EP1098916A1 - Procede de production de dispersions aqueuses de (co-)polymeres, dispersions produites selon ce procede, poudres redispersibles obtenues a partir de ces dispersions et leur utilisation - Google Patents

Procede de production de dispersions aqueuses de (co-)polymeres, dispersions produites selon ce procede, poudres redispersibles obtenues a partir de ces dispersions et leur utilisation

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Publication number
EP1098916A1
EP1098916A1 EP99941448A EP99941448A EP1098916A1 EP 1098916 A1 EP1098916 A1 EP 1098916A1 EP 99941448 A EP99941448 A EP 99941448A EP 99941448 A EP99941448 A EP 99941448A EP 1098916 A1 EP1098916 A1 EP 1098916A1
Authority
EP
European Patent Office
Prior art keywords
polymer
dispersion
monomers
powder
cationic functionality
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.)
Withdrawn
Application number
EP99941448A
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German (de)
English (en)
Inventor
Hongli Willimann
Robert Koelliker
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.)
Celanese Switzerland AG
Original Assignee
Elotex AG
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Filing date
Publication date
Application filed by Elotex AG filed Critical Elotex AG
Publication of EP1098916A1 publication Critical patent/EP1098916A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • 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
    • 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
    • C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/06—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement
    • C09D1/08—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances cement with organic additives

Definitions

  • the present invention relates to processes for the preparation of aqueous dispersions of (co) polymers using a polymer with cationic functionality and, if appropriate, using customary additives.
  • the invention further relates to aqueous dispersions which can be prepared by the process, the redispersible powders obtainable from the dispersions and the use thereof.
  • aqueous polymer dispersions (latices)
  • aqueous polymer dispersions are not thermodynamically stable systems.
  • dispersants are generally added to the dispersions, which have an interface-stabilizing effect.
  • these are water-soluble compounds, which are either in the form of protective colloids or emulsifiers.
  • Emulsifiers which mostly have a molecular weight below 1500, have a stabilizing effect due to their amphiphilic structure by reducing the interfacial tension between the polymer / aqueous dispersion medium.
  • the stabilizing effect of protective colloids is primarily based on steric shielding of the dispersed particles.
  • these protective colloids are themselves polymeric materials, which can therefore impair the effect of the actual modifying polymer.
  • Such stabilizers which can also be used in emulsion polymerization, are, for example, conventional surface-active agents, water-soluble polymers, such as polyvinyl alcohol or polyvinylpyrrolidone, and polymerizable moieties. nomeren.
  • Such polymerizable functional monomers which can serve in polymerized form as a substitute for conventional surface-active agents, are, for example, carboxyl monomers, acrylamides or polymerizable surface-active agents with sulfonate groups.
  • a problem with the use of stabilizing agents is coalescence, i.e. the undesirable confluence of the latex particles in the emulsion, as a result of which no redispersible powder can be obtained.
  • This agglomeration into larger polymer secondary particles (coagulate) is more critical for a given polymer content of the aqueous dispersion, the finer the particles in disperse distribution are, since the interface grows disproportionately with decreasing particle diameter.
  • the powders obtainable by drying from these dispersions are particularly important. Redispersible powders are advantageous because of their ease of handling, easier, space-saving transport, easier dosing and less expensive storage. Because of the readily available dispersion medium "water”, the powder form is also desirable in this regard.
  • the polymer powders produced by drying processes such as freeze or spray drying, it being possible, in particular for spray drying, to produce larger amounts of powder, should be completely reversibly dispersible.
  • results are generally not completely satisfactory. This is due to the fact that during drying the highly disperse particles in the dispersion inevitably come closer to one another until irreversible changes occur when the surfaces of the particles come into contact, such as the coalescence already explained or an aggregation of the particles. As a result, the surface properties of the disperse phase are changed such that when water is added, the affinity of the particles to one another is greater than that to water, so that there is no actual redispersion.
  • the emulsifiers or protective colloids already mentioned, such as polyvinyl alcohol can result in a reduction in the reactivity of the redispersed polymer particles.
  • the redispersible powder can lose some or all of its reactivity and the associated properties after the redispersion.
  • drying aids are water-soluble substances that form a matrix during drying and thus embed the polymer particles. When redispersing with water, the matrix dissolves again and the polymer particles are retained almost unchanged.
  • EP 0 770 640 A2 uses such a technique. It describes the preparation of polymer powders by drying aqueous polymer dispersions, the dispersed polymers which have a positive or negative surface charge being kept in solution with the addition of a drying aid.
  • This drying aid is a polyelectrolyte which dissociates into a polyion and a counterion, the counterion having to have the opposite charge to the surface charge of the polymer.
  • the polyelectrolyte thus fulfills the function of an additional stabilizer that keeps the polymer in solution.
  • the polymer is not polymerized in the presence of the stabilizer, but is already available as a finished polymer.
  • the stabilizing effect is achieved here by another molecule that acts as an emulsifier.
