WO2005014661A2 - Utilisation d'oxydes de polyalkylene pour eviter l'epaississement de dispersions polymeres stabilisees avec des colloides protecteurs - Google Patents

Utilisation d'oxydes de polyalkylene pour eviter l'epaississement de dispersions polymeres stabilisees avec des colloides protecteurs Download PDF

Info

Publication number
WO2005014661A2
WO2005014661A2 PCT/EP2004/007488 EP2004007488W WO2005014661A2 WO 2005014661 A2 WO2005014661 A2 WO 2005014661A2 EP 2004007488 W EP2004007488 W EP 2004007488W WO 2005014661 A2 WO2005014661 A2 WO 2005014661A2
Authority
WO
WIPO (PCT)
Prior art keywords
vinyl
group
use according
polyalkylene oxides
protective colloids
Prior art date
Application number
PCT/EP2004/007488
Other languages
German (de)
English (en)
Other versions
WO2005014661A3 (fr
Inventor
Kurt Stark
Christian HÖGL
Original Assignee
Wacker Polymer Systems Gmbh & Co. Kg
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 Wacker Polymer Systems Gmbh & Co. Kg filed Critical Wacker Polymer Systems Gmbh & Co. Kg
Publication of WO2005014661A2 publication Critical patent/WO2005014661A2/fr
Publication of WO2005014661A3 publication Critical patent/WO2005014661A3/fr

