WO2020245838A1 - Émulsion comprenant un copolymère à base de styrène acrylique et de polysaccharide pour revêtement de surface - Google Patents

Émulsion comprenant un copolymère à base de styrène acrylique et de polysaccharide pour revêtement de surface Download PDF

Info

Publication number
WO2020245838A1
WO2020245838A1 PCT/IN2020/050486 IN2020050486W WO2020245838A1 WO 2020245838 A1 WO2020245838 A1 WO 2020245838A1 IN 2020050486 W IN2020050486 W IN 2020050486W WO 2020245838 A1 WO2020245838 A1 WO 2020245838A1
Authority
WO
WIPO (PCT)
Prior art keywords
biopolymer
emulsion
monomers
polymerization
styrene
Prior art date
Application number
PCT/IN2020/050486
Other languages
English (en)
Inventor
Parimal Jha
Rimita BHAR
Mahesh KHILARE
Rajeev Kumar GOEL
Original Assignee
Asian Paints Ltd.
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 Asian Paints Ltd. filed Critical Asian Paints Ltd.
Publication of WO2020245838A1 publication Critical patent/WO2020245838A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof

Definitions

  • the present invention provides for biopolymer based copolymer emulsion comprising biopolymer doped acrylic latex including copolymers of monomers including styrene and butyl acrylate onto non-degraded, non-gelatinized polysaccharide, including starch/dextrin at low dosage, together with the synthetic monomers in select amounts, thus providing for biopolymer based/doped copolymer, preferably biopolymer doped styrene acrylic latex and emulsions thereof suitable for concrete coating compositions/ high PVC decorative paints, and advantageously having improved opacity and reduced strength, better coverage and ease of application as concrete coatings.
  • Acrylic latex doped with biopolymers such as starch, modified starch such as dextrin and maltodextrin improves its properties and create bio-friendly, naturally degrading material, diminishing negative effect of biopolymer.
  • biopolymers such as starch
  • modified starch such as dextrin and maltodextrin
  • Use of biopolymers in polymer synthesis has been reported in various fields like, paper coating, adhesive, medical industry.
  • this starch or dextrin derived from corn, waxy corn, red milo, white milo, wheat, potato and tapioca is gelatinized with enzyme or persulfate salt before reaction in order to achieve stable viscosity and acts as protective colloid.
  • Unmodified dextrin/starch has limited application in coating industry.
  • Cationic starch has also been used in paper and board coating. Prior art reveals the deficiency of use of unmodified starch/dextrin in small quantity that is used in decorative coating formulation as a sole binder
  • bio-based nanoparticle and composite materials thereof disclosing preparation of a crosslinked nanoparticle comprising a bio-based compound and monomer, oligomer, macromer, and polymer by reactive extrusion process.
  • biopolymers are functionalized to provide double bond or free radical.
  • the prepared nanoparticle is further copolymerized with vinyl monomer forms a bio-synthetic hybrid latex particles as a whole are rendered biodegradable.
  • WO2015084372 is directed to a formaldehyde-free or formaldehyde-reduced binders useful, for example, in a fiber based composite material such as glass or other mineral fiber
  • melamine is used as
  • a preferred polyol is a nanoparticle comprising high molecular weight starch.
  • binders include mixtures of a polyolwith urea and a crosslinker.
  • a multi-component nanoparticle is madeby reacting a polyol such as starch in an extruder with an insolubilizer such as melamineor urea. The resulting particles are mixed with water, optionally with other componentssuch as an additional crosslinker, to create an aqueous binder.
  • binders to be blended with a conventional latexbinder such as polystyreneacrylate is also stated.
  • a resin is first prepared by dispersing polyol (starch), crosslinkers such as glyoxal, citric acid, melamine, urea, reactive amine dissolved in water to form a colloid forming particle, which colloidal solution is suitable for blending with conventional latex such as SA, SB, and PVA for intended application.
  • W02018010094 teaches a cosmetic pickering emulsion composition
  • a cosmetic pickering emulsion composition comprising adispersed fatty phase, and a continuous aqueous phase, and consisting of a hydrophobic gelling agent selected from ester of dextrin and fatty acid, an amphiphilic crosslinked copolymer, an anionic terpolymer, linear or branched together with hydrophobic particles chosen from hydrophobic silica and cellulose, starch, talc, silicone resin powders, hollow hemispherical silicone particles, polyamide powder, hydrophobic pigments.
