DE19636490A1 - Production of aqueous polymer dispersion for adhesives, binders etc. - Google Patents

Abstract

Production of aqueous polymer dispersions (I) comprises radical-initiated aqueous emulsion polymerisation of ethylenic monomers to give a dispersion of a first polymer followed by radical polymerisation of other monomers in one or more subsequent stages (i) in the presence of the first polymer, with the following features: (a) the first polymer has a Tg of Tg1, (b) the monomers polymerised in stages (i) are such that the isolated statistical copolymerisation of these monomers gives a first polymer with a Tg which approaches a limiting value of Tg1 with increasing molecular weight, (c) for each Tgi the difference Tgi - Tg1 = at least 10 deg C, (d) the amount of monomers polymerised in the first polymer is 85-99.9 wt.% of the total amount (TM) polymerised in the entire process, (e) the total amount of monomers polymerised in all stages (i) is 0.1-15 wt.% of TM, (f) in each stage (i), the addition of monomer is carried out so that monomer conversion (polymerisation) does not exceed 50 mol% of the amount already in the reactor at any time up to the end of addition, (g) apart from monomers with two conjugated double bonds, the total amount of monomer polymerised in all stages (i) contains no monomers with more than one ethylenically unsaturated group, and (h) apart from monomers with two conjugated double bonds, the total amount of monomer used for the production of the first polymer includes not more than 5 wt.% monomers with more than one unsaturated group. Also claimed are (a) dispersions (I) obtained by this process; (b) polymer powder obtained by spray drying (I); (iii) polymers obtained by this process; and (iv) aqueous dispersions containing such polymers.

Description

The present invention relates to a method of manufacture aqueous polymer dispersions, in which one first of all having at least one ethylenically unsaturated group Compounds (monomers) according to the radical method aqueous emulsion polymerization in an aqueous medium dispersed polymer 1 produced and there after in one or more successive polymerizations I stage further monomers in the presence of the in the aqueous medium disperse distribution polymer 1 with the proviso radically polymerized that

• a) the polymer 1 has a glass transition temperature Tg¹;
• b) the monomers polymerized in each of the polymerization stages i are such that with isolated static copolymerization of these monomers a polymer i would be obtained whose glass transition temperature tends towards the limit value Tg ⁱ with increasing molecular weight;
• c) for each Tg ⁱ the difference Tg ⁱ -Tg¹ is 10 ° C;
• d) the amount of those used to produce the disperse distribution polymer present 1 polymerized monomers, based on the amount of total polymeri in the process based monomers, <85 (preferably 87 and especially before 90) wt% and 99.9 wt%;
• e) the total amount of i poly in all polymerization stages merized monomers, based on the total amount of Process total polymerized monomers, 0.1 wt% and <15 (preferably 13 and particularly preferably 10)% by weight amounts to;
• f) in each of the polymerization stages i, the monomers to be polymerized in this polymerization stage i are added to the polymerization vessel in such a way that, at the end of the addition, the polymerization conversion U ⁱ of monomers to be polymerized in stage i and already added to the polymerization vessel is never 50 mol% exceeds;
• g) the total amount of i polymerized monomers, apart from two conjugated ones monomers containing ethylenically unsaturated groups,  does not include monomers that are more than one ethylenic have unsaturated group and
• h) the total amount of the polymer 1 polymerized monomers, apart from two conjugated ones monomers containing ethylenically unsaturated groups, comprises no more than 5% by weight of monomers which are more than have an ethylenically unsaturated group.

U ⁱ is defined as the percentage of the monomers already added to the polymerization vessel for the polymerization in the i th polymerization stage, the polymerization of which has already taken place at the time of the addition of further monomers to be polymerized in the polymerization stage i.

A polymerization stage i is defined as the time period within which the rate of polymerization (which per time unit polymerized molar amount of monomers) of one starting from the lowest value increases until after through run a maximum value either by consuming the in this stage to be polymerized monomers and / or the poly merization initiators and / or by targeted external influence (e.g. lowering the polymerization temperature, adding Polymerization inhibitors) decreases again with the onset of increase again in the next polymerization stage.

