, preferably tile adhesive, water proofing membrane, thermal insulation adhesive, and topcoat.
The present invention also relates to the use of the redispersible powder polymer according to the invention or obtained according to the process of the invention to improve the adhesion after water immersion and the flexibility of cementitious composition. In another aspect of the invention, the polymer of the invention may be used to produce coating, paint, primer, ink, adhesives such as pressure sensitive adhesive, textile and leather additive, paper additive, constructions additive.
The polymer of the invention may be advantageously used in coating formulations such as interior or exterior paints, primers, plasters, trowel applied decorative coatings for architectural applications, also for industrial wood and metal coatings, coatings for plastic & composite surfaces, road marking paints, roof coatings, roof tile paints, printings inks, agricultural coatings, dust and sol stabilization coatings, and overprint varnishes, pressure sensitive adhesives such as paper label adhesive, packaging tape adhesive, protective film adhesive, lamination adhesive, contact adhesive, paper tape adhesive, masking tape adhesive, film label adhesive, cold seal-heatseal adhesive, flooring, adhesive, flexible packaging adhesive, tapes, protective films, packaging lamination, specialty paper, paper coating, paper impregnation binder, release binder, paper saturation binder etc., textile and leather applications such as finishing, coating, flocking, nonwoven, printing, wet end, finishing and construction applications such as construction adhesives and coatings as waterproofing and sealing, cement modifiers, sealants, tile adhesives and grouts, mortar and repair mortar, external thermal insulation composite system, self-leveling compounds and redispersible powders.
The polymer of the invention offers a significant advantage in terms of polymer performances, and in terms of green impact. The polymer of the invention can improve the quality and the durability of the construction materials, for example by decreasing the frequency of reparability.
Other Objects of the invention
In another aspect, the invention relates to a water-redispersible powder polymer comprising:
- at least one monomer unit of the monomer of formula (2),
- at least one vinylester of monocarboxylic acid monomer unit,
- optionally at least one vinylacetate monomer unit. (2)
In this aspect of the invention, the at least propoxylated hydroxyalkylvinylether monomer unit is replaced by at least one monomer unit of the monomer of formula (2). The “n” value is preferably comprised between 1 and 20, more preferably between 2 and 15, more preferably between 5 and 12. Preferably the monomer unit of the monomer of formula (2) is Rhodasurf AAE10.
The polymer of this aspect preferably comprises between 0.1 and 15% by weight of at least one monomer unit of the monomer of formula (2), more preferably from 1 to 10 % by weight, more preferably from 2 to 8% by weight.
In this aspect, all the preferences mentioned above in the detailed description concerning the water-redispersible powder polymer, apply to the polymer of this aspect ; it concerns in a nonlimited manner the monomer natures, the monomer concentrations, the Tg, the polymer structures, the crosslinkers, the chain transfer agents, the process, the polymerizations, the initiators, the surfactants, the stabilizers, the polymer forms (emulsion powder), and the uses.
An alternative to this aspect is that the at least one monomer unit of the monomer of formula (2) has “m” propoxylation and not “n” ethoxylation in its structure. The “m” value has the same preferences as the “n” value. Another alternative is that the at least one monomer unit of the monomer of formula (2) has both propoxylation and ethoxylation in its structure.
In another aspect, the invention relates to a water-redispersible powder polymer comprising:
- at least one vinyl ether monomer unit, - at least one vinylester of monocarboxylic acid monomer unit,
- optionally at least one vinylacetate monomer unit.
In this aspect of the invention, the at least propoxylated hydroxyalkylvinylether monomer unit is replaced by at least one vinyl ether monomer unit.
In this aspect, the vinyl ether monomer unit has preferably at least C3, more preferably at least C5, more preferably at least C7, more preferably at least CIO side chain. The vinyl ether monomer unit has preferably at least one OH termination. The vinyl ether monomer unit has preferably at least one propoxylated unit and/or at least ethoxylated unit. The propoxylated versions are preferred.
In this aspect, the polymer of this aspect preferably comprises between 0.1 and 15% by weight of at least one vinyl ether monomer unit, more preferably from 1 to 10 % by weight, more preferably from 2 to 8% by weight.
In this aspect, all the preferences mentioned above in the detailed description concerning the water-redispersible powder polymer, apply to the polymer of this aspect ; it concerns in a nonlimited manner the monomer natures, the monomer concentrations, the Tg, the polymer structures, the crosslinkers, the chain transfer agents, the process, the polymerizations, the initiators, the surfactants, the stabilizers, the polymer forms (emulsion powder), and the uses.