  • a hydrophobic gelling agent selected from ester of dextrin and fatty acid, an amphiphilic crosslinked copolymer, an anionic terpolymer, linear or branched together with hydrophobic particles chosen from hydrophobic silica and cellulose, starch, talc, silicone resin powders, hollow hemispherical silicone particles, polyamide powder, hydrophobic pigments
  • This prior patent in effect thus discloses a cosmetic composition prepared by using an ester of dextrin and fatty acid, an amphiphilic acrylic copolymer, a terpolymer containing acrylic crosslinkers, hydrophobic silica and cellulose, starch, talc, silicone resin powders, hollow hemispherical silicone particles, polyamide powders and hydrophobic pigments.
  • the composition is a cosmetic pickering emulsion which is surfactant free and includes dextrin as an additive and not a binding agent.
  • KR2010002101A teaches organic/inorganic composite composition containing aerogel for heatinsulating coating and manufacture of molded sheet and though involves starch and other inorganic materials and a polymer present inthe composition possibly as an admixture wherein the polymer is a water absorbing polymer.
  • CN108102544A teaches environmental-friendly interior wall emulsion paint that includes the following raw materials: 55-65 parts of modified defatted soy bean paste, 35-45 parts of vinyl acetate/acrylic emulsion, 25-30 parts of starch, 20-25 parts of Portland cement, 15-20 parts of modified wood fiber, and 15-20 parts of propolis powder, 10-15 parts of zeolite, 10-15 parts of KM5 nanoparticles, 5-10 parts of modifiedexpandable graphite, 5-10 parts of extinction powder, 5-10 parts of water-soluble dextran, 20-25 parts of auxiliaries, and 75-95 parts of water.
  • the auxiliaries include the following parts of the raw materials: 4-6 parts of colorant, 2-3 parts of leveling agent, 2-3parts of water retaining agent, 1-2 parts of dispersant, 1-2 parts of defoamer, 1-2 partsof plasticizer, 0.8-1.2 parts of antioxidant and 0.6-0.8 parts of mildew inhibitor.
  • the interior wall emulsion paint enhances smoothness, good antibacterial effect, easyscrubbing, and safety and environmental protection. Teaches the employment of dextrin as an additive and not a monomer substitute to lead to a dextrin modified latex.
  • CN106221332 teaches following raw material: butadiene-styrene emulsion, siliconeacrylicemulsion, nano-titanium oxide concentrated pulp, Bu acrylate, Me methacrylate, ultra-fine wollastonite, titanium dioxide, diatomite, white cement, mung bean modifiedstarch, boron fiber, polyester fiber, hydroxypropyl Me cellulose, glycerol, sodium etc.
  • a paint formulation which involves butadiene-styrene or silicone-acrylic emulsion and a method of making latex paint by incorporation various ingredients such as monomers, emulsions, inorganic materials, surfactant, dispersing agents, catalyst, starch etc. but does not teach any dextrin modified latex.
  • CN 106147330A teaches environmentally friendly emulsion paint, comprising the following raw materials: vinyl acetate-maleic anhydride emulsion 28-40, styrene- acrylate copolymer emulsion 22-35, nano-titanium oxide concentrated pulp 18-25, Bu acrylate 12-16, Me methacrylate 8-12, ultra-fine wollastonite 7- 10, titanium dioxide 4-6, atlapulgite 5-8, white cement 6-9, cassava modified starch 10-17, boron fiber 2-4, polyester fiber 3-6, hydroxypropyl methylcellulose 4-8, glycerol 15-19, dispersing agent NC 1-2, sodium dodecylbenzenesulfonate 0.5-0.8, stearic acid 0.4-0.6, leveling agent DSX2000 0.3-0.6, wetting agent CF- 10 0.2-0.4, colorless cobalt 0.3-0.5, Pt catalyst 0.1-0.2, polyurethane thickener
  • the environmentally friendly emulsion paint of the present invention has high vol. solid content, and can increase paint film thickness, and protect wall surface effectively, and the paint film has strong adhesion, and excellent water tolerance, and alkaline resistance, belonging to low carbon product, and meeting national energy-saving and emission-reduction policy. While the ingredient starch finds mention that is only blended with the latex emulsion does not teach any dextrin modified latex.
  • CN 106147331A similarly teaches preparation method of high performance latex paint that includes mixing, dispersing, sand milling, stirring, adjustingpH, and microwave stirring.
  • the high-performance latex paint contains: butadienestyreneemulsion30-38,acrylateemulsion24-
  • CN106147320 provides a environment-friendly emulsion paint comprising the following rawmaterials: vinyl acetate-maleic anhydride emulsion, styrene-acrylic emulsion, nanotitanium oxide thickened pulp, Bu acrylate, Me methacrylate, ultra-fine wollastonite, titanium dioxide, bentonite, white cement, corn modified starch, carbon fiber, polyesterfiber, hydroxypropyl Me cellulose, glycerol, dispersing agent NC, sodiumdodecylbenzenesulfonate, stearic acid, leveling agent DSX2000, wetting agent CF-10, colorless cobalt, platinum catalyst etc. Similar to the above prior arts in involving the latex blended with corn modified starch thus does not teach any dextrin as a monomer substitute to provide for dextrin modified latex.