Furthermore, the present invention relates to the application of the Aqueous polymer obtainable according to the method of the invention dispersions and their use for coating, gluing, Sealing or impregnation, using as a binder for finely divided mineral and / or organic substances Coating compositions containing fillers and / or pigments or molded body is preferred.

Aqueous polymer dispersions are fluid systems which as disperse phase in aqueous dispersion medium polymer coil (Polymer particles) in a substantially stable disperser Distribution included included.

Just like polymer solutions when the solution evaporates by means of aqueous polymer dispersions on evaporation of the aqueous dispersion medium the ability to polymerize Form films, which is why aqueous polymer dispersions in a lot times as a binder, e.g. B. for paints or masses for coating wood, roofs or leather.  

In numerous cases, both such polymer films or the coating compositions containing them as well as the one with them coated substrate high humidity and / or temperature exposed to fluctuations that are both extreme expansions also contractions of the films and / or the substrate on which they are stick, condition, d. that is, in many cases occur in the films high voltages that only undamaged the films (without Breakage or crack formation) can withstand if the to the necessary work is as high as possible.

A suitable measure to be carried out on a polymer film Ending work is the product according to EP-B 264 903 Elongation at break and tensile strength of the polymer film. Beneficial Polymer films are therefore those whose product is made of tear elongation and tensile strength is increased, being among the one such increased product polymer films preferred are those that are both elevated at the same time Elongation at break as well as an increased tensile strength. The latter objective is particularly difficult to achieve because usually measures to improve the tensile strength Elongation at break and vice versa (usually occurs determining these mechanical properties of a poly merisatfilms at a temperature above its Tg). The object of the present invention was therefore a To provide procedures, its application on the one hand an increase in causing a film to break aqueous polymer dispersion ("a polymer 1") required Work allowed and at the same time at the same time both the highest possible elongation at break as well as possible high tear strength of the polymer film guaranteed.

Accordingly, the process defined at the outset for the production found an aqueous polymer dispersion.

Poly similar to the polymerization process according to the invention Merization processes are from Polymer, 1985, Vol. 26, p. 1359 to 1364, from J. of Appl. Polymer Science, Vol. 56, pp. 793 to 802 (1995), from EP-A 359 562, from EP-A 522 789 and from EP-A 187 505 known. However, a disadvantage of this method is that that they have the mechanical properties desired according to the invention profile of the resulting polymer films either not in are able to set in a satisfactory manner and / or in the after following polymerization stages are mandatory for the copolymerization of polyethylenically (non-conjugated) unsaturated monomers need that are comparatively expensive.  

Furthermore, there are numerous at least two-stage literature Process of radical aqueous emulsion polymerization be known (e.g. US-A 3 562 235 and EP-A 600 478) in which the addition to polymerize in the different polymerization stages the monomers into the polymerization vessel in accordance with their ver need and thus takes place so that until the end of the addition the polymerization conversion of those to be polymerized in one stage and the monomers already added to the polymerization vessel most of the time is above 80 mol%. Disadvantageous However, this method is that they are usually the fiction according to the desired mechanical property profile not to set the polymer films in a satisfactory manner assets and / or comparatively complicated in their implementation are adorned.

It is essential for the process according to the invention that monomers, which are polymerized in stage i, the polymerization be added in such a way that a significant part of them in advance of their polymerization in those already in the polymerisa tion vessel, dispersed in the aqueous medium, Polymer particles can dissolve and thus disper in this gated polymer particles are dissolved (i.e. after Swelling of the dispersed polymer particles) polymerized becomes.