In another aspect, the invention relates to a water-redispersible powder polymer comprising:
- at least one vinyl ester monomer unit (i),
- at least one vinylester of monocarboxylic acid monomer unit,
- optionally at least one vinylacetate monomer unit.
In this aspect of the invention, the at least propoxylated hydroxyalkylvinylether monomer unit is replaced by at least one vinyl ether monomer unit (i).
In this aspect, the vinyl ether monomer unit (i) has preferably at least C3, more preferably at least C5, more preferably at least C7, more preferably at least CIO side chain. The vinyl ether monomer unit (i) has preferably at least one OH termination. The vinyl ether monomer unit (i) has preferably at least one propoxylated unit and/or at least ethoxylated unit. The propoxylated versions are preferred. In this aspect, the polymer of this aspect preferably comprises between 0.1 and 15% by weight of at least one vinyl ester monomer unit, more preferably from 1 to 10 % by weight, more preferably from 2 to 8% by weight.
In this aspect, all the preferences mentioned above in the detailed description concerning the water-redispersible powder polymer, apply to the polymer of this aspect ; it concerns in a nonlimited manner the monomer natures, the monomer concentrations, the Tg, the polymer structures, the crosslinkers, the chain transfer agents, the process, the polymerizations, the initiators, the surfactants, the stabilizers, the polymer forms (emulsion powder), and the uses.
The invention is described in more detail, but not limited to the following examples. The parts and percentages stated in the examples are based on weight unless otherwise stated.
In another aspect, the invention relates to a water-redispersible powder polymer comprising:
- from 0.1 and 15% by weight of at least one propoxylated hydroxyalkylvinylether monomer unit or of a monomer unit of the monomer of formula (2)
- from 1 to 40% by weight of at least one vinylester of monocarboxylic acid monomer unit, said vinylester of monocarboxylic acid monomer unit being such that its homopolymer have a glass transition temperature Tg lower than - 15°C,
- from 30 to 95% by weight of at least one vinylacetate monomer unit, the total weight of monomer unit being 100% by weight based on the total weight of monomer unit in the polymer.
Examples
Water-redispersible powder polymer
The water redispersible powder polymers are obtained by dispersion polymerization and spraydrying of the resulting polymer dispersion.
Monomers are polymerized in seeded polymerization in the presence of a polymeric stabilizer (a hydrolyzed polyvinyl alcohol). Hydrogen peroxide, sodium sulphoxylate and sodium bicarbonate are added in the monomer mixture. The polymerization is conducted at 75°C for 3 hours, and the resulting polymer dispersion is heated at reaction temperature for additional 30 minutes. The temperature is then decreased to 70°C and tert-butyl hydroperoxide dissolved in deionized water is added. A polymer dispersion is obtained. The resulting polymer dispersion is then spray dried to obtain a polymer powder. The resulting polymer dispersion is first heated at 70°C and spray dried in a Niro spray dryer system using an inlet temperature of 140°C. The drying gas is air.
To prevent caking, kaolin is added through other nozzles. The resulting polymer powder can be easily mixed with water to provide a free flowing, blocking resistant and stable dispersion. Four water-redispersible powder polymers according to the invention have been prepared (Example 1 to 4), and six water-redispersible powder polymers not according to the invention have been prepared (Counterexample 1 to 6).
The water-redispersible powder polymers have the following monomer composition.
Table 1 - Polymer compositions Exl to Ex4 are examples corresponding to polymers of the invention. CExl to CEx6 are counterexamples corresponding to polymers out of the invention.
VAM: Vinylacetate
PHAV: Propoxylated hydroxyalkylvinylether monomer having the formula (1).
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
The water-redispersible powder polymers previously prepared are formulated and tested in plaster and tile adhesive applications.
Application tests in Plasters
Water-redispersible powder polymer of Example 1 and of Counter Examples 1 to 4 are formulated and tested in plaster application according to ETAG 004 Standard.
The following plaster formulation is detailed in Table 2.
Table 2 - Plaster formulation
Water-redispersible powder polymer of Example 1 is compared to water-redispersible powder polymer of Counter Examples 1 to 4. “Plaster Exl” corresponds to the plaster formulation made with the water-redispersible powder polymer of Example 1. “Plaster CExl” corresponds to the plaster formulation made with the water-redispersible powder polymer of Counterexample 1, etc...