  • EP 0 441 037 AI Another possibility of obtaining stabilized dispersions from water-insoluble latex is known from EP 0 441 037 AI.
  • the cationic polymers therefore do not support to stabilize the dispersion, but destroy it with precipitation of the latex polymers (so-called breaking of the emulsion) and formation of a coating.
  • EP 0 286 008 B1 describes the use of aqueous cationic plastic dispersions for impregnating and priming absorbent substrates.
  • the cationic dispersion polymers contain 80 to 99% by weight of ethylenically unsaturated monomers from the group of vinyl esters, methacrylic esters, acrylic esters, vinyl aromatics, vinyl chloride, ethylene, acrylonitrile, diesters of maleic acid and / or fumaric acid, vinyl pyrrolidone, 1 to 20% by weight.
  • the monomers are selected so that the minimum cation activity of the dispersions is from 20 to 200 ⁇ mol / g of solid, measured at pH 7, and 60 to 99% of the cationic charge is on the surface of the particles, and the dispersions have a minimum film-forming temperature (MFT) between 0 and 40 ° C.
  • MFT film-forming temperature
  • the polymer particles of the dispersions have an average particle diameter of 0.02 to 0.2 ⁇ m.
  • the cationic dispersions are used for impregnating and priming masonry, concrete, plastered surfaces, polished plaster, plastered surfaces or masonry. However, dispersible powders are not described.
  • an aqueous dispersion of a cationic ethylenically unsaturated polymer which has a glass transition temperature Tg ⁇ 50 ° C. and a cationic water-soluble or water-dispersible ethylenically unsaturated oligomer and / or polymer and / or cationizable ethylenically unsaturated monomers contains aqueous phase.
  • the polymers serve as additives to improve the properties of cement products. This improves the water resistance, water impermeability, strength, adhesion, chemical resistance and durability of a cement product, such as mortar.
  • the emulsion polymerization of these polymers is either by radical polymer Lymerisation of alpha- or beta-ethylenically unsaturated monomers in the presence of cationic water-soluble and / or water-dispersible oligomers and / or polymers or by radical polymerisation of alpha- or beta-ethylenically unsaturated monomers, some of which are achieved by cationic efhyle- nically unsaturated monomers such as Dimethylaminoethyl methacrylate esters of maleic acid, fumaric acid, itaconic acid, etc., are replaced.
  • a disadvantage of this teaching is on the one hand the very limited scope of the polymers that can be used and the very limited field of application for cement formulations.
  • the polymers produced must have a glass transition temperature Tg ⁇ 50 ° C, for example to give mortar the desired properties.
  • the cationic acrylic resin according to this Japanese patent serves as a water dispersant and is used as an additional additive.
  • the use of the cationic water soluble or dispersible oligomer and / or polymer serves to prevent the latex from coagulating in the cement.
  • no redispersible powder is described in JP 55 104 955 A and is also not provided. For the reasons already explained, it is much more difficult to provide a redispersible powder obtainable in addition to a stable dispersion.
  • the invention is based on the object of developing the aqueous dispersions prepared by the processes described at the outset in such a way that the process control and the selection of the starting materials can be made more flexible while maintaining advantageous properties or in individual cases for producing improved properties. Furthermore, the process is intended to reliably stabilize the polymers to be dispersed, irrespective of the respective functionality, in aqueous dispersion. In addition, these dispersions are to be improved to the extent that they lead to improved application products in their end uses, for example in plastic-containing, cement-bound systems, due to desirable subsequent reactions. In addition, it should be possible to obtain a redispersible powder from the dispersions which essentially retains its advantageous properties after redispersion in the aqueous medium. On Stabilizing additives in the form of emulsifiers and protective colloids as well as drying aids or spray aids should be dispensed with.
  • the above object is achieved by a process A) for the preparation of aqueous dispersions of (co) polymers using a polymer with cationic functionality, if appropriate using customary additives, the polymer having cationic functionality being obtained by (co) polymerizing in the aqueous medium from olefinically unsaturated (co) monomers is obtained, in which at least one (co) monomer has a cationic functionality, further (co) monomers are added and the polymerization is carried out in the presence of suitable initiators, the polymers and / or (co) monomers are selected and the process is controlled such that a (co) polymer particle having a heterogeneous morphology is formed and the dispersed (co) polymer obtained has a glass transition temperature Tg of more than about 50 ° C.
  • the polymers with cationic functionality for the (co) polymer formed according to the invention have the effect corresponding to an emulsifier or a protective colloid and already lead to a stabilization of the dispersed copolymerized particles during the emulsion polymerization.
  • a kind of "copolymerization" of the polymer with cationic functionality produces a dispersion-stable latex particle, the latex particles produced by process A) having a heterogeneous morphology with a specific glass transition temperature Tg.
  • “Heterogeneous morphology” need not mean in this context, that two or more different glass transition temperatures Tg must be present. It rather means that regions of different compositions, for example phases, form in the (co) polymer particles.