The process according to the invention is therefore preferably such that, in each polymerization stage i, the monomers to be polymerized in this polymerization stage i are added to the polymerization vessel in such a way that, until the addition is complete, the polymerization conversion U ⁱ of in stage i and the polymerization vessel is polymerized monomers already added never exceed 40 mol%. The above-mentioned U ⁱ is particularly preferably 30 mol% until the end of the addition and very particularly preferably 20 or 10 mol% or 5 mol%. It is particularly expedient to largely interrupt the polymerization when the monomers to be polymerized in stage i are added to the polymerization vessel, ie the polymerization of the monomers to be polymerized in stage i only after addition of the total amount of the monomers to be polymerized in stage i To carry out the polymerization vessel. The total amount of the monomers to be polymerized in stage i, as always in the process according to the invention, can be added to the polymerization vessel either all at once or in portions. As already mentioned, interruption of the polymerization can be brought about by measures such as lowering the temperature, adding polymerization inhibitors (radical scavengers such as hydroquinone), initiator consumption etc.

The swelling of the water in the polymerization vessel Polymer particles in a disperse medium through those to be polymerized at a polymerization stage i Monomers are usually relieved by having them Monomers not pre-emulsified in an aqueous medium, but in pure form admits. Furthermore, it is normally in accordance with the invention advantageous if the addition is essentially interrupted Polymerization at elevated temperature, e.g. B. 50 to 95 ° C or 60 up to 80 ° C. Accelerate such elevated temperatures usually the desired dissolving or swelling process. Last terer is also positively influenced by the fact that sufficient time is made available. In other words, if necessary, they are stored in one Polymerization stage i monomers to be polymerized the poly added to the polymerization vessel and the content of the polymerization vessel, preferably with stirring, with interrupted polymer for a long time (from several minutes to several hours up to several days) at a preferably elevated temperature left to yourself. Such a measure is special often beneficial when the polymer 1 monomers contains polymerized, the two non-conjugated ethylenically have unsaturated groups. The latter network them in one Polymer particles contain polymer chains, which the desired swelling difficult.

According to the invention, it is therefore generally favorable if the Total amount of 1 polymerized to produce the polymer ten monomers, apart from two conjugated ethylenically monomers containing saturated groups, not more than 2% by weight of monomers comprising more than one ethylenically unsaturated Have group. Usually it is according to the invention from Vor partly if the polymer 1 does not crosslink at all polymerized acting monomers contains.

Although two conjugated ethylenically unsaturated groups pointing monomers such as butadiene in the context of a radical aqueous emulsion polymerization normally hardly any characterized networking (the reactivity of the second ethylenically unsaturated group is usually reduced), According to the invention, polymer 1 advantageously does not contain any having two conjugated ethylenically unsaturated groups Polymerized monomers. The same applies to the Polymerisa levels i.  

In the method according to the invention, this preferably follows Production of the polymer 1 is only a polymerization grade i. A part of the polymerization can stage i monomers to be polymerized already in the context of the Her Position of the polymer 1 in the polymerization vessel be that. This is e.g. B. the case when you consider the radical aqueous emulsion polymerization for the preparation of the polymer sats 1 breaks off before entering the polymerization vessel given monomers have been completely polymerized. The remaining monomers then form part of the subsequent polymerization stage i (accordingly can also with several polymerization stages i).

The term glass transition temperature means in this document according to the DSC (Differential Scanning Calorimetry, 20 ° C / min, midpoint) determined glass transition temperature (cf. ASTM D 3418-82).

According to the invention, Tg 1 is expediently frequently from -60 ° C. to + 110 ° C. That is, embodiments of the method according to the invention are z. B. those with Tg¹ from -50 ° C to + 50 ° C, or with Tg¹ of -50 ° C to + 20 ° C, or with Tg¹ from -50 ° C to 0 ° C or with Tg¹ from -40 ° C to -20 ° C.