Results of tests are detailed in Table 3.
Table 3 - Test results of plaster performances
For adhesion tests, higher is the value, better is the adhesion. For impact test, which is related to the flexibility, lower is the value, better is the result.
“Plaster Exl” formulated with the water-redispersible powder polymer according to the invention gives significant better results compared to plasters formulated with the water- redispersible powder polymers of counterexamples 1 to 4.
The initial adhesion on Expanded Polystyrene, the adhesion after water immersion, and the flexibility (resistance to impact) are significantly improved.
The water-redispersible powder polymer according to the invention offers a significant advantage in terms quality and durability of the plaster materials. The green impact is significantly improved thanks to the decrease of the reparability frequency.
The water-redispersible powder polymer according to the invention allows a far better compromise between adhesion after immersion and flexibility. Application tests in Tile Adhesive
Water-redispersible powder polymer of Example 2 to 4 and of Counter Examples 1, 2, 3, 5 and 6 are formulated and tested in tile adhesive application according to EN 12004 Standard.
The following tile adhesive formulation is detailed in Table 4. Table 4 - Tile adhesive formulation
Water-redispersible powder polymer of Example 2 to 4 are compared to water-redispersible powder polymer of Counter Examples 1, 2, 3, 5 and 6. “Tile adhesive Ex2” corresponds to the tile adhesive formulation made with the water-redispersible powder polymer of Example 2. “Tile adhesive CExl” corresponds to the tile adhesive formulation made with the water- redispersible powder polymer of Counterexample 1, etc. . .
Results of tests are detailed in Table 5.
Table 5 - Test results of tile adhesive performances
TAS: Tensile Adhesion Strength (N/mm2)
TAS after heat aging: Adhere tile after 5min waiting on cementitious tile adhesive and condition: 2 weeks climatic room (23°C and 50% Humidity) and 2 weeks at 70°C oven. TAS after water immersion: 1-week climatic room (23°C and 50% Humidity) and 3 weeks in water pool.
TAS open time: Adhere tile after 30min waiting on cementitious tile adhesive and condition: 4 weeks in climatic room (23°C and 50% Humidity).
Tile adhesive formulated with the water-redispersible powder polymers according to the invention (Ex2 to 7) give significant better results compared to tile adhesive formulated with the water-redispersible powder polymers of counterexamples 1, 2, 3, 5 and 6.
The tensile adhesion strengths are improved in all conditions: initial, after heat aging, after water immersion and open time. The transverse deformation is also improved which corresponds to a better flexibility. The water-redispersible powder polymers according to the invention offer a significant advantage in terms quality and durability of the tile adhesive materials. The green impact is significantly improved thanks to the decrease of the reparability frequency.
The water-redispersible powder polymers according to the invention allows a far better compromise between adhesion after immersion and flexibility.

Claims

Claims
1. Water-redispersible powder polymer comprising:
- from 0.1 and 15% by weight of at least one propoxylated hydroxyalkylvinylether monomer unit or of a monomer unit of the monomer of formula (2)
- from 1 to 40% by weight of at least one vinylester of monocarboxylic acid monomer unit, said vinylester of monocarboxylic acid monomer unit being such that its homopolymer have a glass transition temperature Tg lower than - 15°C,
- from 30 to 95% by weight of at least one vinylacetate monomer unit, the total weight of monomer unit being 100% by weight based on the total weight of monomer unit in the polymer.
2. Water-redispersible powder polymer according to claim 1 comprising:
- from 0.1 and 15% by weight of at least one propoxylated hydroxyalkylvinylether monomer unit,
- from 1 to 40% by weight of at least one vinylester of monocarboxylic acid monomer unit, said vinylester of monocarboxylic acid monomer unit being such that its homopolymer have a glass transition temperature Tg lower than - 15°C,
- from 30 to 95% by weight of at least one vinylacetate monomer unit, the total weight of monomer unit being 100% by weight based on the total weight of monomer unit in the polymer.
3. Water-redispersible powder polymer according to any preceding claims, wherein the at least one propoxylated hydroxyalkylvinylether monomer is such that its homopolymer have a glass transition temperature Tg lower than - 25°C.
4. Water-redispersible powder polymer according to any preceding claims, wherein the at least one propoxylated hydroxyalkylvinylether monomer is such that its homopolymer have a glass transition temperature Tg lower than - 50°C.