  • an inverse core-shell morphology can be formed
  • the (co) polymer particle can essentially have an outer phase (shell) in the form of largely hydrophobic regions and essentially an inner phase (core) in the form of largely hydrophilic regions beer structure (raspberry-like structure) can be generated.
  • the emulsion polymerization is preferably carried out in such a way that the proportion of polymer with cationic functionality is greater in the outer phase than in the inner phase.
  • the parameters and conditions which can be varied in this connection are known to the person skilled in the art. For this, reference is made to "Emulsion Polymerization and Emulsion Polymers", PA Lovell and MS El-Aasser, 1997, in particular pp. 293-326.
  • the glass transition temperature is again of great importance.
  • the glass transition temperature can be determined either by measurement, for example by DSC methods, or by theoretical calculation.
  • the glass transition temperatures (midpoint temperature according to ASTM D3418-82) of copolymers are calculated according to an empirical approximation by Fox (TG Fox, Bull. Am. Phy. Soc. (Ser II) 1, 123 (1956) and Ullmann's Encyclopedia of Technical Chemistry, Vol. 19, 4th edition, Verlag Chemie, Weinheim, 1980, pp. 17/18). The following applies to the glass transition temperature:
  • the polymers and / or (co-) monomers are selected so that the dispersed (co) polymer obtained has a glass transition temperature Tg of more than about 50 ° C.
  • Tg glass transition temperature
  • the glass transition temperature Tg can also be modified in each case by the inner phase (core) and the outer phase (shell) in order to enable adaptation to the desired use.
  • the inner phase preferably has a Tg value as low as possible, preferably below 50 ° C., which causes the latex particle to coalesce. This is advantageous if a continuous dispersion film is to be produced, which e.g. is the case with coating applications.
  • the glass transition temperature Tg is above 50 ° C. This can be important in corresponding applications because it increases the stability of redispersible powders and enables higher mechanical properties of the end use to be achieved.
  • the Tg value of the outer phase is as high as possible and at the same time the Tg value of the inner phase is as low as possible. It is particularly advantageous if the outer phase has a glass transition temperature Tg of more than about 50 ° C. and the inner phase of less than about 50 ° C., in particular between about -70 to + 50 ° C. In this way, particularly favorable properties are achieved, since the outer phase gives the sprayed powder increased stability and the inner phase films the product after redispersion.
  • polymer with cationic functionality is not particularly limited, as long as it is obtained from (co) polymerization in the aqueous medium of olefinically unsaturated (co) monomers and at least one cationic function is present in the molecule.
  • polymer fall homopolymers, copolymers, block polymers or graft copolymers as well as oligomers. It is obvious to the person skilled in the art that any (co-) polymerizable starting monomers with olefinically unsaturated functionalities are suitable for this polymer.
  • about 1 part by weight of monomer with cationic functionality falls from 0 to about 50 parts by weight, in particular about 0.1 to 20 parts by weight. Parts of (co) monomer.
  • the polymer results from copolymerizable olefinically unsaturated compounds, these being, for example: a vinyl ester of (G-Ci8) carboxylic acids, for example vinyl acetate, vinyl propionate and the like; a (meth) acrylic ester of (Ci-C ⁇ ) alcohols, for example methyl methacrylate, butyl methacrylate, octyl methacrylate, ethyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate; a vinyl aromatic such as styrene, vinyl toulol, vinyl chloride, an ethylene, an acrylonitrile, a diester of maleic acid and / or fumaric acid, a vinyl pyrrolidone, an amino acrylate or methacrylate ester, a vinyl pyridine, an alkyl amino group-containing vinyl ether, an alkylamino group containing acrylamide / methacrylamide or a
  • the cationic functionality preferably derives from a quaternary ammonium group.
  • Acrylates and / or methacrylates, and also ester and amide compounds are preferably used.
  • the chain length between ester / amide and the quaternary nitrogen is typically C2 to Ct.
  • Amines that are protonated in the acidic pH range can also be used.
  • Monomers which are particularly preferred according to the invention for producing the polymer with cationic functionality are, for example: N, N - [(3-chloro-2-hydroxypropyl) -3-dimethylammoniumpropyl] methacrylamide chloride (DMAPMA-epi), N- [3- (dimethylamino) propyl ] methacrylic amide hydrochloride (DMAPMA-HC1), N- [3- (trimethylammonium) propyl] methacrylic amide chloride (MAPTAC), 2-hydroxy-3-methacryloxypropyltrimethylammonium- Chloride, dimethyldiallylammonium chloride, aziridinylethyl methacrylate, morpholinoethyl methacrylate, trimethylammonium ethyl methacrylate chloride, dimethylaminopropyl methacrylate, 1, 2,2,6,6-pentamethylpiperidinyl methacrylate, aminopropyl vinyl ether, die
  • the polymer with cationic functionality can be prepared according to the invention either in an upstream step by homo- or (co-) polymerization of monomers with cationic functionality or with further comonomers and can be processed immediately without being isolated (in situ further processing); or the polymer with cationic functionality can initially be prepared separately and isolated before further processing according to the invention.