For a given Tg ⁱ for the i-th polymerization stage, a monomer composition to be polymerized in the i-th polymerization stage can be compiled in a simple manner using the Fox equation. After Fox (TG Fox, Bull. Am. Phys. Soc. (Ser. II) 1, 123 (1956) and Ullmann’s Encyklopadie der Technische Chemie, Verlag Chemie, Weinheim, 1980, Vol. 19, 4th edition, p 18) applies to the high molecular weight limit of the glass transition temperature of statistical copolymers in good approximation

where X¹, X²,. . . , X ⁿ the mass fractions of the monomers 1, 2,. . . , n and Tg¹, Tg²,. . . , Tg ^{n are} the high molecular weight limit values of the glass transition temperatures of only one of the monomers 1, 2,. . . , or n assembled polymers in degrees Kelvin mean:

The high molecular limits of the glass transition temperatures for the homopolymers of most monomers are known and z. B. in Ullmann's Encyclopedia of Industrial Chemistry, VCH Weinheim, 1992, fifth edition, Vol. A21, p. 169. Other sources of glass transition temperatures of homopolymers are e.g. BJ Brandrup, EH Immergut, Polymer Handbook 1 ^st Ed. J. Wiley, New York 1966, 2nd Ed. J. Wiley, New York 1975, and 3rd Ed. J. Wiley, New York 1989.

A statistical copolymerization of a monomer composition i of a polymerization stage i can essentially be achieved experimentally by polymerizing a corresponding monomer mixture in the feed process according to the radical aqueous emulsion polymerization method. That is, the monomer mixture is pre-emulsified in the aqueous phase and, depending on consumption, it is run into the polymerization vessel with the addition of initiators so that the polymerization conversion of the monomers already in the polymerization vessel is always 95 mol%. Suitable initiators are preferably sodium peroxodisulfate and the polymerization temperature is normally 60 to 90 ° C. The substances recommended in this document for the preparation of the aqueous polymer dispersions according to the invention can be used as dispersants. The molecular weight can be adjusted in a manner known per se by the use of substances which regulate the molecular weight (for example mercaptans) and / or the amount of initiator used. In the absence of substances regulating the molecular weight and the use of 0.1 to 2% by weight, based on the amount of monomers, of polymerization initiator, an aqueous polymer dispersion can be obtained whose glass transition temperature corresponds to the high molecular weight limit Tg ⁱ .

According to the invention, the difference Tg ⁱ -Tg 1 must be at least 10 ° C. for each Tg ⁱ . Ie, embodiments of the United method are z. B. those in which for each polymerization stage i the difference Tg ⁱ -Tg¹ 10 ° C to 220 ° C, or 30 ° C to 200 ° C, or 50 ° C to 180 ° C, or 80 ° C to 150 ° C , or 100 ° C to 130 ° C.

If the difference Tg ⁱ -Tg¹ has a comparatively small value for all polymerization stages ⁱ , the process according to the invention in particular requires a pronounced increase in the elongation at break. If the difference Tg ⁱ -Tg¹ for all polymerization stages i has a comparatively high value, the process according to the invention in particular requires a pronounced increase in the tensile strength. It is favorable according to the invention if the differences Tg ⁱ -Tg¹ are 60 to 190 ° C.

The above applies in particular if Process according to the invention for the preparation of the polymer 1 only one polymerization stage i follows.  

According to the invention, the weight-average diameter _{w of} the polymer 1 in disperse distribution in an aqueous medium can extend over a wide range. For example, _w can be 50 nm to 2000 nm. Frequently, _{w will be} 100 nm to 1000 nm or 200 nm to 500 nm.

Correspondingly, the number average molecular weight _n of polymer 1 can cover a wide range of values. For example, _n can be 50,000 to 5 · 10⁶ or 100,000 to 3 · 10⁶ or 250,000 to 1 · 10⁶. Of course, the preparation of the polymer 1, the molecular weight regulating substances such. B. mercaptans (mercaptoethanol, tert-dodecyl mercaptan etc.) and / or halogenated hydrocarbons (z. B. methylene chloride, carbon tetrachloride, chloroform, bromoform, dichloroethane, trichloroethane), and / or C₁ to C₄ alcohols such as methanol and allyl alcohol will. The same applies to the polymerization stages i. Preferably, both the polymer 1 and the polymerization stages i are produced without the use of substances which regulate the molecular weight.