  • W02001029091A1 is directed tolow-amylose (preferably ⁇ 2%) starch, preferably modified or derivatized, especially from genetically modified potatoes into which an amylose producing-inhibiting gene has been introduced, is used, optionally together with common emulsifiers or auxiliary agents, as protective colloid during emulsion [co]polymerization and for stabilizing of emulsions, which are suitable for use in the paper, adhesive, paint, or textile industries, as building materials or as coatings for orally administered active substances.
  • common emulsifiers or auxiliary agents as protective colloid during emulsion [co]polymerization and for stabilizing of emulsions, which are suitable for use in the paper, adhesive, paint, or textile industries, as building materials or as coatings for orally administered active substances.
  • Amylopectin does not tend to retrograde and is obtained at low cost by co-suppression from a potato, in which amylose formation is inhibited by antisense inhibition of a GBSS gene, so that the amylose content is ⁇ 5%, especially ⁇ 2%.
  • the potato starch is degraded and used as (half) ester or ether of (in)organic acids as (hydroxy)alkyl ethers, esp. hydroxyethyl and hydroxypropyl ether, carboxyalkyl ethers, cyanoalkyl ethers, allyl ethers or (trialkylammonio)(hydroxy)alkyl ethers.
  • a-amylase (relative to the dry starch) was added, stirred and heated to boiling for enzymic degradation. After 10 min, the amylase was deactivated by addition of glacial acetic acid, the mixture cooled to 85° and 7 g of a 1% FeS0 solution and 0.7 g of 30% H 2 0 2 were added.
  • US5795928A teaches a prior process for preparing a latex system that has a tendency to flocculate because of grafting, the improvement comprises aqueous emulsion polymerization of >1 unsaturated monomer (e.g., acrylic acid, methacrylic acid, Bu acrylate, Me methacrylate, acrylic esters, styrene, vinyl ethers, vinyl, vinylidene halides, N-vinyl pyrrolidone, ethylene, C3 or greater alpha-olefins, allyl amines, allyl esters of saturated monocarboxylic acids and amides thereof, propylene, 1-butene, 1-pentene, 1-hexene, 1-decene, allyl amines, allyl acetate, allyl propionate, allyl lactate and derivatives) in the presence of a water-soluble protective colloid.
  • >1 unsaturated monomer e.g., acrylic acid, methacryl
  • the protective colloid has a wt.- av. mol. wt. ⁇ 75,000, and is selected from CM-cellulose and derivatives having a carboxyl degree of substitution lower limit of about 0.7, hydroxyethylcellulose, Et hydroxyethylcellulose, methylcellulose, Me hydroxypropylcellulose, hydroxypropylcellulose, poly(acrylic acid) and alkali metal salts thereof, ethoxylated starch derivatives, sodium and other alkali metal polyacrylates, water soluble starch glue, gelatin, water soluble alginates, casein, agar, natural and synthetic gums, partially and fully hydrolyzed poly(vinyl alcohol), polyacrylamide, poly(vinyl pyrrolidone), poly(Me vinyl ether-maleic anhydride), gelatin, and casein.
  • the latex has improved mechanical and shear stability. This latex provides coating manufacturers the flexibility of either eliminating surfactants altogether from coating or to use small amounts thereof.
  • cellulose ether acts as protective colloid and can replace surfactants fully or partially, starch is used as an additive and in a derivatized form.
  • EP343833A2 emulsion comprises particles (0.2-3.0 pm) of 0.5-90 parts 1- 50: 50-99 unsaturated carboxylic acid-vinyl compound copolymer (A) and 99.5- 10 parts another vinyl compound copolymer (B) (0.05-0.5 pm), wherein copolymer B is prepared in the presence of neutralized copolymer A seed particles.
  • This prior art uses phosphated starch binder and not dextrin as a raw material during emulsion synthesis.
  • biopolymer based copolymer including starch/ dextrin, which biopolymer would act as a secondary binding agent that would provide for starch/ dextrin modified latex especially suitable for paints including high PVC (pigment volume concentration) emulsion paint.
  • biopolymer based copolymer preferably of select synthetic monomers of styrene and butyl acrylate onto starch/dextrin, which starch/dextrin being free of any degradation or gelatinization, derivatization, thinning taken at low dosage would be compatible with said select synthetic monomers andwould enable biopolymer/dextrin based/doped copolymer suitable for concrete coating compositions.