5. Water-redispersible powder polymer according to any preceding claims, wherein the at least one propoxylated hydroxyalkylvinylether monomer is the monomer of Formula (1)
6. Water-redispersible powder polymer according to any preceding claims, wherein the at least one vinylester of monocarboxylic acid monomer unit is the vinylester of 2-ethyl hexanoic acid.
7. Water-redispersible powder polymer according to any preceding claims, wherein the polymer comprises:
- from 0.1 and 15% by weight of at least one propoxylated hydroxyalkylvinylether monomer unit,
- from 1 to 40% by weight of at least one vinylester of monocarboxylic acid monomer unit, said vinylester of monocarboxylic acid monomer unit being such that its homopolymer have a glass transition temperature Tg lower than - 15°C,
- from 30 to 95% by weight of at least one vinylacetate monomer unit,
- from 0.1 to 30% by weight of at least one vinylester of an alpha-branched monocarboxylic acid having between 7 to 17 carbon atoms.
The total weight of monomer unit being 100% by weight based on the total weight of monomer unit in the polymer.
8. Process to prepare a water-redispersible powder polymer comprising: Preparing an aqueous emulsion or suspension by polymerizing at least one propoxylated hydroxyalkylvinylether monomer and at least one vinylester of monocarboxylic acid monomer, in the presence of a free radical initiator and optionally in the presence of a surfactant and/or a stabilizer, - Drying the resulting aqueous polymer emulsion or dispersion to obtain a powder.
9. A cementitious composition comprising at least one water-redispersible powder polymer according to claim 1 to 7 or obtained according to the process of claim 8, wherein the amount of water-redispersible powder polymer in said cementitious composition is comprised between 0,1 to 30 % by weight.
10. Use of the water-redispersible powder polymer according to claim 1 to 7 or obtained according to the process of claim 8 in cementitious composition, preferably tile adhesive, water proofing membrane, thermal insulation adhesive, and topcoat.
11. Use of the water-redispersible powder polymer according to claim 1 to 7 or obtained according to the process of claim 8 to improve the adhesion after water immersion and the flexibility of cementitious composition.
PCT/EP2025/052400 2024-01-30 2025-01-30 Water-redispersible powder polymer, process to prepare them, and the use thereof in cementitious compositions Pending WO2025163070A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004031970A1 (en) * 2004-07-01 2006-01-19 Wacker Polymer Systems Gmbh & Co. Kg New plasticized polyvinyl ester-solid resin (obtained by radical initiated mass- or solution polymerization of e.g. vinyl ester and ethylenic unsaturated monomer components) useful e.g. as lacquers and adhesives and in laminates
JP4218856B2 (en) * 1999-04-14 2009-02-04 日本合成化学工業株式会社 Emulsion dispersion stabilizer and emulsion using the same, redispersible emulsion powder
JP2010235763A (en) * 2009-03-31 2010-10-21 Kuraray Co Ltd Synthetic resin emulsion powder and method for producing the same
WO2017012691A1 (en) * 2015-07-22 2017-01-26 Organik Kimya Sanayi Ve Tic. A.S. Redispersible polymer powder compositions with improved impact resistance
WO2020192735A1 (en) * 2019-03-26 2020-10-01 Sika Technology Ag High water reduction powder preparation for dry mortar

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4218856B2 (en) * 1999-04-14 2009-02-04 日本合成化学工業株式会社 Emulsion dispersion stabilizer and emulsion using the same, redispersible emulsion powder
DE102004031970A1 (en) * 2004-07-01 2006-01-19 Wacker Polymer Systems Gmbh & Co. Kg New plasticized polyvinyl ester-solid resin (obtained by radical initiated mass- or solution polymerization of e.g. vinyl ester and ethylenic unsaturated monomer components) useful e.g. as lacquers and adhesives and in laminates
JP2010235763A (en) * 2009-03-31 2010-10-21 Kuraray Co Ltd Synthetic resin emulsion powder and method for producing the same
WO2017012691A1 (en) * 2015-07-22 2017-01-26 Organik Kimya Sanayi Ve Tic. A.S. Redispersible polymer powder compositions with improved impact resistance
WO2020192735A1 (en) * 2019-03-26 2020-10-01 Sika Technology Ag High water reduction powder preparation for dry mortar

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
no. 27274-31-3

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