  • any commercially available polymer with cationic functionality that meets the above requirements can also be used.
  • the (co) polymer obtained about 1 part by weight of monomer (with cationic functionality) of the polymer with cationic functionality is preferably about 2 to 250 parts by weight, in particular about 10 to 150 parts by weight of other (co) parts. Monomers. According to the invention, the (co) polymer produced contains about 0.001 to 50 mol%, in particular about 0.1 to 35 mol, monomer units with cationic functionality.
  • the present invention is not particularly limited in the choice of the (co) monomers which are polymerized in the presence of the cationic polymer.
  • All (co-) polymerizable monomers known to the person skilled in the art can be used. Examples include: alpha, beta-ethylenically unsaturated monomers, such as acrylate esters, methacrylate esters and carboxylate esters, acids and their salts, such as acrylic acid, maleic acid, itaconic acid, vinylsulfonic acid, vinyltoluenesulfonic acid and unsaturated dibasic acids, their half esters and salts, alpha-beta unsaturated amides, vinyl esters, vinyl-substituted aromatic compounds, heterocyclic compounds with vinyl groups, vinylidene halides, alpha-olefins, diallyl phthalates, divinylbenzenes, alkyl acrylates, trimethylolpropane trimethyl acrylates, Esters of acrylic and methacrylic acid with
  • cationic monomers In addition to cationic monomers, it is also preferred to copolymerize monomers whose protonated reactive group (s) are (are) deprotonated when the pH is raised accordingly. Such groups are known to the person skilled in the art.
  • at least one anionic functionality can also be present in the (co) monomers. This creates amphoteric systems which are stable as such and do not coagulate.
  • process A) according to the invention can be carried out continuously, semi-continuously or as a batch process. This also depends on whether the polymer with cationic functionality is produced separately or is processed further immediately after in situ production. For example, after the cationic polymer has been prepared, the process can be carried out in batches.
  • radical initiators are used to carry out the polymerization.
  • the present invention is not subject to any relevant restriction in the selection of the initiators.
  • the free radical initiators used in the context of the invention are either water-soluble or water-insoluble, ie they are then monomer-soluble.
  • Suitable water-soluble initiators are sodium, potassium and ammonium peroxodisulfate, hydrogen peroxide and water-soluble azo compounds such as 2,2'-azobis (2-amidinopropane dihydrochloride), 2,2'-azobis [2-methyl-N- (2-hydroxy ethy l) propionamide], and 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride.
  • Suitable monomer-soluble initiators are organic hydroperoxides, such as tert-butyl hydroperoxide, pinane hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide and diisopropylphenyl hydroperoxide, organic peroxides, such as dibenzoyl peroxide, dilauryl peroxide and diacetyl peroxide, and monomer-soluble azo compounds such as azo compounds. Mixtures of initiators can also be used. Instead of a radical initiator, it is also possible to use an initiator system which consists of a radical initiator of the type described above and a water-soluble reducing agent.
  • the actual radical initiator is accordingly formed during the polymerization, which can be done, for example, by thermal decomposition of the initiator above, but also by reaction of the initiator with an aqueous reducing agent.
  • the water-soluble reducing agents act as activators for the initiators. Suitable reducing agents are ascorbic acid, sodium, potassium and ammonium sulfite, bisulfite and metabisulfite, sodium formaldehyde sulfoxylate, tartaric acid, citric acid and glucose. They can be used in combination with a heavy metal salt.
  • the reducing agents are generally used in an amount of 0.01 to 2% by mass, based on the total monomers added. They are usually metered in during the polymerization.
  • the initiators or the initiator combination are generally used in an amount of 0.01 to 2% by mass, based on the total monomers.
  • Usual additives can be used depending on the application conditions. Examples include thickeners, pigments, flameproofing substances, crosslinking agents, fillers, reinforcing agents, filming aids, antioxidants, fungicides, defoamers, plasticizers, preservatives, wetting agents, rheology modification aids, crosslinking agents, resins, adhesive aids, anti-blocking agents and the like, which are customary Amounts can be added.
  • the dispersion is preferably prepared without the addition of an emulsifier, but a small amount of emulsifier can optionally also be used.
  • the proportion of emulsifier is advantageously less than about 3% by weight, in particular less than about 1.5% by weight.
  • the emulsifier content is preferably even below 1.0% by weight, very particularly preferably below 0.5% by weight or above all below 0.2% by weight.
  • the polymerization is preferably carried out between approximately 50 and 100 ° C., in particular between approximately 60 and 90 ° C.
  • the temperature can depend, for example, on the initiator system used.
  • the initial temperature is preferably about 70 ° C in individual cases.