  • biopolymer based copolymer and emulsion thereof that would be suitable for use in high PVC decorative paint to have a cost-effective alternate to pure styrene acrylic backbone.
  • biopolymer based copolymer emulsion comprising biopolymer doped acrylic latex including copolymer of monomers including styrene and butyl acrylate onto non- degraded, non-gelatinized polysaccharide that is a stable flowable polymer dispersion having solid content in the range of 30-50% by wt. free of any phase separation, viscosity increase and gelation upon storage.
  • said biopolymer based copolymer emulsion is provided wherein said polysaccharide as a secondary binding agent is a non-ionic, non-degraded, non- gelatinized starch, dextrin, maltodextrin, preferably non-degraded, non- gelatinized tapioca starch.
  • said biopolymer based copolymer emulsion comprises acrylic polymer with polysaccharide incorporation in the levels of 3% to 10% in said acrylic polymer that is a low molecular wt. polysaccharide having mol. wt. in the range of 100-5000g/mol.
  • said biopolymer based copolymer emulsion wherein said emulsion comprising acrylic polymer includes a monomer ratio of styrene: butyl acrylate in the ratio range of above 50: 50 to below 70:30, preferably 55:45 having Tg in the range of 5-20 °C.
  • said biopolymer based copolymer emulsion comprises monomers including methyl methacrylate, ethyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, styrene, acrylic acid, methacrylic acid, hydroxyl ethyl methacrylate, hydroxyl propyl methacrylate free of monomers including isobornyl methacrylate, isobornyl acrylate, C18 PEG methacrylate, amino methacrylates, benzyl methacrylate, VAM monomer, present together with surfactants, and non- polymerizable crosslinkers.
  • monomers including methyl methacrylate, ethyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, styrene, acrylic acid, methacrylic acid, hydroxyl ethyl methacrylate, hydroxyl propyl methacryl
  • said surfactant/emulsifiers are selected from anionics including Polyoxyethylene alkyl ether sulfate, Alkyl sulfate, Alkyl benzene sulfonate; nonionics including polyoxyethylene alkyl ether, Polyoxyalkylene fatty alcohol, Sorbitan fatty acid esters stabilizing the emulsion for at least 1 year in viscosity range of 50-100g.
  • said biopolymer based copolymer emulsion wherein said biopolymer doped acrylic latex comprises fine particle aggregates including said copolymer of styrene, butyl acrylate including unsaturated carboxylic acid, onto polysaccharides, as biopolymer that exist homogeneously in each aggregate particle having diameter in the range of 100 to 200 nm for sufficient desired opacity and strength and adhesion in terms of washability and scrub resistance, adapted for anyone of high PVC emulsion paint with reduced inorganic pigment, binder for concrete coating, having the characteristics improved opacity and reduced strength, better coverage and ease of application in concrete coatings based on the involvement of said low molecular weight nonionic polysaccharide/sta rch.
  • a process for the synthesis of biopolymer based copolymer emulsion comprising sequential seeded multi stage free- radical aqueous polymerization of monomers including styrene and butyl acrylate as essential monomers in the presence of non-degraded, non-gelatinized polysaccharide and obtaining therefrom biopolymer doped acrylic latex including copolymer of styrene and butyl acrylate onto non-degraded, non-gelatinized polysaccharide as a stable flowable polymer dispersion having solid content in the range of 30-50% by wt. free of any phase separation, viscosity increase and gelation upon storage.
  • said process comprises the steps of
  • aqueous polymer dispersion comprising monomers including styrene and butyl acrylate as essential monomers taken in the ratio range of styrene: butyl acrylate in the ratio range of above 50: 50 to below 70 :30, preferably 55:45, and polymerizing said monomers by free radical aqueous polymerization in the presence of non-degraded, non-gelatinized polysaccharide preferably tapioca dextrin at emulsion polymerization temperature of 65 to 95°C, preferably from 75 to 85°C.
  • said monomer as 100 parts by weight monomer or mixed monomer comprises 0 to 70% by weight of vinyl aromatic monomer, 0 to 50 % by weight of an ethylenically unsaturated monomer together with unsaturated carboxylic acid selected from unsaturated monobasic acids such as methacrylic acid and acrylic acid preferably acrylic acid in an amount of 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight, per 100 parts by weight of total monomers making up said copolymer, which said monomers are polymerized in a sequential seeded multistage semi-continuous process in presence of 3 to 10 % by weight dextrins free of any derivatization, gelantization and thinning.