According to the invention, the total amount of all polymerizations stages i polymerized monomers, based on the amount of im Polymerization of the process according to the invention as a whole ten monomers, 0.1% by weight to <15% by weight, particularly preferably 0.1 up to 10% by weight. In many cases, it is useful to have one in ent speaking total amount obtained in all polymers stages i polymerized monomers from 0.5% by weight to 8% by weight or from 1% by weight to 6% by weight or from 2% by weight to 6% by weight.

In principle, according to the invention, all monoethylenically unsaturated monomers which can be polymerized by free radicals are suitable for the preparation of polymer 1 and for polymerization in polymerization stages i. These are monomers such as styrene, α-methylstyrene, o-chlorostyrene, α-phenyl styrene or vinyl toluenes, esters of vinyl alcohol and monocarboxylic acids having 1 to 18 carbon atoms such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters from allyl alcohol and monocarboxylic acids having 1 to 18 carbon atoms, such as allyl acetate, allyl propionate, allyl n-butyrate, allyl laurate and allyl stearate, esters of α, β-monoethylenically unsaturated mono- and dicarboxylic acids preferably having 3 to 6 carbon atoms, such as, in particular, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, with alkanols generally having 1 to 12, preferably 1 to 8 and in particular 1 to 4, carbon atoms, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate , isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, hexyl acrylate, hexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, 2-ethylhexylac rylate, 2-ethylhexyl methacrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, iso-bornyl acrylate, iso-bornyl methacrylate, norbornyl acrylate, 4-tert-butylcyclohexyl acrylate, 4-tert-butylcyclohexyl methacrylate, 3,3,5-trimethyl cyclohexyl 5-Trimethylcyclohexyl methacrylate, maleic acid dimethyl ester or maleic acid n-butyl ester and nitriles of α, β-monoethylenically unsaturated carboxylic acids such as acrylonitrile and methacrylonitrile. Suitable C _4-8 conjugated dienes are e.g. B. 1,3-butadiene and isoprene. Also of importance are commercially available monomers VEOVA® 9-11 (VEOVA X is a trade name of Shell and stands for vinyl esters [of carboxylic acids, which are also referred to as Versatic® X acids] of the general formula

where R¹, R² and R³ are alkyl radicals, the total number of Carbon atoms (R¹ + R² + R³) is X minus 2).

As a rule, the above-mentioned monomers are recruited Main parts of the polymer 1 and the polymerization stage fen i. As a rule, the main proportion combines more than 75% by weight of polymer 1 or the respective polymerization stage i yourself. Monomers that polymerize by themselves usually homo polymers result in increased water solubility have, are both in the polymer 1 and in the polymer levels i usually only in modifying quantities, usually less than 25% by weight, usually 0.1 to Contain 10 wt .-% or 0.1 to 5 wt .-%.

Examples of such monomers are 3 to 6 carbon atoms α, β-monoethylenically unsaturated mono- and dicarboxylic acids and whose amides such as B. acrylic acid, methacrylic acid, maleic acid, Fumaric acid, itaconic acid, acrylamide and methacrylamide, further Vinyl sulfonic acid, acrylamidopropane sulfonic acid and water soluble Salts of the aforementioned acids. More examples of such Monomers form monoesters from dihydric alcohols and 3 to 6 carbon atoms containing α, β-monoethylenically unsaturated carbon acids such as hydroxyethyl acrylate, n-hydroxypropyl acrylate, n-hydro xybutyl acrylate and the corresponding methacrylates. More common as a result of a copolymerization of the aforementioned monomers an increased stability of the disperse distribution of the result the polymer in an aqueous medium.  

The polymerization stages i preferably comprise none of the above mentioned monomers with increased water solubility. Rather are the monomers to be polymerized in the polymerization stages i with advantage those with particularly low water solubility. in the As a rule, i exclusively in the polymerization stages polymerized such monomers, their molar solubility in water (at 1 atm and 25 ° C) is equal to or less than the corresponding one Solubility of methyl methacrylate in water.