Links

Classifications

    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents

Definitions

  • the invention relates to the use of polyalkylene oxides to avoid the thickening of polymer dispersions stabilized with protective colloids.
  • Protective colloid-stabilized polymers are used primarily in the form of their aqueous dispersions or water-redispersible polymer powders in a variety of applications, for example as coating agents or adhesives for a wide variety of substrates, such as cement tiles.
  • Polyvinyl alcohols are generally used as protective colloids. The use of polyvinyl alcohol is desirable because, in comparison to systems that are stabilized by low molecular weight compounds (emulsifiers), it itself contributes to strength.
  • a disadvantage of using protective colloids to stabilize polymer dispersions is the increase in the viscosity of the polymer dispersion with increasing service life.
  • the object was therefore to modify aqueous polymer dispersions stabilized with protective colloids in such a way that their viscosity remains virtually unchanged even after a long service life.
  • polyalkylene oxides are polymers which contain ethylene oxide (EO) and propylene oxide (PO) blocks, that is to say block copolymers which do not contain the alkylene oxide units in a statistical distribution, and thus show aggregation behavior, as is also the case occurs with emulsifiers.
  • EP-A 1114833 describes the production of high solids, aqueous vinyl acetate-ethylene copolymer dispersions by means of polymerization in the presence of a mixture of polyvinyl alcohol and polyethylene glycol.
  • EP-A 305585 discloses the production of vinyl acetate homo- and copoly dispersions in the presence of polyvinyl alcohol and compounds having an alcoholic OH group.
  • the invention relates to the use of polyalkylene oxides to avoid the thickening of aqueous polymer dispersions stabilized with protective colloids, characterized in that in the preparation of aqueous polymer dispersions by means of radical-initiated polymerization of one or more ethylenically unsaturated monomers in an aqueous medium in the presence of one or more protective colloids, one or more polyalkylene oxides, which in the case of alkylene oxide copolymers contain the alkylene oxide units in statistical distribution, are added before or during the polymerization.
  • Suitable polyalkylene oxides include those with identical or different structural units from the group
  • End groups R '' are to be understood as those which are located at the ends of the polyalkylene oxide chain: R "[- (CH 2 ) n -0] m -R" or R "[-CH 2 -CHR-0] m -” or R "[-CH2--CHOR' 0] m -R” preferably, R is a Ci to C 4 - alkyl group;. preferably R 'is H, Ci to C4 alkyl; preferably R "' is a Residue from the group comprising H, OH group, alkyl group and O-alkyl group, where the alkyl or alkoxy radical can be unbranched or branched and particularly preferably contains a C ⁇ ⁇ to C 4 radical.
  • Most preferred are polyethylene glycol (PEO), polypropylene glycol (PPO) and copolymers which contain ethylene oxide and propylene oxide units in a statistically distributed manner.
  • the number average molecular weight Mn of the polyalkylene oxides is 100 to 100,000 g / mol, preferably 1000 to 50,000 g / mol. In general, 0.1 to 10% by weight, preferably 0.5 to 5% by weight, of polyalkylene glycol, based in each case on the total weight of the monomers, is used.
  • Suitable ethylenically unsaturated monomers are those from the group comprising vinyl esters of unbranched or branched alkyl carboxylic acids with 1 to 15 C atoms, methacrylic acid esters and acrylic acid esters of alcohols with 1 to 15 C atoms, vinyl aromatics, olefins, dienes and vinyl halides.
  • Suitable vinyl esters are vinyl esters of unbranched or branched carboxylic acids having 1 to 15 carbon atoms.
  • Preferred vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate, vinyl pivalate and vinyl esters of ⁇ -branched monocarboxylic acids with 5 to 13 carbon atoms, for example VeoVa9 R or VeoVal0 R (trade name of Shell).
  • Most preferred is vinyl acetate a combination of vinyl acetate with ⁇ -branched monocarboxylic acids having 5 to 11 carbon atoms, such as VeoVa9 R and VeoValO R, is preferred.
  • Suitable monomers from the group of the esters of acrylic acid or methacrylic acid are esters of unbranched or branched alcohols having 1 to 15 carbon atoms.
  • Preferred methacrylic acid esters or acrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-, iso- and t-butyl acrylate, n-, iso- and t-butyl ethacrylate, 2-ethylhexyl acrylate, Norbornyl acrylate.
  • Methyl acrylate, methyl methacrylate, n-, iso- and t-butyl acrylate, 2-ethylhexyl acrylate and norbornyl acrylate are particularly preferred.
  • Suitable dienes are 1,3-butadiene and isoprene.
