DE10322788A1 - Process for the preparation of polymer powders - Google Patents

Abstract

Process for the preparation of polymer powders by evaporating the volatile constituents from aqueous dispersions of film-forming polymers P, characterized in that the aqueous polymer dispersion, before the volatile constituents are evaporated, also has drying aids T which are present in an amount of 0.1 to 80% by weight, based on the polymer P of the dispersion, wherein proteins or protein degradation products are used as drying aids. Gelatin hydrolyzates are preferably used as drying aids.

Description

The The present invention relates to a method for producing Polymer powders by evaporating the volatile components from aqueous Dispersions of film-forming polymers P, which is characterized is that the watery Polymer dispersion still desiccant before the volatiles are evaporated T, which in an amount of 0.1 to 80 wt .-%, based on the polymer P of the dispersion are present, with as drying aids T proteins or protein breakdown products can be used.

Farther The present invention relates to those obtainable by this process Polymer powder, its use as a binder, and mineral Binders that contain such polymer powder.

Aqueous dispersions Film-forming polymers are widely used, for example as Cobinder for mineral building materials or as binders, especially for synthetic resin plasters or highly pigmented interior paints, adhesives or coating agents. Frequently however, is it desirable not the aqueous polymer dispersion itself, but to use the polymer contained therein in powder form.

Around Obtaining the film-forming polymer in powder form becomes the dispersion subjected to a drying process in which the volatile Components of the dispersion by a suitable method, for example by means of spray drying or freeze drying. It should be noted, that the polymer particles of the aqueous dispersion on evaporation of the watery Dispersing medium irreversibly aggregate with each other and secondary particles can form. The secondary particle formation leads to poorer redispersibility, usually associated with poorer application properties of the powder. Also leads they form deposits on the dryer walls and thus reduce the powder yield.

Around the irreversible secondary particle formation to prevent or at least reduce in powder production, one uses drying aids. In many cases, too as a spraying aid referred to as spray drying particularly promotes the formation of irreversibly agglomerated secondary particles. This Effect is all the more pronounced the lower the glass transition temperature (and thus the softening temperature or the minimum film formation temperature) of the polymer particles, especially when they are below the drying temperature lies.

simultaneously drying aids usually reduce the formation of The polymer wall adheres to the dryer wall and thus causes a increase the powder yield.

As Drying aids are common, and not least because of their low price, the salts, preferably the alkali metal, alkaline earth metal or ammonium salts of condensation products aromatic sulfonic acids with formaldehyde (arylsulfonic acid-formaldehyde condensation products) used.

The DE-A-24 45 813 describes a pulverulent polymer which is redispersible in aqueous systems and contains 1 to 20% by weight of a water-soluble, sulfonic acid or sulfonate group-containing condensation product of aromatic hydrocarbons and formaldehyde, for example phenolsulfonic acid or naphthalenesulfonic acid / formaldehyde condensates, as drying aids.

WO 98/03577 discloses salts of naphthalenesulfonic acid-formaldehyde condensation products with a number-average molecular weight M _n below 1500 daltons, which have particularly good spray auxiliary properties.

Similarly, the EP-A-407 889 the use of a water-soluble alkali or alkaline earth metal salt of a phenolsulfonic acid-formaldehyde condensation product as a spraying aid for the preparation of polymer powders redispersible in water.

From WO 98/03576 salts of phenolsulfonic acid-formaldehyde condensation products are also known, which have a number average molecular weight M _n below 1500 daltons and particularly good spray auxiliary properties.

The Use of drying agents, in particular arylsulfonic acid-formaldehyde condensation products, has the disadvantage, however, that the necessary for the application Film formation of the powder particles in the redispersed state disadvantageous being affected.

Furthermore, in the DE-A 10040826 discloses a process for drying dispersions based on styrene-butadiene copolymers, in which spray drying is carried out in the presence of salts of oligomeric arylsulfonic acid-formaldehyde condensates as drying aids. The dispersions described therein contain at least 1.5% by weight of an anionic surface-active compound with at least one C ₆ -C ₃₂ alkyl group. The process described there is distinguished, inter alia, by good redispersibility and filming of the powders obtained. However, these are not completely neutral to some materials, such as cement, and are therefore not very suitable for some areas of application.

In the EP-B 134451 and WO 98/13411 describes the use of various polymeric natural substances in the production of spray-dried dispersion powders.

It is also the subject of EP-A 1036101 a process for the preparation of emulsifier-free, protective colloid-stabilized copolymers based on vinyl aromatics and 1,3-dienes. From the DE-A 19853450 emulsifier-free dispersion powders based on copolymers of styrene and butadiene are also known. The emulsifier-free, protective colloid-containing styrene-butadiene dispersions obtained in this way are, however, very coarse and therefore have high concentrations of the malodorous Diels-Alder product 4-phenylcyclohexene.

Usual spray aids (Drying aids) such as polyvinyl alcohol, naphthalenesulfonic acid-formaldehyde condensates, Phenolsulfonic acid-formaldehyde condensates, polymaleic or polyacrylic acid form after spray drying with acrylamide-free dispersions based on copolymers of styrene and butadiene among the usual Conditions at subsequent Filming often cracked films. A faultless filming of the redispersed dispersion powder is for an application in many systems, for example in mortar modification or necessary in the painting.

The The present invention was therefore based on the object, the described To remedy disadvantages and a process for the preparation of polymer powders to develop which one if possible easy to do and leads to polymer powders, which among others are colorless and odorless behave neutrally in many materials, good redispersibility and filming show and about it cement rheology if possible little influence.