According to the invention, polymer 1 can also not have two or more conjugated ethylenically unsaturated monomers such as B. the di-esters of dihydric alcohols with α, β-mono polymerized ethylenically unsaturated monocarboxylic acids ent hold. Preferred di-unsaturated di-esters are those acrylic acid and methacrylic acid. Listed as an example be alkylene glycol diacrylates and dimethyl acrylates such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, propylene glycol diacrylate, 1,6-hexanediol diacrylate, Di propylene glycol diacrylate, tripropylene glycol diacrylate and tri methylolpropane triacrylate. As cross-linking components of polymer 1 there are also monomers such as divinylbenzene, Vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, Diallyl maleate, diallyl fumarate, methylenebisacrylamide, cyclopenta dienyl acrylate or triallyl cyanurate.

In many cases it is favorable if the polymer 1 and / or one or more of the polymerization stages i in subordinate Amounts, usually in amounts of 0.5 to 5 wt .-%, such Have monomers that only ver during film formation condition network. Carbonyl groups are mentioned as examples pointing monomers such as acrolein, methacrolein, diacetone acrylamide and methacrylamide and vinyl acetoacetate. The aforementioned Monomers cause e.g. B. then post-crosslinking when the aqueous Polymer dispersion at the same time a corresponding amount of Contains polyamine compound added. As such are suitable in particular the dihydrazides of 2 to 10 carbon atoms aliphatic dicarboxylic acids. Examples include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, Glutaric acid dihydrazide, adipic acid dihydrazide or sebacic acid dihydrazide.

Another post-crosslinking monomer is e.g. B. 2-Aceto acetoxyethyl methacrylate (alone or in combination with poly amines or polyaldehydes such as glyoxal). They are also suitable for post-crosslinking such polymer building blocks that hydrolyze have bare Si-organic bonds. Named as an example be the copolymerizable monomers methacryloxypropyltri  methoxysilane and vinyltrimethoxysilane. Other suitable polymer Modules of a corresponding type can be found in DE-A 43 41 260. If the dispersed polymer particles have carboxyl groups, post-crosslinking can also be carried out by adding polyvalent ones Cause metal salts containing cations (e.g. Mg, Ca, Zn or Zr salts). Epoxy and / or N-alkylol groups are also suitable having monomers such. B. glycidyl acrylate, N-methylolacrylic amide and N-methylol methacrylamide for the purpose of post-crosslinking. Post-crosslinking can also be done by copolymerization of minor Amounts of unsaturated benzophenone or acetophenone derivatives and achieve later photo initiation. Alternatively, you can corresponding saturated benzophenone or acetophenone derivatives in the aqueous polymer dispersions obtainable according to the invention be stirred.

At this point, however, it should be noted that, according to the invention, there is no need for the use of postcrosslinking constituents in order to achieve the desired mechanical property profile of the dispersion polymer films. If the process according to the invention comprises postcrosslinking systems, the glass transition temperatures Tg 1 and Tg ⁱ mean the glass transition temperatures to be determined by excluding these crosslinking constituents which are contained only in minor amounts.

Furthermore, the polymer 1 and / or the polymerization levels i in minor amounts, usually 0.1 to 5% by weight, containing adhesive monomers (e.g. containing nitrogen), to the adhesion of the film of the resulting aqueous polymer dispersion on numerous materials such as wood, metal, Minerals, paper, textiles and plastics, but especially on old paints based on drying oils and / or Alkyd resins, to increase and the sensitivity of the adhesion to reduce the influence of moisture and wetness (increased wet grip).

Adhesive monomers containing nitrogen come in particular radically polymerizable monomers with at least one Amino, ureido or N-heterocyclic groups into consideration. A variety of such suitable adhesive monomers can be found in EP-B 421 185, in EP-B 379 892 on page 3, in the EP-A 609 756 on page 2, in DE-A 43 34 178 and in DE-A 39 02 067 on pages 3/4.