  • unsaturated carboxylic acid selected from unsaturated monobasic acids such as methacrylic acid and acrylic acid preferably acrylic acid in an amount of 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight, per 100 parts by weight of total monomers making up said copolymer, which said monomers are polymerized in
  • said process comprises the steps of
  • emulsified monomer mixture and catalyst are fed into the polymerization reactor over a period of 45 to 75 minutes while maintaining the polymerization temperature.
  • polymerization initiators include persulfates of potassium persulfate, sodium persulfate and ammonium persulfate; organic peroxides such benzoyl hydroperoxide, redox initiators by combining them with a reducing agent such as sodium formaldehyde sulphoxalate; and wherein said surface active agent is includes anionic surface active agent, a nonionic surface active agent or a combination thereof includinganionic surface active agent comprising sodium alkylsulfate, sodium dialkylsulfosuccinate, nonionic surface active agents including polyoxyethylene alkyl ether and polyoxyethylenealkylphenol ether in amounts of 0.5 to 5 parts by weight per 100 parts by weight of all monomers.
  • said process providing for biopolymer doped acrylic latex comprises fine particle aggregates of biopolymer doped acrylic latex onto polysaccharides obtained of a mixture including styrene, butyl acrylate, unsaturated carboxylic acid and said biopolymer wherein said biopolymer exist homogeneously in each aggregate particle having diameter in the range of 100 to 200 nm for sufficient desired opacity and strength and adhesion in terms of washability and scrub resistance.
  • Fig. 1 illustrates at lower magnification (a) Standard batch (Cryo SEM); (b) dextrin post blended in latex (Cryo SEM);
  • Fig. 2 illustrates at higher magnification (a) Standard batch (Cryo SEM); (b) dextrin post blended in latex (Cryo SEM).
  • the present invention provides for a biopolymer based copolymer emulsion comprising biopolymer doped acrylic latex including copolymer of monomers including styrene and butyl acrylate on to non-degraded, non-gelatinized polysaccharide starch including starch/dextrin at low dosage together with the synthetic monomers in select amounts, thus providing for biopolymer based copolymer, preferably biopolymer doped acrylic latex and emulsions thereof suitable for concrete coating compositions.
  • the starch/dextrin was locally bought as a packaged product and employed advantageously without any degradation or gelatinization or derivatization or thinning.
  • the emulsion is especially useful for a high PVC (pigment volume concentration) emulsion paint.
  • presence of biopolymers at 3% to 10% in acrylic polymer was made using sequential polymerization process.
  • Said biopolymer based copolymer emulsion of the present invention comprising copolymer of monomers including styrene and butyl acrylate onto non-degraded, non-gelatinized polysaccharide was found to be surprisingly stable as a flowable polymer dispersion having solid content in the range as high as 30-50% by wt. free of any phase separation, viscosity increase and gelation upon storage. Solid content beyond this range could not be stabilized and below this range would not be suitable for concrete coating compositions.
  • biopolymer based copolymer dispersions preferably biopolymer doped acrylic latex and dispersions thereof comprising monomers, surfactants, initiator and non- polymerizablecrosslinkers adapted as a binder for concrete coating, said copolymer dispersion being surfactant stabilized.
  • Starch/dextrin based thermoplastic polymer of the present invention is made using free radical emulsion polymerization to find application in water based decorative paint for concrete surface.
  • According to another aspect in the process of the present invention is based on sequential free-radical polymerization wherein synthetic monomers belonging to the class of water insoluble hydrophobic monomer including styrene is used free of any VAM monomer, having no affinity for dextrin, and wherein styrene acrylic copolymer emulsion synthesized in presence of dextrin in the monomer mixture results in intimately dextrin modified latex with substantially reduced water leachability of dextrin.
  • a copolymer composition made using sequential polymerization that greatly enhance the compatibility among the components (starch and polymers) and in turn forms a network structure by combining polymers.
  • the resulting low molecular weight nonionic starch /Dextrin preferably Tapioca starch based styrene acrylic thermoplastic polymer employed to make high PVC emulsion paint of the present invention display improved opacity and reducing strength, better coverage and ease of application in concrete.