  • the development of heat due to the exothermic reaction during the polymerization can be used to set the reaction temperature between 80 and 90 ° C., cooling being necessary if necessary in order not to exceed the specified temperature range.
  • the total amount of heat generated can also be dissipated in order to maintain or even drop below the initial temperature of about 70 ° C. in the course of the reaction.
  • an autoclave can be used, which opens up the possibility of carrying out the polymerization above 100 ° C.
  • the pH of the aqueous dispersion medium is generally 2 to 10 during the free radical aqueous emulsion polymerization. After the end of the polymerization, the pH can be adjusted to a value of about 2 to 12.
  • the present invention also relates to a process B) for preparing aqueous dispersions of (co) polymers using a polymer with cationic functionality, optionally using customary additives, the polymer having cationic functionality being obtained by (co) polymerizing in the aqueous medium from olefinically unsaturated (co) monomers is obtained, in which at least one (co) monomer has a cationic functionality, further (co) monomers are added and is polymerized in the presence of suitable initiators, the polymer having cationic functionality in the presence of a Seed is formed in situ.
  • the properties of these polymers with cationic functionality with regard to the (co) polymer formed according to the invention are comparable to those of emulsifiers or protective colloids, as a result of which the copolymerized particles are stabilized in dispersion.
  • a kind of "copolymerization" of the polymer with cationic functionality makes it stable in dispersion Generated latex particles, but method B) results from seed polymerization.
  • a latex with a uniform particle size is introduced.
  • the monomers to be polymerized are metered into this seed latex in the monomer feed procedure.
  • the polymerization is carried out in such a way that the latex particles present increase in volume while maintaining the monodispersity of the system, but do not increase in number.
  • the number of particles is proportional to the proportion of the original, and a narrow particle size distribution is obtained.
  • about 0.1 to 25% by weight, in particular about 0.5 to 20% by weight, of the (co) monomer, based on the finished (co) polymer is used to form the seeds.
  • the (co) monomers can be the monomers used for the production of the cationic polymer or any other monomer (foreign latex); the monomers for the production of the seeds are generally independent of the monomers used below.
  • the (co) polymer particles produced according to the invention by means of the upstream seed polymerization have an extremely homogeneous particle size, i.e. , the particles are (largely) monodisperse.
  • “monodisperse” means that the average particle diameters preferably vary by approximately ⁇ 10%.
  • Such homogeneous particle sizes are not always possible with the known methods of the prior art or are often associated with very great outlay in terms of process engineering and low yields.
  • the particle size of the (co) polymer produced can also be set in a targeted manner.
  • the latex particles formed preferably have an average diameter of approximately 30 to 1000 nm, in particular approximately 50 to 600 nm.
  • the polymer with cationic functionality can be a homopolymer, copolymer, block polymer or graft copolymer as well as an oligomer and is not subject to any particular restriction provided that the cationic polymer has arisen and at least from the (co) polymerisation of olefinically unsaturated monomers has a cationic functionality.
  • Preferred monomers with cationic functionality are also monomers containing quaternary ammonium groups. It is obvious to the person skilled in the art that any (co-) polymerizable olefinically unsaturated starting monomers are suitable for this polymer.
  • the polymer with cationic functionality preferably contains about 1 part by weight of monomer with cationic functionality from 0 to about 50 parts by weight, in particular about 0.1 to 20 parts by weight of (co) monomer.
  • the polymer with cationic functionality is thus prepared according to the invention in a preceding step by homo- or (co-) polymerizing olefinically unsaturated (co-) monomers, at least one (co-) monomer having a cationic functionality, by means of seed polymerization and is immediately - further processed without being isolated (further processing in situ); or the polymer with cationic functionality can first be prepared, isolated and then processed independently of the method according to the invention.
  • any commercially available polymer with cationic functionality that meets the above requirements can also be used.
  • the (co) polymer obtained about 1 part by weight of monomer (with cationic functionality) of the polymer with cationic functionality is preferably about 2 to 250 parts by weight, in particular about 10 to 150 parts by weight of other (co) parts. Monomers. According to the invention, the (co) polymer produced can contain about 0.001 to 50 mol%, in particular about 0.1 to 35 mol%, of monomer units with cationic functionality.
  • the present invention is not subject to any relevant restriction with regard to the choice of the (co) monomers which are polymerized in the presence of the cationic polymer.
  • All (co-) polymerizable monomers known to the person skilled in the art can be used.
  • the comonomers which can be used reference is made to the comonomers listed in detail in process A).
  • the polymers and / or (co) monomers are preferably selected such that the dispersed (co) polymer obtained has a glass transition temperature Tg of more than about 50.degree. In this regard, reference is made to the explanations in method A).
  • the (co) monomers in addition to the cationic monomers, it is also possible to copolymerize monomers whose protonated reactive group (s) is (are) deprotonated when the pH is raised accordingly.
  • the (co) monomers can have at least one anionic functionality.
  • amphoteric systems can be obtained which are in stable form and do not coagulate.