This Task became surprising solved by a process for the production of polymer powders, at which one first the fleeting Ingredients from aqueous Dispersions of film-forming polymer P evaporate, which thereby is characterized that the watery Polymer dispersion and drying aids before the volatiles are evaporated T, which in an amount of 0.1 to 80 wt .-%, based on the polymer P of the dispersion are present, with as drying aids T proteins or protein breakdown products can be used.

film-forming means that the polymer particles of the aqueous dispersion or Powder particles in an aqueous Redispergat when evaporating the water (drying) above one for her specific temperature, the minimum film forming temperature MFT, merge and a coherent Form polymer film. aqueous Redispergate means an aqueous Dispersion of the polymer powder.

The Proteins or protein breakdown products used as drying aids T. are according to the inventive method in an amount of 0.1 to 80% by weight, in particular in an amount from 1 to 50% by weight, preferably in an amount of 2 to 30% by weight and particularly preferably in an amount of 5 to 20 wt .-%, based on the polymer of the dispersion.

It is advisable to use such proteins or protein breakdown products as drying aids, which have a molar mass (weight average, M _w ) of 200 to 500000 g / mol, in particular 500 to 100000 g / mol and particularly preferably 500 to 10000 g / mol.

A protein or protein degradation product is used as a drying aid in the process according to the invention. Suitable starting proteins are obtained, for example, from animal or vegetable sources. These include, for example, animal proteins, such as gelatin, casein or fish proteins, which are obtained, for example, from hair, horns, hooves, claws, nails, bones or milk by conventional methods. Vegetable proteins include, for example, proteins from rice, wheat, potatoes or oil seeds, which are also obtained in the usual way. To produce protein breakdown products, these starting proteins can be broken down into oligo- and polypeptides with a lower molecular weight than the starting proteins with the aid of acids, alkalis or enzymes. Particularly suitable drying aids are gelatin, Gelatin degradation products or gelatin hydrolyzates. Heavily degraded gelatin derivatives, such as the Gelita ^® brands from the German gelatin factories, such as Gelita ^® Sol D, are preferably used.

• (a) 80 bis 100 Gew.-% wenigstens eines Monomers, das ausgewählt ist unter vinylaromatischen Verbindungen, Estern aus α,β-monoethylenisch ungesättigten C₃-C₆-Carbonsäuren und C₁-C₁₂-Alkanolen, vorzugsweise C₁-C₈-Alkanolen, Vinyl- und Allylestern von C₁-C₁₂-Carbonsäuren und konjugierten C₄-C₁₀-Diolefinen, und
• (b) 0 bis 20 Gew.-% wenigstens eines sonstigen Monomers, das wenigstens eine ethylenisch ungesättigte Gruppe aufweist.

Suitable polymers for the process according to the invention and the polymer powder likewise according to the invention are essentially all film-forming polymers which form aqueous dispersions or can be prepared as an aqueous dispersion. These are usually polymers which are composed of ethylenically unsaturated monomers, for example from:

• (a) 80 to 100% by weight of at least one monomer selected from vinyl aromatic compounds, esters of α, β-monoethylenically unsaturated C ₃ -C ₆ carboxylic acids and C ₁ -C ₁₂ alkanols, preferably C ₁ -C _8- alkanols, vinyl and allyl esters of C ₁ -C ₁₂ carboxylic acids and conjugated C ₄ -C ₁₀ diolefins, and
• (b) 0 to 20% by weight of at least one other monomer which has at least one ethylenically unsaturated group.

All Quantities for Monomers are at 100% by weight, i.e. on the total amount to be polymerized Monomers related.

Examples of vinyl aromatic compounds are styrene, α-methylstyrene, C ₁ -C ₄ -alkylstyrenes such as o-vinyltoluene and tert-butylstyrene.

at the esters of α, β-monoethylenic unsaturated carboxylic acids it is in particular to esters of acrylic acid and methacrylic acid. Examples for such Esters are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate or dodecyl (meth) acrylate.

useful Vinyl and alkyl esters are vinyl acetate, vinyl propionate, vinyl n-butyrate, Vinyl laurate and vinyl stearate and the corresponding allyl esters.

Suitable conjugated C ₄ -C ₁₀ diolefins include butadiene and isoprene.