  • the aqueous polymer dispersion according to the present invention is preferably prepared by polymerizing the monomers by the free radical aqueous polymerization process in the presence of tapioca dextrin.
  • the emulsion polymerization temperature is generally from 65 to 95°C, preferably from 75 to 85°C.
  • the polymerization medium is water.
  • 100 parts by weight monomer or mixed monomer consisting of 0 to 70% by weight of vinyl aromatic monomer, 0 to 50 % by weight of an ethylenically unsaturated monomer are polymerized in a multistage semicontinuous process in presence of 0 to 10 % by weight dextrins, and in which the content of dextrin having low molecular weight preferably Tapioca starch being free of any derivatization, gelantisation and thinning.
  • the entire amount of the aqueous dextrin solution is charged into the polymerization reactor followed by surface active agents. The whole composition is intensely and homogeneously mixed before the addition of monomer mixture.
  • the emulsion polymerization can be carried out either as a batch process or in the form of a feed process. Preference is given to the feed process, in which part of the polymerization batch is heated to the polymerization temperature and partially polymerized, and the remainder of the polymerization batch is subsequently fed to the polymerization zone continuously, usually via a separate feed streams, while maintaining the polymerizationtemperature.
  • the initially introduced emulsified monomer mixture contains small amounts of emulsifiers, in order to reduce the surface tension of the dispersion medium and thus to simplify stirring in. The monomers are therefore frequently fed to the polymerization zone after pre-emulsification with these assistant emulsifiers.
  • Preparation of a dextrin polymer dispersion in accordance with the invention may be accomplished by charging water, tapioca dextrin and surfactant into a reaction vessel.
  • the initial solid content is preferably from about 15 to 20% by weight.
  • polymerization is accomplished by a dual feed process wherein emulsified monomer mixture and catalyst are fed in the reaction vessel over a period Of 45 to 75 minutes. Additionally, a second stage of polymerization is carried out by adding additional emulsified monomers and catalyst to the dextrin polymer dispersion to about 150 to 180 minutes.
  • the unsaturated carboxylic acid used in the present invention is selected from unsaturated monobasic acids such as methacrylic acid and acrylic acid. Acrylic acids are preferred.
  • the unsaturated carboxylic acid is used in an amount of 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight, per 100 parts by weight of total monomers used in making copolymer. If the amount is less than 0.5 parts by weight the kettle hygiene and coagulum formulation is very high. If the amount is greater than 5 parts by weight the resulting polymer particle will be poor in water resistance and alkali resistance.
  • the surface active agent is used in the present invention can be an anionic surface active agent, a nonionic surface active agent or a combination thereof.
  • Useful anionic surface active agents include, for example, sodium alkylsulfate and sodium dialkylsulfosuccinate.
  • Useful nonionic surface active agents include, for example, polyoxyethylene alkyl ether and polyoxyethyleneaikylphenol ether.
  • the amount of surface active agent used is critical in stabilizing polymer particle in aqueous medium. It is usually used in an amount of about 0.5 to 5 parts by weight per 100 parts by weight of all monomers.
  • polymerization initiator there can be used any of various polymerization initiators that are commonly used in emulsion polymerization.
  • Useful polymerization initiators include, for example, persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate; organic peroxides such benzoyl hydroperoxide. If desired, they can also be used as redox initiators by combining them with a reducing agent such as sodium formaldehyde sulphoxalate.
  • the polymer thus obtained comprises fine particle aggregates formed from a mixture of a copolymer of styrene and butyl acrylate composed of an unsaturated carboxylic acid and a biopolymer exist homogeneously in each aggregate particle, the aggregate particles formed from polymer component have a diameter of 100 to 200 nm. If the diameter of the particles formed is smaller than 100 nm, the resulting emulsion will fail to provide sufficient desired opacity and reducing strength, while if it is larger than 200 nm, the resulting emulsion will be poor in opacity, reducing strength and adhesion in terms of washability and scrub resistance.