  • Such groups are known to the person skilled in the art.
  • the process B) according to the invention can be carried out continuously, semi-continuously or as a batch process, depending on whether the polymer with cationic functionality has been prepared separately or in situ, the principles of emulsion polymerization, of course, to be considered. If the cationic polymer is further processed in situ, the process can be carried out, for example, continuously or as a batch process.
  • the polymerization is carried out in the customary manner between about 50 and 100 ° C., in particular between about 60 and 90 ° C.
  • the temperature can depend, for example, on the initiator system used.
  • free radical initiators are used, individually, as a mixture or, if appropriate, with suitable activators which correspond to those already mentioned in the explanation of process A).
  • the initiators or the initiator combination are generally used in an amount of 0.01 to 2% by mass, based on the total monomers.
  • Customary additives known to the person skilled in the art can be added in suitable amounts depending on the intended use.
  • the use of emulsifiers is largely avoided, the amount of emulsifier advantageously being less than about 3% by weight or less than about 1.5% by weight, preferably less than 1.0% by weight, very particularly preferably less than 0%, 5 wt .-% or especially less than 0.2 wt .-%.
  • the invention also relates to the stabilized aqueous dispersions which are obtainable by processes A) or B) described above. These are characterized in particular by their high stability and the flexibility of the starting materials.
  • a further aqueous dispersion (dispersion 2) with other latex particles can be mixed into the aqueous dispersion obtained (dispersion 1) with one type of latex particle.
  • the dispersion 1 is preferably present in a weight ratio of about 5:95 to 95: 5, preferably about 10:90 to 90:10, in particular about 20:80 to 80:20, to dispersion 2.
  • This dispersion 2 can be an aqueous dispersion of homo- or copolymers. Examples of monomers are vinyl acetate, ethylene, vinyl versatate, acrylate, methacrylate, styrene and / or butadiene. Of course, other monomers known to the person skilled in the art can also be used within the scope of the invention.
  • the properties can be optimized accordingly by adding a further dispersion.
  • the invention also relates to redispersible powders which can be obtained by removing the water from the aqueous dispersions described above.
  • the water is removed in the customary manner by drying, in particular by spray or freeze drying.
  • the redispersible powder according to the invention preferably contains a (co) polymer of about 0.01 to 50% by weight of cationic monomers and about 50 to 99.99% by weight of (co) monomers; optionally, about 0 to 5% by weight of emulsifier and conventional additives can be added.
  • the redispersible powder can be used as a powdery ready-made mixture which only has to be mixed with water. Depending on the desired application, it can be redispersed in water in more or less concentrated form. In the present invention, it is particularly advantageous to achieve a high solids content in the dispersion prepared, a dispersion with up to about 75% solids content in the aqueous medium being possible.
  • An aqueous dispersion having a solids content of approximately 20 to 60%, in particular approximately 30 to 50%, is expediently prepared as a rule.
  • the properties can be optimized accordingly by adding another powder to this powder obtained.
  • a powder 1 of one type of latex particle is mixed with another powder 2 of other latex particles.
  • the weight ratio of powder 1 to powder 2 is preferably approximately 5:95 to 95: 5, preferably approximately 10:90 to 90:10, in particular approximately 20:80 to 80:20.
  • the powder 2 can be composed of homo- or copolymers which are selected from the following monomers: vinyl acetate, ethylene, vinyl versatate, acrylate, methacrylate, styrene and / or butadiene. This list is only exemplary and not restrictive, any other monomers can be used.
  • the aqueous dispersion and the redispersible powder according to the present invention can be used in a variety of ways.
  • the dispersions according to the invention are thus suitable for use in composite and coating mortars, cement paints and adhesives, plastic-based cement-bound systems, in particular in mortar, and plastic-bound cement-free binders, in particular in cement-free mortars, plaster mortars, primers, plasters, carpets, wood, powder and floor adhesives, as well as in wallpaper paste, dispersion powder paints and glass fiber composite systems.
  • aqueous (co) polymer dispersions and the redispersible (co) polymer powders obtainable from them by drying are particularly suitable for modifying cementitious building adhesives and for increasing the water resistance.
  • use in general cement-containing products is also possible.
  • the (co) polymer is usually added in an amount of 3 to 30% by weight, advantageously in an amount of 7 to 20% by weight.
  • various additives such as cellulose, fibers and the like can be added as required.
  • the (co) polymers produced in the form of the redispersible powder, starting from the seed polymerization are particularly suitable as filling material for columns in chromatographic separation processes, such as in gas chromatography or high-pressure liquid chromatography (HPLC), and as calibration material for devices for measuring the particle size, since the particles have largely the same diameter due to the manufacturing process, ie are homogeneous or monodisperse.
  • Redispersible powders according to the invention can moreover be used as carriers for delayed release for active substances of all kinds.
  • the active compounds can be added either by copolymerization into the (co) polymer particles or by addition during redispersion of the particles.