• – ethylenisch ungesättigte Monomere mit Säuregruppe wie Mono- und Dicarbonsäuren mit 3 bis 8 C-Atomen wie Acrylsäure, Methacrylsäure, Crotonsäure, Acrylamidoglykolsäure, Vinylessigsäure, Maleinsäure, Itaconsäure und die Halbester der Maleinsäure mit C₁-C₄-Alkanolen, ethylenisch ungesättigte Sulfonsäuren wie Vinylsulfonsäure, Allylsulfonsäure, Styrolsulfonsäure, 2-Acrylamidomethylpropansulfonsäure, und ethylenisch ungesättigte Phosphonsäuren, z. B. Vinylphosphonsäure, Allylphosphonsäure, Styrolphosphonsäure und 2-Acrylamido-2-Methylpropanphosphonsäure und ihre wasserlöslichen Salze, beispielsweise ihre Alkalimetallsalze, vorzugsweise Acrylsäure und Methacrylsäure. Derartige Monomere können in den Polymeren P in einer Menge von bis zu 10 Gew.-%, z.B 0,1 bis 10 Gew.-%, vorzugsweise 0,1 bis 4 Gew.-%, enthalten sein;
• – Amide ethylenisch ungesättigter Carbonsäuren, wie Acrylamid und Methacrylamid, sowie die N-Alkylolamide, vorzugsweise die N-Methylolamide ethylenisch ungesättigter Carbonsäuren, wie N-Methylolacrylamid und N-Methylolmethacrylamid. Derartige Monomere können in den Polymeren P in einer Menge von bis zu 10 Gew.-%, z.B 0,1 bis 10 Gew.-%, vorzugsweise 0,1 bis 4 Gew.-%, enthalten sein;
• – Hydroxyalkylester ethylenisch ungesättigter Carbonsäuren, insbesondere Hydroxyethyl- und Hydroxypropylester, z. B. Hydroxyethylacrylat, Hydroxypropylacrylat, Hydroxyethylmethacrylat und Hydroxypropylmethacrylat. Derartige Monomere können in den Polymeren P in einer Menge von bis zu 10 Gew.-%, z.B 0,1 bis 10 Gew.-%, vorzugsweise 0,5 bis 6 Gew.-%, enthalten sein
• – Acrylnitril und Methacrylnitril. Derartige Monomere können in den Polymeren P in einer Menge von bis zu 10 Gew.-%, z.B 0,5 bis 10 Gew.-% enthalten sein.
• – Reaktive Monomere: Zu den reaktiven Monomeren zählen solche, die eine zur Vernetzung geeignete reaktive Funktionalität aufweisen. Hierzu zählen neben den vorgenannten ethylenisch ungesättigten Carbonsäuren, ihren N-Alkylolamiden und Hydroxyalkylestern Monomere, die eine Carbonylgruppe oder eine Epoxygruppe aufweisen, beispielsweise N-Diacetonacrylamid, N-Diacetonmethacrylamid, Acetylacetoxyethylacrylat und Acetylacetoxyethylmethacrylat, Glycidylacrylat und Glycidylmethacrylat. Derartige Monomere können in den Polymeren P in einer Menge von bis zu 10 Gew.-%, z.B 0,5 bis 10 Gew.-% enthalten sein.
• – und vernetzende Monomere. Zu den vernetzenden Monomeren zählen solche die wenigstens zwei nicht konjugierte ethylenisch ungesättigte Bindungen aufweisen, z. B. die Di- und Triacrylate bzw. -methacrylate von Di- und trifunktionellen Alkoholen, z. B. Ethylenglykoldiacrylat, Diethylenglykoldiacrylat, Triethylenglykoldiacrylat, Butandioldiacrylat, Hexandioldiacrylat, Trimethylolpropantriacrylat und Tripropylenglykoldia crylat. Derartige Monomere können in den Polymeren P in einer Menge von bis zu 2 Gew.-%, vorzugsweise nicht mehr als 1 Gew.-%, z.B 0,01 bis 2 Gew.-%, vorzugsweise 0,01 bis 1 Gew.-%, enthalten sein. In einer bevorzugten Ausführungsform enthalten die Polymere P kein vernetzendes Monomer einpolymerisiert.

Examples of the monomers (b) are:

• - Ethylenically unsaturated monomers with an acid group such as mono- and dicarboxylic acids with 3 to 8 carbon atoms such as acrylic acid, methacrylic acid, crotonic acid, acrylamidoglycolic acid, vinyl acetic acid, maleic acid, itaconic acid and the half esters of maleic acid with C ₁ -C ₄ alkanols, ethylenically unsaturated sulfonic acids such as Vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, 2-acrylamidomethylpropanesulfonic acid, and ethylenically unsaturated phosphonic acids, e.g. B. vinylphosphonic acid, allylphosphonic acid, styrenephosphonic acid and 2-acrylamido-2-methylpropanephosphonic acid and their water-soluble salts, for example their alkali metal salts, preferably acrylic acid and methacrylic acid. Such monomers can be present in the polymers P in an amount of up to 10% by weight, for example 0.1 to 10% by weight, preferably 0.1 to 4% by weight;
• Amides of ethylenically unsaturated carboxylic acids, such as acrylamide and methacrylamide, and also the N-alkylolamides, preferably the N-methylolamides of ethylenically unsaturated carboxylic acids, such as N-methylolacrylamide and N-methylolmethacrylamide. Such monomers can be present in the polymers P in an amount of up to 10% by weight, for example 0.1 to 10% by weight, preferably 0.1 to 4% by weight;
• - Hydroxyalkyl esters of ethylenically unsaturated carboxylic acids, especially hydroxyethyl and hydroxypropyl esters, e.g. B. hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate. Such monomers can be present in the polymers P in an amount of up to 10% by weight, for example 0.1 to 10% by weight, preferably 0.5 to 6% by weight
• - acrylonitrile and methacrylonitrile. Monomers of this type can be present in the polymers P in an amount of up to 10% by weight, for example 0.5 to 10% by weight.
• - Reactive monomers: reactive monomers include those which have a reactive functionality suitable for crosslinking. In addition to the aforementioned ethylenically unsaturated carboxylic acids, their N-alkylolamides and hydroxyalkyl esters, these include monomers which have a carbonyl group or an epoxy group, for example N-diacetone acrylamide, N-diacetone methacrylamide, acetylacetoxyethyl acrylate and acetylacetoxyethyl methacrylate, glycidyl acrylate and glycidyl methacrylate. Monomers of this type can be present in the polymers P in an amount of up to 10% by weight, for example 0.5 to 10% by weight.
• - and crosslinking monomers. Crosslinking monomers include those which have at least two non-conjugated ethylenically unsaturated bonds, e.g. B. the di- and triacrylates or methacrylates of di- and trifunctional alcohols, for. B. ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol koldiacrylate, butanediol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate and tripropylene glycol diacrylate. Such monomers can be present in the polymers P in an amount of up to 2% by weight, preferably not more than 1% by weight, for example 0.01 to 2% by weight, preferably 0.01 to 1% by weight , be included. In a preferred embodiment, the polymers P contain no crosslinking monomer copolymerized.

• – 10 bis 90 Gew.-%, vorzugsweise 20 bis 80 Gew-%, insbesondere 40 bis 75 Gew.-% Styrol und gegebenenfalls ein oder mehrere, davon verschiedene vinylaromatische Monomere,
• – 10 bis 90 Gew.-%, vorzugsweise 20 bis 80 Gew.-%, insbesondere 25 bis 60 Gew.-% 1,3-Butadien, gegebenenfalls in Mischung mit einem anderen konjugierten Diolefin wie Isopren und gegebenenfalls
• – bis 20 Gew.-%, vorzugsweise bis 10 Gew.-%, z.B. 0,1 bis 20 Gew.-%, vorzugsweise 0,1 bis 10 Gew.-% ein oder mehrere der vorgenannten Monomere (b).