  • the particle diameter ca n be controlled by varying the amount of first and second stage copolymer composition, the amount of surface active agent used in the reactor cha rge a nd the amount of initiator used for polymerization .
  • a process could be achieved for the production of dextrin polymer dispersion which ca n be ca rried out in a simple manner and which results in stable, flowable, aq ueous polymer dispersion having low viscosity and a solid content of at least 30% by weight an d most preferably above 40% by weig ht.
  • the dextrin polymer dispersion composition thus described does not have the problems of phase sepa ration, undue increase in viscosity upon storage and gelation .
  • a surfactant stabilized styrene acrylic polymer emulsion involving sta rch in select a mounts, free of any derivatization, gelantisation and thinning, could be employed as asecondary binding agent that allows styrene and butyl acrylate being two hydrophobic monomers to polymerize without any difficulty in the presence of a macromolecule like sta rch .
  • This differentiation is as against a dextrin post blended styrene acrylic latex or paint of equivalent composition Fig. la, lb.
  • the standard batch shows presence foreign (dextrin) particles as filler in between polymer matrix. But in post blended latex, no such filler was visible. Also the alkali resistance of post blended latex is poor as compared to standard batch when dextrin was used during reaction.
  • Said biopolymer doped acrylic latex of the present invention comprises fine particle aggregates including said copolymer of styrene, butyl acrylate including unsaturated carboxylic acid, onto polysaccharides, as biopolymer that exist homogeneously in each aggregate particle having diameter in the range of 100 to 200 nm for sufficient desired opacity and strength and adhesion in terms of washability and scrub resistance.
  • a synthetic monomer ratio of 47: 53 (BA: STY) in the emulsion composition together with starch/dextrin in select amounts displaying optimum MFFT (minimum film formation temperature) of the polymer film. In isolation of these either the film becomes tacky or brittle.
  • the select monomer ratio helps in maintaining optimum hardness during film formation.
  • the emulsion in being used for high PVC coating application, it is important to exhibit a balance between softness and hardness of the film. It was found that whenever the ratio is changed, the glass transition temperature (Tg) either increases or decreases. An increased Tg results in hard film and hence poor adhesion to substrate and also cracks in film. When Tg is decreased, a softer film is formed that leads to poor dirt repellency in exterior application.
  • Styrene and butyl acrylates are the two most hydrophobic monomers that are difficult to polymerize in presence of oligomers like starch/dextrin in their non-degraded, non-derivatized, non- gelantinized and non-thinned form, yet which polymerization however, could be achieved based on select sequential free-radical polymerization based process by employing styrene and butyl acrylate monomers in select ratios together with other monomers.
  • non-compatible monomers can be incorporated in the biopolymer based copolymer emulsion of the present invention to be able to incorporate non-gelatinized, non-degraded starch only when the desired styrene and butyl acrylate monomer ratio is met.
  • the dextrin-based copolymer composition is responsible for improved opacity and reducing strength, better coverage and ease of application in concrete coatings.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une émulsion de copolymère à base de biopolymère comprenant un latex acrylique dopé à un biopolymère comprenant des copolymères de monomères comprenant du styrène et de l'acrylate de butyle sur un polysaccharide non dégradé, non gélatinisé, comprenant de l'amidon/de la dextrine à faible dose, conjointement avec les monomères synthétiques dans des quantités sélectionnées, ce qui permet d'obtenir un copolymère dopé à un/à base d'un biopolymère, de préférence un latex acrylique de styrène dopé à un biopolymère et des émulsions associées appropriés pour des compositions de revêtement de béton/des peintures décoratives à haute teneur en PVC, et présentant avantageusement une opacité et une résistance réduite, une meilleure couverture et une facilité d'application en tant que revêtements de béton.
PCT/IN2020/050486 2019-06-03 2020-06-02 Émulsion comprenant un copolymère à base de styrène acrylique et de polysaccharide pour revêtement de surface WO2020245838A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN201921021879 2019-06-03
IN201921021879 2019-06-03