  • the active ingredient contained is then released with a delay, which can be done, for example, by adding or introducing it into an active ingredient-dissolving medium.
  • the active ingredients used can be used in the agricultural sector, for example fungicides, herbicides, phytohormones, insecticides, nematicides, rodenticides and acaricides.
  • vitamins, minerals and the like are suitable as active ingredients which are released in delayed form by means of the redispersible powder.
  • the redispersible powders according to the invention are also used in the pharmaceutical sector in the form of carrier materials for the absorption of any pharmaceuticals to be released later.
  • the desired improved properties of the dispersions according to the invention and of the powders obtainable by drying are based on the fact that a polymer with cationic functionality in an emulsion polymerization process partially or completely functions as a surface-active agent or protective colloid takes over, regardless of other functionalities in the molecule. It does not matter whether the polymer with the cationic functionality is in homo- or copolymerized form.
  • the advantages associated with the invention are complex.
  • the processes A) and B) according to the invention are surprisingly flexible in terms of the quantitative and qualitative framework conditions compared to the above-described teachings of the prior art. This is only limited by one condition in each case: in method A) by the formation of a heterogeneous morphology and adjustment of the glass transition temperature Tg above 50 ° C. and in method B) by the additional seed polymerization.
  • emulsifiers are not absolutely necessary. This completely eliminates the disadvantages associated with such stabilizing additives. There is even no need for any other stabilizing agents. Nevertheless, the process products obtained show very favorable properties, such as improved processability, better setting behavior (adhesion), good water resistance and higher storage stability.
  • a particular advantage is that the process product obtained leads to improved properties in the end uses mentioned.
  • the redispersible powders according to the invention can also be used particularly advantageously as inert carrier materials for a large number of active ingredients, for example from the agricultural sector, the food and pharmaceuticals sector. As a result, these active substances can be metered more easily and, due to the delayed release, can be used more specifically.
  • the methods A) and B) according to the invention can be combined in a particularly advantageous manner, as a result of which the advantageous properties can be combined in the desired manner and can thus be individually adjusted for each application.
  • By selecting the Glass transition temperature can also be adapted to the desired purpose.
  • VEOVA ® -10 vinyl ester from Versatic 10 ® (VEOVA ® X is a Shell brand and stands for vinyl esters of carboxylic acids, which are also known as Versatic ® X acids), Triton '® brand from Rohm & Haas for Assortment of non-ionic surfactants,
  • Example 1 was repeated, but the aqueous DMAPMA-epi solution was metered in parallel with the monomer mixture consisting of 252 g of methyl methacrylate, 24 g of acrylic acid, 2.4 g of methacrylic acid and 252 g of butyl acrylate. Coagulation occurred after 30 minutes of the monomer feed.
  • Example 1 was repeated, except that 520 g of vinyl acetate, 25 g of acrylic acid and 2.5 g of methacrylic acid were metered in as a monomer mixture over the course of 3.0 hours.
  • the example shows that the colloid polymerized in situ as a stabilizer is not only effective in the case of acrylate-based comonomers in emulsion polymerization, but also works with other monomers.
  • the solids content of this dispersion was 49.5%, the viscosity 96 mPas; the pH was 2.7.
  • Example 4 Example 4
  • Example 1 was repeated, except that 380 g of vinyl acetate, 150 g of VEOVA ® -10, 25 g of acrylic acid and 2.5 g of methacrylic acid as a monomer mixture for 3.0 hours. Added.
  • the example shows that the colloid polymerized in situ can generally be used as a stabilizer in emulsion polymerizations.
  • the stabilization according to the invention is also achieved with the monomer composition described.
  • the solids content was 49.4%, the viscosity 173 mPas; the pH was 2.7.
  • Example 5 Example 1 was repeated, but 220 g of styrene, 200 g of butyl acrylate, 40 g of acrylic acid and 10 g of glycidyl methacrylate were metered in as a monomer mixture over the course of 3.0 hours.
  • the solids content was 46.1%, the viscosity 95 mPas; the pH was 2.8.
  • Example 1 was repeated except that 35 g of a 50% aqueous solution of N- [3- (trimethylammonium) propyl] methacrylamide chloride (hereinafter referred to as MAPTAC) was added in place of DMAPMA-epi in the first stage.
  • MAPTAC N- [3- (trimethylammonium) propyl] methacrylamide chloride
  • the MAPTAC monomer also has a quaternary ammonium group and can therefore also be used to form an in-situ colloid that acts as a latex stabilizer.
  • the solids content was 50.5%, the viscosity 497 mPas; the pH was 2.5.
  • Example 7 In a 21-glass reactor equipped with a stirrer and a temperature control, 3.6 g of dodecyl mercaptan, 1.0 g of sodium hydrogen carbonate and 660 g of deionized water were added to the reactor in succession. The mixture was then flushed with nitrogen and heated to 60 ° C. with stirring. The aqueous monomer solution consisted of 73.8 g MAPTAC and the one-hour monomer feed consisted of 99.7 g methyl methacrylate, 11.1 g butyl acrylate and 36.9 g VEOVA ® 9. One minute later, 1.3 g V-50 were added in one Portion added.