The process according to the invention is preferably suitable for the production of polymer powders based on styrene-butadiene copolymers. The term copolymer is not to be understood as restrictive in this context and also includes those polymers which, in addition to styrene and butadiene, also contain other ethylenically unsaturated monomers in copolymerized form. Styrene-butadiene copolymers are usually made up of:

• 10 to 90% by weight, preferably 20 to 80% by weight, in particular 40 to 75% by weight, of styrene and optionally one or more vinyl aromatic monomers different therefrom,
• - 10 to 90 wt .-%, preferably 20 to 80 wt .-%, in particular 25 to 60 wt .-% 1,3-butadiene, optionally in a mixture with another conjugated diolefin such as isoprene and optionally
• Up to 20% by weight, preferably up to 10% by weight, for example 0.1 to 20% by weight, preferably 0.1 to 10% by weight, of one or more of the aforementioned monomers (b).

The weight ratio of vinyl aromatic monomers to butadiene is usually in the Range from 1: 9 to 9: 1, especially in the range from 4: 1 to 1: 4 and very particularly preferably in the range from 3: 1 to 1: 1.

• – 20 bis 80 Gew.-%, insbesondere 40 bis 75 Gew.-% Styrol
• – 20 bis 80 Gew.-%, insbesondere 25 bis 60 Gew.-% Butadien, und gegebenenfalls
• – 0,1 bis 10 Gew.-%, vorzugsweise 0,1 bis 5 Gew.-% Carboxylgruppen enthaltendende Monomere, insbesondere Acrylsäure, Methacrylsäure und/oder Itaconsäure.

In a preferred embodiment of the present invention, the polymer P is composed of:

• - 20 to 80 wt .-%, in particular 40 to 75 wt .-% styrene
• - 20 to 80 wt .-%, in particular 25 to 60 wt .-% butadiene, and optionally
• 0.1 to 10% by weight, preferably 0.1 to 5% by weight, of monomers containing carboxyl groups, in particular acrylic acid, methacrylic acid and / or itaconic acid.

Especially the method according to the invention is suitable for the production of polymer powders in which the polymer in the Dispersion a glass transition temperature (DSC, midpoint temperature, ASTM D 3418-82) of 65 ° C, in particular 50 ° C, especially preferably 30 ° C does not exceed. Generally the glass transition temperature is the polymers at least -60 ° C, preferably at least -40 ° C and in particular at least -20 ° C. The glass transition temperature of a polymer corresponds approximately the minimum film-forming temperature or is slightly higher.

wobei X¹, X², ..., Xⁿ die Massenbrüche 1, 2, ..., n und T_g ¹, T_g ², ..., T_g ⁿ die Glasübergangstemperaturen der jeweils nur aus einem der Monomeren 1, 2, ..., n aufgebauten Polymeren in Grad Kelvin bedeuten. Letztere sind z.B. aus Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol. A 21 (1992) S. 169 oder aus J. Brandrup, E.H. Immergut, Polymer Handbook 3^rd ed., J. Wiley, New York 1989 bekannt.It is often helpful to estimate the glass transition temperature T _{g of} the dispersed polymer. According to Fox (TG Fox, Bull. Am. Phys. Soc. (Ser. II) 1, 123 [1956] and Ullmanns Encyklopadie der Technische Chemie, Weinheim (1980), pp. 17, 18) the following applies to the glass transition temperature of copolymers large molar masses in good nutrition

where X ¹ , X ² , ..., X ^{n are} the mass fractions 1, 2, ..., n and T _g ¹ , T _g ² , ..., T _g ^{n are} the glass transition temperatures of only one of the monomers 1 , 2, ..., n mean polymers in degrees Kelvin. The latter are, for example, from Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol. A 21 (1992) p 169 or ^rd ed from J. Brandrup, EH Immergut, Polymer Handbook 3rd, J. Wiley, New York 1989 known.

Preferred polymer dispersions are also those in which the weight-average diameter d _{w of} the dispersed polymer particles is ≥ 100 nm. Usually the weight average diameter d _w ≤ 2000 nm.

The d _w value of the particle size is, as usual, defined as the weight average particle size, as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymer 250 (1972) pages 782 to 796. The ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or less than a certain size.

The preparation of the polymer dispersions to be dried is known and is carried out in the case of polymers which are composed of ethylenically unsaturated monomers, generally by means of a radical aqueous emulsion polymerization, ie the monomers are surface-coated in an aqueous emulsion in the presence chemically active substances and at least one radical initiator polymerized.

As Free radical initiators (polymerization initiators) come all those Compounds that are capable of a radical, aqueous Trigger emulsion polymerization. Which includes both organic and inorganic peroxides and hydroperoxides, as well as azo compounds. Redox initiator systems are also suitable, which are usually a peroxide compound and a reducing agent, for example ascorbic acid, hydroxymethanesulfinic Bisulfite adduct with acetone, sodium sulfite or hydrogen sulfite, and / or a transition metal ion, that change its value can, e.g. in the form of water soluble Salts such as iron, vanadium or copper salts and water-soluble complexes of which include. Preferred initiator systems are the peroxides and Hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, and Isopropyl hydroperoxide. The preferred initiators are also the salts peroxidic sulfuric acid, especially their alkali metal salts (e.g. potassium and sodium salts) and / or their ammonium salts. Usually the radical initiator is obtained in an amount of 0.1 to 3% by weight used on the monomers to be polymerized.