  • Examples of copolymerizable olefins are ethene and propene.
  • Styrene and vinyl toluene can be copolymerized as vinyl aromatics. From the group of vinyl halides, vinyl chloride, vinylidene chloride or vinyl fluoride, preferably vinyl chloride, are usually used.
  • auxiliary monomers can also be copolymerized.
  • auxiliary monomers are ethylenically unsaturated mono- and dicarboxylic acids or their salts, preferably crotonic acid, acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated carboxylic acid amides and nitriles, preferably acrylamide and acrylonitrile; Mono- and diesters of fumaric acid and maleic acid such as the diethyl and diisopropyl esters and maleic anhydride, ethylenically unsaturated sulfonic acids or their salts, preferably vinylsulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid.
  • Cationic monomers such as are also suitable as auxiliary monomers Diallyldimethylammonium chloride (DADMAC), 3-trimethylammonium propyl (meth) acrylamide chloride (MAPTAC) and 2-trimethylammonium ethyl (meth) acrylate chloride.
  • DMDMAC Diallyldimethylammonium chloride
  • MATAC 3-trimethylammonium propyl (meth) acrylamide chloride
  • 2-trimethylammonium ethyl (meth) acrylate chloride are also suitable as vinyl ethers, vinyl ketones, other vinyl aromatic compounds, which may also have heteroatoms.
  • Suitable auxiliary monomers are also polymerizable silanes or mercaptosilanes.
  • Preferred are ⁇ -acrylic or ⁇ -methacryloxypropyltri (alkoxy) silanes, ⁇ -methacryloxymethyltri (alkoxy) silanes, ⁇ -methacryloxypropylmethyldi (alkoxy) silanes, vinylalkyldi (alkoxy) silanes and vinyltri (alkoxy) silanes, where, for example, methoxy, ethoxy, methoxyethylene, ethoxyethylene, methoxypropylene glycol ether or ethoxypropylene glycol ether radicals can be used as alkoxy groups.
  • Examples of these are vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-propoxysilane, vinyltriisopropoxysilane, vinyltris (1-methoxy) isopropoxysilane, vinyltributoxysilane, vinyltriacetoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxacryloxysilane, 3-methacryloxacryloxysilane, 3-methacryloxacryloxysilane, 3-methacryloxacryloxysilane, 3-methacryloxacryloxysilane, 3-methacryloxypropoxysilane, methoxyethoxy) silane, vinyltrichorsilane, vinylmethyldichlorosilane, vinyltris- (2-methoxyethoxy) silane, trisacetoxyvinylsilane, 3- (triethoxysilyl) propylsuccinic acid anhydride silane. 3-Mercaptopropyltrieth-oxys
  • acrylates in particular epoxy-functional ones such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, or hydroxyalkyl functional such as hydroxyethyl (meth) acrylate, or substituted or unsubstituted aminoalkyl (meth) acrylates, or cyclic monomers, such as N-vinylpyrrolidone.
  • epoxy-functional ones such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, or hydroxyalkyl functional such as hydroxyethyl (meth) acrylate, or substituted or unsubstituted aminoalkyl (meth) acrylates, or cyclic monomers, such as N-vinylpyrrolidone.
  • polymerizable silicone macros with at least one unsaturated group such as linear or branched polydialkylsiloxanes with Ci to C ⁇ alkyl, and with a chain length of 10 to 1000, preferably 50 to 500 SiO (C n H 2n + ⁇ ) 2 _ Units containing one or two ter inals, or one or more chain-linked, polymerizable groups (functional groups).
  • examples include polydialkylsiloxanes with one or two vinyl, acryloxyalkyl, methacryloxyalkyl or mercaptoalkyl groups, where the alkyl groups can be the same or different and contain 1 to 6 carbon atoms.
  • pre-crosslinking comonomers such as polyethylenically unsaturated comonomers, for example divinyl adipate, divinylbenzene, diallyl aleate, allyl methacrylate, butanediol diacrylate or triallyl cyanurate, or post-crosslinking comonomers, for example acrylic idoglycolic acid (AGA), methyl acrylate (AMA), methyl acrylate (AMA), methyl acrylate -Methylolacrylamide (NMA), N-methylol methacrylamide, N-methyl olallyl carbamate, alkyl ethers such as the isobutoxy ether or ester of N-methylol acrylamide, N-methylol methacrylamide and N-methylolallyl carbamate.
  • pre-crosslinking comonomers such as polyethylenically unsaturated comonomers, for example divinyl adipate, divinylbenz
  • copolymer compositions mentioned below which may also contain the auxiliary monomers mentioned: Polymers of vinyl acetate;
  • Vinyl ester copolymers of vinyl acetate with other vinyl esters such as vinyl laurate, vinyl pivalate, vinyl 2-ethylhexanoic acid ester, vinyl ester of an alpha-branched carboxylic acid, especially vinyl versatic acid (VeoVa9 R , VeoValO R );
  • Vinyl ester-ethylene copolymers such as vinyl acetate-ethylene copolymers, which may also contain other vinyl esters, such as vinyl laurate, vinyl pivalate, vinyl 2-ethylhexanoic acid ester, vinyl ester of an alpha-branched carboxylic acid, in particular vinyl versatic acid (VeoVa9 R , VeoValO R ), or fumaric acid or contain maleic acid diesters;