  • dispersions from Examples 6 and 7 were spray-dried by the customary method. Before spraying, dispersion 7 was mixed with 10 parts of partially hydrolyzed polyvinyl alcohol (degree of hydrolysis 88%; viscosity 4 mPas as a 4% solution) to 90 parts of dispersion. The solids content was adjusted to 25% with water and sprayed through a two-component nozzle. Air pre-compressed to 4 bar was used as the atomizing component; the drops formed were dried with 110-115 ° C hot air in cocurrent. A free-flowing, redispersible powder resulted in both cases.
  • Stoneware tiles (EN 176) with dimensions 50 mm x 50 mm were used. After an insertion time of 5 minutes after application, 20 N was applied for 30 seconds. The adhesive tensile test was carried out after 28 days, stored at 50% relative humidity and at 23 ° C (standard climate).
  • Stoneware tiles (EN 176) with dimensions 50 mm x 50 mm were used. After an insertion time of 5 minutes after application, 20 N was applied for 30 seconds. The adhesive pull test was carried out after 7 days of normal climate and 20 days under water.
  • the resulting% number corresponds to the water resistance. The smaller the number, the worse the water resistance.
  • This (co) polymer according to the invention produced with in situ polymer with cationic functionality offers improved adhesion after wet storage.
  • the (co) polymer according to the invention shows improved adhesion after wet storage.
  • the mortar modified according to the invention thus has excellent adhesive strength on mineral substrates, especially after wet storage.
  • adhesive mortars modified in this way have a very good processability when ready for use, as is required by the processor.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Analytical Chemistry (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de production permettant de produire des dispersions aqueuses de (co-)polymères. Ce procédé consiste à : utiliser un polymère de fonction cationique et éventuellement des additifs usuels. Le polymère de fonction cationique est obtenu par (co-)polymérisation dans un milieu aqueux de (co-)monomères oléfiniquement insaturés, au moins un (co-)monomère présentant une fonction cationique. Ce procédé consiste ensuite à ajouter d'autres (co-)monomères et à effectuer la polymérisation en présence d'initiateurs appropriés. Les polymères et/ou les (co-)monomères sont sélectionnés et le procédé est mis en oeuvre de telle façon qu'une particule de (co-)polymère a une morphologie hétérogène et le (co-)polymère dispersé obtenu a une température de transition vitreuse Tg de plus d'environ 50 DEG C. L'invention concerne également un procédé selon lequel le polymère de fonction cationique est formé en présence d'une semence in situ. L'invention concerne enfin des poudres redispersibles ainsi que leur utilisation.
EP99941448A 1998-07-22 1999-07-21 Procede de production de dispersions aqueuses de (co-)polymeres, dispersions produites selon ce procede, poudres redispersibles obtenues a partir de ces dispersions et leur utilisation Withdrawn EP1098916A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19833066A DE19833066A1 (de) 1998-07-22 1998-07-22 Verfahren zur Herstellung wäßriger Dispersionen von (Co-)Polymerisaten, die danach erhältlichen Dispersionen, aus den Dispersionen erhältliche redispergierbare Pulver sowie deren Verwendung
DE19833066 1998-07-22
PCT/EP1999/005206 WO2000005283A1 (fr) 1998-07-22 1999-07-21 Procede de production de dispersions aqueuses de (co-)polymeres, dispersions produites selon ce procede, poudres redispersibles obtenues a partir de ces dispersions et leur utilisation

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EP1897926A1 (fr) 2006-09-11 2008-03-12 National Starch and Chemical Investment Holding Corporation Poudre et composition adhésive à base d'eau
WO2011141400A1 (fr) 2010-05-12 2011-11-17 Akzo Nobel Chemicals International B.V. Émulsion ou poudre de polymère redispersable d'un polymère comprenant un biomonomère, leur procédé de préparation et leur utilisation dans des compositions de matériau de construction
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EP1897926A1 (fr) 2006-09-11 2008-03-12 National Starch and Chemical Investment Holding Corporation Poudre et composition adhésive à base d'eau
WO2011141400A1 (fr) 2010-05-12 2011-11-17 Akzo Nobel Chemicals International B.V. Émulsion ou poudre de polymère redispersable d'un polymère comprenant un biomonomère, leur procédé de préparation et leur utilisation dans des compositions de matériau de construction
WO2012175460A1 (fr) 2011-06-22 2012-12-27 Akzo Nobel Chemicals International B.V. Polymérisat contenant un macromonomère

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CA2338095A1 (fr) 2000-02-03
AU5506099A (en) 2000-02-14
BR9912676A (pt) 2001-05-02
JP2002521511A (ja) 2002-07-16
US6559236B1 (en) 2003-05-06
DE19833066A1 (de) 2000-02-03

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