Suitable surface-active substances are both protective colloids, ie water-soluble polymers with a molecular weight (number average) M _n ≥ 2000, and also anionic or neutral surface-active compounds (emulsifiers) which, in contrast to the protective colloids, generally have a molecular weight M _n <2000 and have in particular <1000. The surface-active substances are usually used in amounts of up to 10% by weight, preferably 0.1 to 5% by weight, based on the monomers to be polymerized, anionic emulsifiers (compounds AO) generally not more than 1% by weight .-%, for example 0.1 to 1% by weight of the monomers to be polymerized.

suitable Protective colloids are polyvinyl alcohols, starch and cellulose derivatives, polyacrylic acids, Copolymers of acrylic acid and methacrylic acid with hydrophobic monomers and / or with hydroxyl groups Polymers containing monomers, polyacrylamide or vinyl pyrrolidone.

Suitable anionic emulsifiers include salts of such compounds which have at least one C ₆ -C ₃₂ alkyl group, in particular a C ₈ -C ₂₂ alkyl group and a functionality suitable for salt formation with a base, for example a carboxyl, sulfonyl, phosphonyl, phosphate - Or have a sulfate group, preferably a sulfate or sulfonate group. Preferred salts have, as counterions, alkali metal, alkaline earth metal or ammonium ions and in particular sodium, potassium and calcium ions. Such compounds are known, inter alia, from Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208.

Examples of suitable anionic emulsifiers are salts of alkyl sulfates which are derived from linear or branched alcohols, for example fatty or oxo alcohols (alkyl radical: C ₈ -C ₃₂ ), from sulfuric acid semi-esters of ethoxylated alkanols, which are derived from linear or branched alcohols, for example fatty or Oxoalcohols are derived (EO grade: 2 to 50, alkyl radical: C ₈ to C ₃₂ ), from sulfuric acid semi-esters of ethoxylated alkylphenols with preferably linear alkyl radicals (EO degree: 2 to 50, alkyl radical: C ₆ -C ₂₂ ), from alkyl sulfonic acids ( Alkyl radical: C ₈ -C ₃₂ ), of dialkyl esters of sulfosuccinic acid (alkyl radical: C ₆ to C ₃₂ ) and of alkylarylsulfonic acids with a preferably linear alkyl radical (alkyl radical: C ₆ to C ₃₂ ). Suitable anionic emulsifiers include the salts of the di-C ₆ -C ₃₂ alkyl derivatives of bis (phenylsulfonyl) ether, and technical mixtures thereof, for example as DOWFAX ^® 2A1 from Dow Chemical Co. are commercially available.

worin
R¹ für eine C₆-C₃₂-Alkyl- und vorzugsweise eine C₈-C₂₂-Alkylgruppe steht,
R² für Wasserstoff, C₁-C₄-Alkyl, einen annellierten Benzolring, der gegebenenfalls mit C₁-C₄-Alkyl substituiert ist, oder einen Phenoxyrest steht, der gegebenenfalls eine C₆-C₃₂-Alkylgruppe und/oder eine Sulfonat-Gruppe aufweist, und
X ein Kationenäquivalent, bedeutet und vorzugsweise für ein Alkalimetallkation, insbesondere für ein Natrium- oder Kaliumion, für ein Äquivalent eines Erdalkalimetallkations, insbesondere 1/2 Ca²⁺ oder für ein Ammoniumion steht.The compounds of the general formula I are also preferred,

wherein
R ^{1 represents} a C ₆ -C ₃₂ alkyl and preferably a C ₈ -C ₂₂ alkyl group,
R ^{2 represents} hydrogen, C ₁ -C ₄ alkyl, a fused benzene ring which is optionally substituted by C ₁ -C ₄ alkyl, or a phenoxy radical which optionally has a C ₆ -C ₃₂ alkyl group and / or a sulfonate Group, and
X is a cation equivalent, and is preferably an alkali metal cation, in particular a sodium or potassium ion, an equivalent of an alkaline earth metal cation, in particular 1/2 Ca ²⁺ or an ammonium ion.

R ² in formula I is particularly preferably hydrogen. R ¹ is particularly preferably in para position bound to the sulfonate group.

In addition to the anionic emulsifiers mentioned, the polymer dispersion used in the process according to the invention can also contain nonionic surface-active compounds (nonionic emulsifiers). Preferred nonionic emulsifiers are araliphatic emulsifiers, for example ethoxylated mono-, di- and trialkylphenols (EO grade: 3 to 50, alkyl radical: C ₆ -C ₃₂ ), or aliphatic emulsifiers based on alkyl-substituted aromatics, for example ethoxylates of long-chain alcohols, for example from oxo - or fatty alcohols (EO grade: 3 to 50, alkyl radical: C ₈ -C ₃₂ ). These emulsifiers can be present in the polymer dispersion in amounts of up to 10% by weight, preferably up to 4% by weight and in particular up to 2% by weight, for example 0.1 to 10, preferably 0.1 to 4% by weight and in particular 0.2 to 2 wt .-% may be included.

The used surface active Substances can the polymer dispersion to be dried during the drying process or preferably also be added beforehand. It is advisable, the surface active Substances already during the production of the aqueous Use polymer dispersion.

The according to the invention as drying aids Proteins or protein breakdown products used can both while the actual drying process, as well as the aqueous one beforehand Polymer dispersion added become. The proteins or the protein degradation products are preferred before the drying process but after the production of the aqueous Polymer dispersion added to this. The addition of the proteins or the protein breakdown products to the aqueous polymer dispersion can also in portions at certain times after the end of production the watery Polymer dispersion happen.

to Setting the desired one Molecular weight can small amounts during polymerization, e.g. 0.01 to 2% by weight regulating substances are also used on the monomers to be polymerized. Suitable controllers are e.g. Compounds that have a thiol group and / or have a silane group (e.g. t-dodecyl, n-dodecyl mercaptan or mercaptopropyltrimethoxysilane), allyl alcohols or aldehydes, such as formaldehyde, acetaldehyde and the like.