  • vinyl esters such as vinyl laurate, vinyl pivalate, vinyl 2-ethylhexanoic acid ester, vinyl ester of an alpha-branched carboxylic acid, in particular vinyl versatic acid (VeoVa9 R , VeoValO R ), or fumaric acid or contain maleic acid diesters;
  • Vinyl ester-ethylene copolymers such as vinyl acetate-ethylene copolymers, which optionally also contain other vinyl esters such as vinyl laurate, vinyl pivalate, vinyl 2-ethylhexanoic acid ester, vinyl ester of an alpha-branched carboxylic acid, in particular
  • VeoVa9 R Versatic acid vinyl ester (VeoVa9 R , VeoValO ⁇ ) and contain at least one polymerizable silicone macromer;
  • Vinyl ester-ethylene-vinyl chloride copolymers vinyl acetate and / or vinyl propionate and / or one or more copolymerizable vinyl esters such as vinyl laurate, vinyl pivalate, vinyl-2-ethylhexanoic acid ester, vinyl ester of an alpha-branched carboxylic acid, in particular vinyl vinyl versatate (VeoVa0 R , R ) are included;
  • Styrene-1, 3-butadiene copolymers and styrene (meth) acrylic ester copolymers such as styrene-butyl acrylate, styrene-methyl methacrylate-butyl acrylate or styrene-2-ethylhexyl acrylate, it being possible to use n-, iso-, tert-burylacrylate as the butyl acrylate.
  • vinyl ester-ethylene copolymers such as vinyl acetate-ethylene copolymers, and copolymers of vinyl acetate and ethylene and vinyl esters of an ⁇ -branched
  • Carboxylic acid with 9 or 10 carbon atoms (VeoVa9 R , VeoValO R ), and in particular copolymers of vinyl acetate, ethylene, vinyl ester of an ⁇ -branched carboxylic acid with 9 or 10 C atoms (VeoVa9 R , VeoVal0 R ) with copolymerizable silicone macromers; with an ethylene content of preferably 2 to 30 wt .-%, which may optionally also contain auxiliary monomer in the amounts specified.
  • the ethylenically unsaturated monomers are preferably selected so that aqueous copolymer dispersions and aqueous redispersions of the copolymer powders result, with a glass transition temperature Tg of from -50 ° C. to +50 ° C.
  • the glass transition temperature Tg of the polymers can be determined in a known manner by means of differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • Tg n the glass transition temperature in Kelvin of the homopolymer of the monomer n. Tg values for homopolymers are listed in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).
  • the dispersions are prepared by means of radical polymerization in an aqueous medium, preferably emulsion polymerization. provides.
  • the polymerization is usually carried out in a temperature range from 20 ° C. to 100 ° C., in particular between 40 ° C. and 80 ° C.
  • the initiation is carried out by means of the customary free radical formers, which are preferably used in amounts of 0.01 to 5.0% by weight, based on the total weight of the monomers.
  • Inorganic peroxides such as ammonium, sodium, potassium peroxodisulfate or hydrogen peroxide are preferably used as initiators, either alone or in combination with reducing agents such as sodium sulfite, sodium hydrogen sulfite, sodium formaldehyde sulfoxylate or ascorbic acid. It is also possible to use water-soluble organic peroxides, for example t-butyl hydroperoxide, cumene hydroperoxide, usually in combination with a reducing agent, or else water-soluble azo compounds.
  • reducing agents such as sodium sulfite, sodium hydrogen sulfite, sodium formaldehyde sulfoxylate or ascorbic acid.
  • water-soluble organic peroxides for example t-butyl hydroperoxide, cumene hydroperoxide, usually in combination with a reducing agent, or else water-soluble azo compounds.
  • copolymerization with gaseous monomers such as ethylene and vinyl chloride is carried out under pressure, generally between 1 and 100 bar a bs.-
  • regulators can be used during the polymerization. If regulators are used, they are usually used in amounts of between 0.01 and 5.0% by weight, based on the monomers to be polymerized, and metered in separately or premixed with reaction components. Examples of such substances are n-dodecyl mercaptan, tert. -Dodecyl mercaptan, mercaptopropionic acid, methyl mercaptopropionate, isopropanol and acetaldehyde.
  • Suitable protective colloids are polyvinyl alcohols; Polyvinyl acetals; polyvinylpyrrolidones; Polysaccharides in water-soluble form such as starches (amylose and amylopectin), celluloses and their carboxymethyl, methyl, hydroxyethyl, hydroxypropyl derivatives derivatives; Proteins such as casein or caseinate, soy protein, gelatin; lignin; synthetic polymers such as poly (meth) acrylic acid, copolymers of (meth) acrylates with carboxyl-functional comonomer units, poly (meth) acrylamide, polyvinylsulfonic acids and their water-soluble copolymers; Melamine formaldehyde sulfonates, naphthalene formaldehyde sulfonates, styrene maleic acid and vinyl ether maleic acid copolymers.