Publications (1)

Publication Number Publication Date
WO2020245838A1 true WO2020245838A1 (fr) 2020-12-10

Family

ID=73651947

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2020/050486 WO2020245838A1 (fr) 2019-06-03 2020-06-02 Émulsion comprenant un copolymère à base de styrène acrylique et de polysaccharide pour revêtement de surface

Country Status (1)

Country Link
WO (1) WO2020245838A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024110248A1 (fr) * 2022-11-23 2024-05-30 Basf Se Dispersions polymères aqueuses appropriées enn tant qu'opacifiants dans des formulations liquides, procédé de production et leur utilisation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KUMAR M. N. SATHEESH, SIDDARAMAIAH: "Studies on Cornstarch-filled Poly(styrene-co-butyl acrylate) Latex-reinforced Polyester Nonwoven Fabric Composites", JOURNAL OF REINFORCED PLASTICS AND COMPOSITES, vol. 24, no. 18, 1 December 2005 (2005-12-01), pages 1985 - 1994, XP055767183, DOI: 10.1177/0731684405054379 *
KUMAR M. N. SATHEESH, SIDDARAMAIAH: "Studies on Poly(Styrene-co-Butyl Acrylate) Latex-reinforced Polyester Nonwoven Fabric Thermoplastic Composites", JOURNAL OF REINFORCED PLASTICS AND COMPOSITES, vol. 24, no. 13, 1 September 2005 (2005-09-01), pages 1413 - 1423, XP055767177, DOI: 10.1177/0731684405049881 *
SATHEESH KUMAR M. N., YAAKOB Z., SIDDARAMAIAH: "Poly(styrene-co-butyl acrylate) Latex-Reinforced Polyester Nonwoven Fabric Composites: Thermal and Morphological Studies", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 114, no. 1, 8 June 2009 (2009-06-08), pages 467 - 474, XP055767182, DOI: 10.1002/app.30518 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024110248A1 (fr) * 2022-11-23 2024-05-30 Basf Se Dispersions polymères aqueuses appropriées enn tant qu'opacifiants dans des formulations liquides, procédé de production et leur utilisation

Similar Documents

Publication Publication Date Title
TW523539B (en) Pressure sensitive adhesives composition
EP0031964B1 (fr) Procédé en séquence de polymérisation en émulsion pour l'obtention de latex à particules structurées
CA1184688A (fr) Copolymere greffe liquide et stable de l'amidon
JP3667341B2 (ja) 乳化重合分散液中のセルロースエーテル類
EP0606431B1 (fr) Liants pour revetement de carton comprenant de l'amidon cationique et de l'acetate de vinyle
US3513120A (en) Production of dispersions of polymers of styrene and esters of acrylic or methacrylic acid
CN101313028B (zh) 可再乳化的树脂粉末、含水乳液和包含这些物质的粘合剂组合物
AU751224B2 (en) Environmentally friendly aqueous architectural coating compositions
US6123996A (en) Composition, use of a cellulose ether as thickening agent and production of a coated cellulose-based two-dimensional product
WO2001030905A1 (fr) Composition polymere a base d'eau comportant un biopolymere et une resine polymere
CA2385285C (fr) Procede de polymerisation en emulsion
US4322322A (en) Method for preparing a water-containing vinyl acetate polymer dispersion, dispersion thus prepared and protective colloid used thereby
US5563187A (en) Grafted polymer composition
WO2020245838A1 (fr) Émulsion comprenant un copolymère à base de styrène acrylique et de polysaccharide pour revêtement de surface
CN108699775B (zh) 用于改性有色涂料的流变性的组合物、其用途和有色涂料
MXPA02000895A (es) Color de revestimiento.
US5635566A (en) Process for preparing dispersions stabilized with protective colloid
CA2500126A1 (fr) Solution et dispersion polymeres et procede de preparation correspondant
US7358297B2 (en) Preparation of multimodal polymer dispersions using polymeric stabilizer, and use thereof
KR102496601B1 (ko) 제지용 표면 사이즈제
CA2334796A1 (fr) Nouveaux colloides protecteurs de latex a formation de film amelioree a basses temperatures
JPH0521935B2 (fr)
WO2023126576A1 (fr) Procédé de préparation d'une émulsion à base de polysaccharide pour des applications de liaison et de revêtement
JP2001040016A (ja) 合成樹脂エマルジョンおよびその粉末
JPH06313090A (ja) 樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20819197

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20819197

Country of ref document: EP

Kind code of ref document: A1