The emulsion polymerization can be carried out either continuously or according to the batch procedure, preferably according to a semi-continuous process. The monomers to be polymerized can be fed continuously to the polymerization batch, including step or gradient procedures. For this purpose, the monomers can be fed to the polymerization both as a monomer mixture and as an aqueous monomer emulsion. In addition to the seed-free production method, to set a defined polymer particle size, the emulsion polymerization can be carried out by the seed latex process or in the presence of seed latex prepared in situ. Methods for this are known and can be found in the prior art (see EP-B 40419 and "Encyclopedia of Polymer Science and Technology", vol. 5, John Wiley & Sons Inc., New York 1966, p. 847).

In a preferred embodiment The present invention uses the polymerization in the presence from 0.01 to 3% by weight and in particular 0.05 to 1.5% by weight of one Seed latex (solids content of the seed latex, based on the total amount of monomers), preferably carried out with seed latex (seed). The Latex usually has a weight-average particle size of 10 up to 400 nm, preferably 20 to 120 nm and in particular 20 to 50 nm on. Its constituent monomers are, for example, styrene, Methyl methacrylate, n-butyl acrylate and mixtures thereof, the Seed latex to a minor extent also ethylenically unsaturated Carboxylic acids, z. B. acrylic acid and / or methacrylic acid and / or their amides, preferably less than 10% by weight polymerized onto the total weight of the polymer particles in the seed latex may contain.

in the Generally one works at polymerization temperatures between Room temperature and 120 ° C, preferably at temperatures from 40 to 110 ° C and particularly preferably between 50 and 100 ° C at a pressure in the range of 1 to 10 bar.

Following the actual polymerization reaction, it may be necessary to make the aqueous polymer dispersions according to the invention largely free of odor carriers, such as residual monomers and other organic volatile constituents. This can be achieved physically in a manner known per se by removal by distillation (in particular by steam distillation) or by stripping with an inert gas. The lowering of the residual monomers can continue chemically by radical postpolymerization, in particular under the action of redox initiator systems, such as z. B. in the DE-A 44 35 423 . DE-A 44 19 518 as well as in the DE-A 44 35 422 are listed. The is preferred Postpolymerization with a redox initiator system made of at least one organic peroxide and an organic sulfite.

On polymer dispersions with polymer contents up to 80% by weight, based on the total weight of the dispersion, is accessible. As a rule, the solids content of those produced in this way Polymer dispersions are in the range from 40 to 60% by weight. The so available Polymer dispersions can then, if necessary, to the one desired for drying Solids content by dilution with a suitable solvent, for example with water or a water-emulsifier mixture and / or by adding an aqueous solution of the drying agent can be set.

The Solids content of the polymer dispersion to be dried, which already contains drying aids, is usually in the range of 10 to 60 wt .-%, preferably in the range from 20 to 55% by weight (each calculated as polymer + Drying aids, based on the total weight of the dispersion).

The Evaporating the volatile Ingredients from the aqueous Polymer dispersion (hereinafter also referred to as drying) takes place in the usual Way, for example by freeze-drying or preferably by Spray drying.

at spray drying the polymer dispersions to be dried in the presence of the Drying aid in a drying tower through which a flow of warm air flows guided is dried. The temperature of the hot air flow is in Usually at the entrance of the drying tower 100 to 200 ° C, preferably 110 to 170 ° C, and on Tower exit approx. 30 to 100 ° C, preferably 50 to 80 ° C. The polymer dispersion to be dried can counteract the flow of warm air or preferably be introduced in parallel into the hot air flow. The addition can be over Single or multi-component nozzles or about a rotating disc. The deposition of the polymer powder takes place in the usual Manner, e.g. using cyclones or filter separators.

Basically, they can used as drying agent T, proteins or protein breakdown products during the Drying process in the form of solutions, for example as aqueous or water-alcoholic Solutions, be added to the polymer dispersion to be dried. Preferably the drying aid is added to the polymer dispersion before drying. The drying agent can be either as a solid or preferably as a solution, z. B. as an aqueous-alcoholic solution or in particular as an aqueous solution be given to the dispersion.

Further you can the polymer dispersion to be dried during the Add an anticaking agent (anti-caking agent) to the drying process. This is a fine-particle inorganic oxide, for example a finely divided silica or a finely divided silicate, e.g. B. talc. Preferably points the finely divided inorganic oxide has an average particle size in the range of 0.01 to 0.5 μm on. Finely divided silica with an average particle size in the range is particularly preferred from 0.01 to 0.5 μm, which can be both hydrophilic and hydrophobic. Most notably mixtures of hydrophilic and hydrophobized are preferred Anti-caking agents are used. The anti-caking agent can be used before or during the Drying of the polymer dispersion can be added. In another embodiment the anticaking agent is placed in a mixing device suitable for solids, for example a vibrator, Wheelchair screw mixer or similar, to the polymer powder.

Provided he wishes, will the anti-caking agent in an amount of 0.5 to 15 wt .-% and preferably in an amount of 2 to 12% by weight based on the polymer powder (or the sum of polymer P + drying aid in the watery Polymer dispersion).

The according to the invention Polymer powders obtained by processes are also the subject of present invention. In the presence of water stand out aqueous Redispergate of the polymer powder and others through an improved film composition. Surprisingly does that invention Process also for better results in spray drying, for example to an elevated Powder yield and reduced deposit formation. Other application technology Properties are surprisingly not adversely affected.

• i wenigstens ein filmbildendes Polymer P,
• ii 0,1 bis 80 Gew.-%, bezogen auf das Polymer P, Proteine bzw. Proteinabbauprodukte als Trocknungshilfsmittels T,
• iii gegebenenfalls oberflächenaktive Verbindungen in einer Menge bis 10 Gew.-%, bezogen auf das Polymer P, und
• iv gegebenenfalls Füllstoffe, Pigmente, Anticakingmittel und/oder übliche Hilfsmittel, z.b. Trocknungshilfsmittel des Standes der Technik, Biozide und/oder Entschäumer.