  • Partially saponified, hydrophobically modified polyvinyl alcohols with a degree of hydrolysis of 80 to 95 mol% and a Höppler viscosity in 4% aqueous solution of 1 to 30 mPas are also preferred.
  • Examples of this are partially saponified copolymers of vinyl acetate with hydrophobic comonomers such as isopropenyl acetate, vinyl pivalate, vinyl ethylhexanoate, vinyl esters of saturated alpha-branched monocarboxylic acids with 5 or 9 to 11 carbon atoms, dialkyl maleate and dialkyl fumarates such as diisopropyl maleate and vinyl ether such as vinyl ether and vinyl isopropyl fumarate Vinyl butyl ether, olefins such as ethene and decene.
  • the proportion of the hydrophobic units is preferably 0.1 to 10% by weight, based on the total weight of the partially hydrolyzed polyvinyl alcohol. Mixtures of the polyvinyl alcohols mentioned can also be used.
  • polyvinyl alcohols with a degree of hydrolysis of 85 to 94 mol% and a Höppler viscosity, in 4% aqueous solution of 3 to 15 mPas (Höppler method at 20 ° C., DIN 53015).
  • the protective colloids mentioned are accessible by means of processes known to the person skilled in the art and are generally in a total amount of 0.3 to 20 wt .-%, based on the total weight of the monomers, added during the polymerization.
  • Nonionic or anionic emulsifiers are preferably used, also in the form of a mixture.
  • the nonionic emulsifiers used are preferably condensation products of ethylene oxide or propylene oxide with linear or branched alcohols having 8 to 18 carbon atoms, alkylphenols or linear or branched carboxylic acids of 8 to 18 carbon atoms. The use of a mixture of these nonionic emulsifiers is also preferred.
  • Suitable anionic emulsifiers are, for example, alkyl sulfates, alkyl sulfonates, alkylaryl sulfates, and sulfates or phosphates of condensation products of ethylene oxide with linear or branched alkyl alcohols and with 3 to 25 EO units, alkylphenols, and mono- or diesters of sulfosuccinic acid. If an additional emulsifier is used, its content is at least 0.2% by weight, based on the total weight of the monomers used.
  • the polymerization can be carried out independently of the polymerization process with or without the use of seed latices, with presentation of all or individual constituents of the reaction mixture, or with partial presentation and replenishment of the or individual constituents of the reaction mixture, or according to the metering process without presentation.
  • the comonomers and, if appropriate, the auxiliary monomers can all be introduced to prepare the dispersion (batch process), or some of the monomers are introduced and the rest are metered in (semibatch process).
  • the polyalkylene oxides and protective colloids can be introduced for the preparation of the dispersion, or added, or a part is introduced and the rest is metered.
  • the substances mentioned can also be metered in alone or as a pre-emulsion with the comonomers.
  • the desired amount is introduced by setting a certain pressure.
  • the pressure at which the gaseous monomer is introduced can initially be set to a certain value and decrease during the polymerization, or the pressure is left constant throughout the polymerization. The latter embodiment is preferred.
  • post-polymerization can be carried out using known methods to remove residual monomers, for example by post-polymerization initiated with a redox catalyst.
  • Volatile residual monomers and other volatile, non-aqueous constituents of the dispersion can also be removed by distillation, preferably under reduced pressure, and if appropriate by passing or passing through inert entraining gases such as air, nitrogen or water vapor.
  • aqueous dispersions obtainable by the process according to the invention have a solids content of 25 to 70% by weight, preferably 45 to 65% by weight.
  • the aqueous dispersions are dried, if appropriate after the addition of protective colloids as a spraying aid, for example by means of fluidized-bed drying, freeze drying or spray drying.
  • the dispersions are preferably spray-sprayed dries.
  • Spray drying is carried out in conventional spray drying systems, and atomization can be carried out using one-, two- or multi-component nozzles or with a rotating disc.
  • the outlet temperature is generally selected in the range from 45 ° C. to 120 ° C., preferably 60 ° C. to 90 ° C., depending on the system, the Tg of the resin and the desired degree of drying.
  • the atomization aid is used in a total amount of 3 to 30% by weight, based on the polymeric constituents of the dispersion.
  • Suitable colloidal aids are the protective colloids already mentioned.
  • a content of up to 1.5% by weight of antifoam, based on the base polymer has often proven to be advantageous.
  • the powder obtained can be equipped with an antiblocking agent (antibacking agent), preferably up to 30% by weight, based on the total weight of polymeric constituents.
  • antiblocking agents are calcium carbonate or magnesium carbonate, talc, gypsum, silica, kaolins, silicates.
  • aqueous polymer dispersions stabilized with protective colloids or polymer powders derived therefrom which are redispersible in water are obtained and are distinguished by constant viscosity, high stability and a very advantageous particle size distribution.
  • the polymers in the form of their aqueous dispersions and powders redispersible in water are suitable for use in adhesives and coating materials, for the consolidation of fibers or other particulate materials, for example for the textile sector. They are also suitable as modifiers and as water repellents. You can, especially in the copolymerization of silicon compounds, further in Polish, and in cosmetics, such as hair care, can be used to advantage. They are also suitable as binders in adhesives and coating materials, and also as protective coatings, for example for metals, foils, wood or release coatings, for example for paper treatment.
  • binders for paints, adhesives and coatings in the construction sector.
  • binders for paints, adhesives and coatings in the construction sector.
  • cements Portableland, aluminum, trass, metallurgical, magnesia, phosphate cement
  • gypsum and water glass
  • construction adhesives in particular tile adhesives and Full thermal protection adhesive
  • plasters fillers, floor fillers, leveling compounds, sealing slurries, grout and paints
  • grout and paints in particular for use in low-emission plastic emulsion paints and plastic dispersion plasters, both for indoor and outdoor use.
  • PEG polyethylene glycol. The number indicates the number average molecular weight Mn in g / mol.
  • Mersolat Na alkyl sulfonate with 12 to 14 carbon atoms in the alkyl radical.
  • Airvol V513 Na alkyl sulfonate with 12 to 14 carbon atoms in the alkyl radical.
  • Example 1 1.80 kg of water, 771.80 g of Airvol V513 (polyvinyl alcohol; 10% solution), 170.75 g of Genapol X 150 (40% aqueous solution), 125.99 g of Mersolat (30% aqueous solution) were placed in a 19 liter pressure autoclave Solution), 54.64 g of sodium vinyl sulfonate (25% in water), 512.25 g of vinyl acetate, 136.60 g of PDMS mixture and 512.25 g of VeoVa 10. The pH was adjusted to 5 with 10% formic acid.
  • an emulsifier metering was run in at a rate of 373 g per hour.
  • the emulsifier dosage contained 683.00 g PEG 35000 (polyethylene glycol 35000, 10% solution) and 1.37 kg Genapol PF 80 (20% aqueous solution).
  • the total metering time for the monomer metering was 5.8 hours, the emulsifier metering was 5.5 hours.
  • the APS dosage was reduced to 42.2 g per hour and the Na sulfite dosage to 52.7 g per hour.
  • the “GMA metering” was run in 30 minutes after the end of the emulsifier metering. Composition of the “GMA metering”: 136.60 g of vinyl acetate, 20.49 g of Veova 10 and 40.98 g of glycidyl methacrylate. The dosing time was 30 minutes (rate: 400 g per hour). After the end of the “GMA metering”, the APS and Na sulfite metering was continued for a further hour.
  • Dispersion analyzes: solids content: 55.0%, pH value: 5.0; Brookfield viscosity 20 (spindle 5): 4120 mPas; MFT: 3 ° C; Glass transition temperature Tg:
  • Dispersion analyzes: solids content: 56.7%, pH value: 5.4; Brookfield viscosity 20 (spindle 6): 3650 mPas; MFT: 3 ° C; Glass transition temperature Tg: 7.2 ° C; average particle size: 301.4 nm (Nanosizer) Coulter: Dn 0.113 ⁇ m; Dv 0.321 ⁇ m; Surface 24.7m 2 / g polymer dispersion
  • Example 5 As example 2, but with polyethylene glycol 8000 in the emulsifier metering. Dispersion Analyzes:
  • Solids content 56.6%, pH value: 4.8; Brookfield viscosity 20 (spindle 5): 3860 mPas; MFT: 2 ° C; Glass transition temperature Tg: 6.0 ° C; average particle size: 300.0 nm (Nanosizer) Coulter: Dn 0.102 ⁇ m; Dv 0.365 ⁇ m; Surface 25.4m 2 / g polymer dispersion
  • Comparative Example 6 76.87 kg water, 29.64 kg W 25/140 (polyvinyl alcohol; 10% solution), 5.25 kg Genapol X 150 (40% aqueous solution), 3.76 kg Mersolat (40% aqueous solution) were placed in a 572 liter pressure autoclave ), 2.10 kg sodium vinyl sulfonate (25% in water), 26.23 kg vinyl acetate, 5.25 kg PDMS mixture and 26.23 kg VeoVa 10. The pH was adjusted to 5 with 10% formic acid. Furthermore, 314 ml of Trilon B (EDTA; 2% aqueous solution) and 991 ml of iron ammonium sulfate (1% solution) were added. The kettle was heated to 70 ° C.
  • Trilon B EDTA; 2% aqueous solution