The polymer powders obtained by the process according to the invention comprise:

• i at least one film-forming polymer P,
• ii 0.1 to 80 wt .-%, based on the polymer P, proteins or protein breakdown products as drying aids by means of T,
• iii optionally surface-active compounds in an amount of up to 10% by weight, based on the polymer P, and
• iv optionally fillers, pigments, anticaking agents and / or customary auxiliaries, for example drying aids of the prior art, biocides and / or defoamers.

The invention Polymer powders are suitable as cobinders in mineral binders and ready-to-use binders, as binders in paints, varnishes, adhesives, coating and sealing compounds, Construction adhesives, e.g. Floor adhesive and in particular tile adhesive, as well as in synthetic resin plasters.

In The polymer powders obtainable according to the invention are particularly suitable as Cobinders in mineral binders or ready-to-use Preparations of these building materials, as well as in building adhesives. These are also subject of the present invention.

Under understands mineral binders and their preparations compositions containing at least one mineral binder such as lime, plaster, clay and / or cement and possibly mineral Supplements contain. The ready-to-use preparation is made by mixing with Water is transferred to the actual building material preparation, which is then when it is left to yourself is in the air or under water, possibly under the action increased Temperature solidified like a stone. In addition to the mineral supplements included mineral building material preparations also common aids, e.g. B. each Depending on the application, thickeners or condensers and defoamers.

preferred mineral binders contain 70 to 100 wt .-% cement and 0 to 30% by weight of gypsum. In particular, cement is the sole mineral Binder. The effect according to the invention is essentially independent of the type of cement. ever according to plans so blast furnace cement, oil shale cement, Portland cement, hydrophobized Portland cement, quick cement, swelling cement or alumina cement, the use of Portland cement as particularly cheap proves.

In typically the dry compositions contain mineral Binders, based on the amount of mineral binder, 0.1 to 30 wt .-%, in particular 0.5 to 10 wt .-% modifying Polymer powders. The weight fraction of polymer to mineral Binder is usually in the range of 1: 100 to 1: 1.

to The mineral is used to improve their processing properties Binders often contain cellulose derivatives and microsilica. First usually work thickening and the latter usually form thixotropic agents, which is the fluidity of the aqueous mortar to further lower his solidification in angry retirement. By adding defoamers (From the aspect of "dry mortar" preferably in Powdered) can have a practical air pore content in the solidified state (5 to 20 vol .-%) of the solidified cementitious mortar can be achieved.

Sand, e.g. Quartz sand, and optionally fillers such as calcium carbonate and pigments such as titanium dioxide or iron oxide, natural and synthetic fibers usually form the rest Surcharges.

Construction adhesives include e.g. B. Floor adhesive and tile adhesive. They contain as an adhesive component at least one polymer powder according to the invention and, depending on the type of formulation, plasticizers, fillers, Dispersing agents, biocides, and optionally water, defoamers, thickeners, Thioxotropic agents and other additives. In a preferred embodiment they also contain a mineral binder, e.g. B. cement. Such preparations are used in particular as tile adhesives. Due to the mineral binder, they are also mineral Binding building materials.

Typical mineral binders and other construction adhesives such as tile adhesives, especially as mineral binders dry preparations, (based on the total weight of the solids contained in them):
10 to 60, preferably 15 to 50% by weight of mineral binder (preferably exclusively cement, in particular Portland cement)
0.1 to 20 frequently 0.2 to 15% by weight, in particular 0.5 to 10% by weight, especially 2 to 8% by weight of polymer powder according to the invention,
up to 25% by weight of conventional auxiliaries, for example defoamers, thickeners, liquefiers and thixotropic agents, and the remainder 30 to 80% by weight of additives, for example sand, fillers (for example CaCO ₃ ), pigments (for example TiO ₂ ) na natural and / or synthetic fibers. Defoamers are generally used in an amount of 0.1 to 2% by weight, thixotropic agents to 2% by weight, plasticizers to 1% by weight.

typical embodiments Mineral binders are cementitious repair or Armierungsmörtel. Here usual Armierungsmörtel to increase their crack bridging ability still natural or synthetic fibers from materials such as Dralon (length e.g. 1 to 10 mm, length-related Mass e.g. 3 to 10 dtex) in an amount of up to 10% by weight. An overview of auxiliary substances and surcharges gives H. Reul in "Handbuch der Bauchemie, publisher for chemical industry, H. Zielkowsky KG, Augsburg, 1991.

A further preferred embodiment mineral binders are tile adhesives. typical As dry preparation, tile adhesives contain, in addition to the polymer powder, that, based on 100% by weight dry preparation, as a rule 0.5 accounts for up to 10% by weight, in particular 2 to 8% by weight, 15 to 50% by weight mineral binder, especially cement, 30 to 80% by weight usual surcharges for this, in particular Quartz sand, e.g. B. with a sieve line of 0.063-0.4 mm, and / or Calcium carbonate, as well as usual aids like thickeners, defoamers, Biocides, dispersing agents, plasticizers (plasticizers), Film forming aids etc. in an amount of 0.1 to 25 wt .-%.

The inventive method for the production of polymer powders is technically easy perform and leads to polymer powders, which include are colorless and odorless compared to many materials et al across from Cement neutral, a useful redispersibility and Show filming and above also practically do not affect cement rheology. The polymer powder according to the invention are readily available and have a very good binding power compared to calcium carbonate and other fillers. Furthermore, it proves to be advantageous that the used Drying aid is a natural product.