  • the emulsifier dosage contained 37.25 kg water and 27.55 kg Genapol X 150 (40% aqueous solution).
  • Genapol X 150 50% aqueous solution.
  • the total metering time for the monomer metering was 5.8 hours and for the emulsifier metering it was 5.5 hours. 15 minutes after the start of the reaction, the APS dosage was reduced to 636 g per hour and the Na sulfite dosage to 1226 g per hour.
  • the “GMA metering” was run in 30 minutes after the end of the emulsifier metering.
  • Composition of the “GMA metering” 5.25 kg of vinyl acetate, 787.02 g of Veova 10 and 1.57 kg of glycidyl methacrylate.
  • the dosing time was 30 minutes (rate: 15.2 kg per hour).
  • the APS and Na sulfite dosing was continued for 1 hour. After relaxation, the dispersion was used to minimize residual monomers Treated with water vapor ("stripped") and then preserved with Hydro W. Dispersion analysis:
  • Solids content 59.7%, pH: 4.84; Brookfield viscosity 20 (spindle 5): 2840 mPas; MFT: 5 ° C; Glass transition temperature Tg: 11.2 ° C; average particle size: 568.6 nm (Nanosizer); Coulter: Dn 0.357 ⁇ m; Dv 0.848 ⁇ m; Surface 11.2 m / g polymer dispersion
  • Dispersion analyzes solids content: 60.0%, pH value: 4.8; Brookfield viscosity 20 (spindle 6): 4050 mPas; MFT: 5 ° C; Glass transition temperature Tg: 11.7 ° C; average particle size: 291.2 nm (Nanosizer) Coulter: Dn 0.116 ⁇ m; Dv 2,182 ⁇ m; Surface area 17.0 m 2 / g polymer dispersion
  • the boiler was heated to 70 ° C and 13 bar of ethylene were injected.
  • a 10.0% ammonium peroxodisulfate solution (APS solution) was added at 1023 g per hour and run a 5.05% sodium sulfite solution at 1976 g per hour. 25 minutes later, a mixture of 187.77 kg of vinyl acetate, 32.96 kg of VeoVa 10 and 1.38 kg of vinyltrimethoxysilane (Wacker Silan XL 10) was started to be metered at a rate of 38.3 kg per hour (monomer metering).
  • the emulsifier dosage contained 56.29 kg Genapol PF 80 (20% aqueous solution).
  • the total metering time for the monomer metering was 5.8 hours and for the emulsifier metering it was 5.5 hours.
  • the APS dosage was reduced to 636 g per hour and the Na sulfite dosage to 1226 g per hour.
  • the “GMA metering” was run in 30 minutes after the end of the emulsifier metering. Composition of the “GMA metering”: 5.40 kg of vinyl acetate, 810.52 g of Veova 10 and 1.62 kg of glycidyl methacrylate. The dosing time was 30 minutes (rate: 15.68 kg per hour). After the “GMA metering” had ended, the APS and Na sulfite metering was continued for a further hour.
  • Dispersion analyzes: solids content: 59.8%, pH value: 5.3; Brookfield viscosity 20 (spindle 6): 8000 mPas; MFT: 5 ° C; Glass transition temperature Tg: 11.5 ° C; average particle size: 304.1 nm (Nanosizer); Coulter: Dn 0.207 ⁇ m; Dv 0.826 ⁇ m; Surface 18.9m 2 / g polymer dispersion
  • Dispersions stabilized with polyvinyl alcohol tend to increase their viscosity after storage (comparative examples V6 to V9).
  • the viscosity build-up can amount to well over 100%, as demonstrated by the comparative examples.
  • PEG polyethylene glycol
  • Example 1 With the series consisting of Examples 1, 2 and 3, where the amount of PEG 35000 was increased from Example 1, in Example 2 to 3 times, in Example 3 to 5 times, it was possible to show that the viscosity build-up of PVAL-stabilized dispersions is increasingly reduced or ultimately avoided with an increasing amount of PEG. Already in Examples 2 and 3 a constant viscosity during storage can be seen, while the increase in viscosity in Example 1 was still 58%. Examples 2, 4 and 5 show that the general suitability of PEG for avoiding viscosity build-up in PVAL-stabilized dispersions does not depend on the type of polyalkylene glycol.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne l'utilisation d'oxyde de polyalkylène pour éviter l'épaississement de dispersions polymères aqueuses stabilisées avec des colloïdes protecteurs. Ladite invention se caractérise en ce que lors de la production de dispersions polymères aqueuses par polymérisation initiée par voie radicalaire d'un ou de plusieurs monomères insaturés par voie éthylénique dans un milieu aqueux, en présence d'un ou de plusieurs colloïdes protecteurs, un ou plusieurs oxydes de polyalkylène, qui contiennent dans le cas de polymérisats mixtes d'oxyde d'alkylène, les unités d'oxyde d'alkylène en répartition statique, sont ajoutés avant ou après la polymérisation.
PCT/EP2004/007488 2003-07-17 2004-07-08 Utilisation d'oxydes de polyalkylene pour eviter l'epaississement de dispersions polymeres stabilisees avec des colloides protecteurs WO2005014661A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2003132527 DE10332527A1 (de) 2003-07-17 2003-07-17 Verwendung von Polyalkylenoxiden zur Vermeidung der Eindickung von mit Schutzkolloiden stabilisierten Polymerdispersionen
DE10332527.1 2003-07-17

Publications (2)

Publication Number Publication Date
WO2005014661A2 true WO2005014661A2 (fr) 2005-02-17
WO2005014661A3 WO2005014661A3 (fr) 2005-06-16

Family

ID=34041919

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2004/007488 WO2005014661A2 (fr) 2003-07-17 2004-07-08 Utilisation d'oxydes de polyalkylene pour eviter l'epaississement de dispersions polymeres stabilisees avec des colloides protecteurs

Country Status (2)

Country Link
DE (1) DE10332527A1 (fr)
WO (1) WO2005014661A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9780316B2 (en) 2015-03-16 2017-10-03 Universal Display Corporation Organic electroluminescent materials and devices
US10851186B2 (en) 2017-04-24 2020-12-01 Dow Global Technologies Llc Aqueous polymer dispersion

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005022853A1 (de) * 2005-05-18 2006-11-23 Wacker Polymer Systems Gmbh & Co. Kg Verfahren zur Herstellung von kationischen Polyvinylacetalen
DE102005042752A1 (de) 2005-09-08 2007-03-15 Wacker Chemie Ag Hydrophile Silikonorganocopolymere
WO2012123082A1 (fr) 2011-03-16 2012-09-20 Clariant International Ltd Polyalkylèneglycoléthers ramifiés en tant qu'agents mouillants et dispersants de désaération pour des peintures en dispersion aqueuse
DE102012019789A1 (de) 2012-10-09 2014-04-10 Clariant International Limited Phosphorgruppenhaltige Polyalkylenglykol-Blockcopolymere und deren Verwendung als Emulgatoren für die Emulsionspolymerisation

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1114833A2 (fr) * 1999-12-10 2001-07-11 Air Products And Chemicals, Inc. Emulsions de copolymères d' acetate de vinyle et d' éthylène stabilisées avec un mélange de polyéthylèneglycol et polyalcoolvinylique

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1114833A2 (fr) * 1999-12-10 2001-07-11 Air Products And Chemicals, Inc. Emulsions de copolymères d' acetate de vinyle et d' éthylène stabilisées avec un mélange de polyéthylèneglycol et polyalcoolvinylique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9780316B2 (en) 2015-03-16 2017-10-03 Universal Display Corporation Organic electroluminescent materials and devices
US10851186B2 (en) 2017-04-24 2020-12-01 Dow Global Technologies Llc Aqueous polymer dispersion

Also Published As

Publication number Publication date
WO2005014661A3 (fr) 2005-06-16
DE10332527A1 (de) 2005-02-10

Similar Documents

Publication Publication Date Title
EP1308468B1 (fr) Copolymères modifiés de manière hydrophobe
EP1916275B1 (fr) Compositions de polymères de dispersion en forme de poudre comprenant des tensioactives "gemini"
EP0741759B1 (fr) Composition pulverulente en dispersion, modifiee au silicium, pouvant etre redispersee, son procede de fabrication et d'utilisation
EP1023331B1 (fr) Procede de preparation de polymeres stabilises par colloides protecteurs
EP1713844B1 (fr) Procede de production de polymeres melanges contenant de la silicone
EP1585775B1 (fr) Procede pour produire des polymerisats silicones
EP1833865B1 (fr) Copolymeres reticulables modifies par des silanes
EP1420033B1 (fr) Dispersions aqueuses de polymères stabilisés par un colloide protecteur et poudres redispersables dans l'eau
EP1352915B1 (fr) Procédé continu de polymérisation en émulsion pour la préparation de polymères stabilisés par des colloides protecteurs
WO2007093551A1 (fr) Procédé de préparation de compositions de poudres polymères à stabilisation cationique redispersibles dans l'eau
EP1215218B1 (fr) Procédé de préparation de polymères ayant un contenu réduit de composants volatiles
EP1215219B1 (fr) Polymères greffés polyvinylacétal
EP2488557A1 (fr) Procédé de polymérisation en émulsion continue
DE102005051588A1 (de) Silan-modifizierte Dispersionspulver
EP1587849A2 (fr) Polymerisats aux silicones
EP2714751A1 (fr) Procédé de production de polymères stabilisés par des colloïdes protecteurs
EP1065224B1 (fr) Procédé de préparation de polymères stabilisés par l'alcool polyvinylique
WO2005035645A2 (fr) Compositions polymeres contenant des polyvinylalcools modifies
WO2005014661A2 (fr) Utilisation d'oxydes de polyalkylene pour eviter l'epaississement de dispersions polymeres stabilisees avec des colloides protecteurs
EP2935142B1 (fr) Utilisation de copolymères hybrides comme colloïdes protecteurs pour des polymères
DE10253045A1 (de) In Wasser redispergierbare Polymerpulver-Zusammensetzungen mit abbindebeschleunigender Wirkung
EP1646664B2 (fr) Procede de fabrication de dispersions polymeres aqueuses exemptes d alcools polyvinyliques

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DPEN Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101)
122 Ep: pct application non-entry in european phase