Examples

I. Feed materials:

Polymer dispersion D ₁ : aqueous styrene-butadiene dispersion containing 50% by weight of polymer with a glass transition temperature T _g of approx. 4 ° C., the 53% by weight of styrene, 42% by weight of butadiene and 4.5% by weight of acrylic acid and contains 0.5% by weight of itaconic acid in copolymerized form and which is also stabilized with 0.5% by weight, based on the polymer, of a sulfated fatty alcohol ethoxylate (degree of ethoxylation of 2 to 3) as emulsifier. The polymer dispersion had a particle size of 130 nm and corresponded to the dispersion D ₁ described below in DE-A 10040826 on page 7.

The aqueous Polymer dispersion was used in Examples 1 to 3 and Comparative Examples A and B, each with 10% by weight on the polymer of the aqueous Dispersion of a partially or completely water-soluble drying aid T offset.

Polymer dispersion D ₂ : Aqueous styrene-acrylate dispersion corresponds to the dispersion D ₁ described in EP-B 914366 on page 6, from line 28 in paragraph 1.1. This aqueous dispersion was used in Examples 4 to 6 according to the invention.

II. Preparation of the polymer powder

The Polymer dispersions of Examples 1 to 6 according to the invention and of Comparative Examples A and B were in a pilot dryer spray dried. The drying aid T was in each case in an amount of 10% by weight, based on the polymer P of the aqueous Dispersion, added, served as a flow aid, a commercially available Antiblocking agent based on silica gel. The solids content of the spray food was 30% by weight. The atomization was done via a Teflon two-component nozzle (Gap width 1.3 mm), the inlet temperature was 130 ° C, the outlet temperature 60 ° C.

The following drying aids were used:
T ₁ : Gelatine hydrolyzate Solugel LM from PB Gelatins GmbH (Belgium),
Molecular weight (weight average) approx. 3000 g / mol; IEPS (isoelectric point): 4.8-5.2
T ₂ : Gelatine hydrolyzate Solugel P from PB Gelatins GmbH (Belgium),
Molecular weight (weight average) approx. 3800 g / mol; IEPS: 4.8-5.2
T ₃ : collagen hydrolyzate Gelita Sol D from the German gelatine factories, collagen hydrolyzate from bovine split; mol weight (weight average) 2000 to 4000 g / mol; IEPS 3.5-6 corresponds to type B gelatin
T ₄ : Naphthalenesulfonic acid-formaldehyde condensation product as calcium salt prepared according to Example 2.1 (spray aid S ₁ ) EP-B 914366 .
T ₅ : Copolymer of 50 parts by weight of acrylic acid and 50 parts by weight of maleic acid, molecular weight (weight average) approx. 3000 g / mol

II.Ergebnisse

The Results of the examples according to the invention 1 to 6 and Comparative Examples A and B are in the following Table 1 reproduced.

table 1 shows the results of spray drying. The with the drying aid according to the invention Powders produced could be spray dried with high yield without problems are redispersible and show faultless filming.

redispersibility: 30 g of the polymer powder prepared according to II was in a standing cylinder dispersed in 70 ml of deionized water and 4 hours at room temperature leave and then visually assess how strong the Polymer phase had separated from the water phase.

Filming: A polymer film was cast from the redispersed dispersions, and then dried at room temperature for 4 days. The quality of the film was assessed visually as shown in Table 1.

Claims (14)

A process for the preparation of polymer powders by evaporating the volatile constituents from aqueous dispersions of film-forming polymers P, characterized in that the aqueous polymer dispersion, before the volatile constituents are evaporated, also has drying agents T, which in an amount of 0.1 to 80% by weight, based on the polymer P of the dispersion, wherein proteins or protein degradation products are used as drying aids. A method according to claim 1, characterized in that the proteins or protein breakdown products used as drying aids T. in an amount of 1 to 50 wt .-%, based on the polymer P Dispersion are present. Method according to claims 1 or 2, characterized in that the proteins or protein degradation products used as drying aids T have a molar mass (weight average, M _w ) of 500 to 50,000 g / mol. Method according to claims 1 to 3, characterized in that as drying aid T gelatin or gelatin hydrolyzate is used. Method according to one of claims 1 to 4, characterized in that that the polymer in the dispersion is a styrene-butadiene copolymer. Method according to one of claims 1 to 5, characterized in that the polymer in the dispersion has a glass transition temperature T _g below 65 ° C. Method according to one of claims 1 to 6, characterized in that that the polymer dispersion additionally at least one emulsifier in an amount of up to 10% by weight contains on the polymer. Method according to one of claims 1 to 7, characterized in that that the evaporation of the volatile Ingredients from the aqueous Polymer dispersion after a spray drying process he follows. Polymer powder obtainable by a process according to one of the claims 1 to 8. A polymer powder according to claim 9, comprising: i at least one film-forming polymer P, ii 0.1 to 80% by weight, based on the polymer P, proteins or protein breakdown products as Drying aids T iii if necessary, neutral surface-active Compounds in an amount up to 10 wt .-%, based on the polymer P, and iv optionally fillers, Pigments, anti-caking agents and / or usual auxiliaries. Use of the polymer powder according to claim 9 or 10 as cobinder in mineral binders and ready - to - use binders, as binders in Paints, varnishes, adhesives, coating and sealing compounds, Building adhesives and in synthetic resin plasters. Mineral binding building material containing a polymer powder according to one of claims 9 or 10. Mineral binding material according to claim 12 in the form of a dry mortar preparation, consisting of - 10 to 60% by weight of mineral binder, - 0.1 to 30% by weight of polymer powder according to one of Claims 9 or 10, - up to 25% by weight auxiliaries and additives customary for mineral binding materials - as a residual quantity, additives such as sand, fillers, pigments, natural fibers and / or synthetic fibers. Mineral binder building material according to claim 12 in Form of a construction adhesive dry preparation consisting of - 15 to 50% by weight mineral binder 0.5 to 10% by weight of polymer powder, according to one of the claims 9 or 10 - 0.1 up to 25% by weight for Building adhesives usual aid - 30 up to 80 wt% for Building adhesives usual Supplements