Examples include aminoethyl acrylate and methacrylate, Dimethylaminoethyl acrylate and methacrylate, diethylaminoethyl acrylate and methacrylate, dimethylaminopropyl acrylate and  methacrylate, 3-dimethylamino-2,2-dimethylpropyl-1-acrylate and methacrylate, 2-N-morpholinoethyl acrylate and methacrylate, 2-N-piperidinoethyl acrylate and methacrylate, N- (3-dimethylamino propyl) acrylamide and methacrylamide, N-dimethylaminoethylacryl amide and methacrylate, N-diethylaminoethyl acrylamide and meth acrylamide, N- (4-morpholinomethyl) acrylamide and methacrylamide, Vinylimidazole and monoethylenically unsaturated derivatives of Ethylene urea such as N- (2-acryloyloxyethyl) ethylene urea, N- (α-acrylamidoethyl) ethylene urea, N-2- (allyl carbamato) aminoethylimidazolidinone, N- (3-allyloxy-2-hydroxypropyl) amino ethyl ethylene urea, N-vinyl ethylene urea, N-vinyloxy ethylene urea, N-methacryloxyacetoxyethylethylene urea, N- (acrylamidoethylene) ethylene urea, N- (methacrylamidoethylene) ethylene urea, 1- (2-methacryloyloxyethyl) imidazolin-2-one and N- (methacrylamidoethyl) ethylene urea. More suitable Ureide monomers are described in a review by R.W. Circle, AT THE. Sherman, Developments in "Ureido Functional Monomer for Promoting Wet Adhesion in Latex Paints, Water-Borne and Higher Solids Coating Symposium from February 3rd to 5th, 1988, New Orleans, Called Lousiana ".

The inventive method is favored if the mono mers that build the polymer 1, and the monomers that are polymerized in the polymerization stages i, each other are chemically similar. That is, polymer 1 becomes predominant from alkyl esters of acrylic and methacrylic acid or from their Mixture with styrene and / or aryl nitrile, it is from before partly, although in the polymerization stages i predominantly alkyl esters of acrylic and methacrylic acid either by themselves or in Polymerized mixture with styrene and / or acrylonitrile. In contrast, the polymer 1 is predominantly made of vinyl esters or their mixture polymerized with ethylene, it is advantageous if also in the polymerization stages i predominantly vinyl esters or their mixture are polymerized with ethylene. If the poly exists merisat 1 predominantly from butadiene or from its mixture with Acrylonitrile and / or styrene, is favorable if acrylonitrile and / or styrene also the main components of the polymerization step fen i form. That is, the polymer 1 can be used in the inventive Procedure of at least 75% by weight only from esters of acrylic and / or methacrylic acid with C₁ to C₈ alkanols or too little at least 75% by weight from their mixture with styrene and / or acrylonitrile be constructed. But also a structure of at least 75% by weight Vinyl esters and / or ethylene is conceivable.

Accordingly, the method according to the invention is applicable to Polymers 1, the radicalized polymerized form of 90 (preferably 95) to 100% by weight of esters of acrylic  and / or methacrylic acid with C₁ to C₈ alkanols and 0 to 10 (preferably up to 5)% by weight of 3 to 6 carbon atoms α, β-monoethylenically unsaturated carboxylic acids, their amides and / or alkali metal salts are built up.

However, it is also applicable to polymers 1 which are in radicals misch polymerized form from 95 to 100 wt .-% of esters of Acrylic and / or methacrylic acid with C₁-C₈ alkanols and styrene and 0 to 5% by weight of 3 to 6 carbon atoms containing α, β-mono ethylenically unsaturated carboxylic acids, their amides and / or Alkali metal salts are built up.

Preferably, recruit for the structure of the polymer 1 whose monomers from the group comprising ethyl acrylate, methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl meth acrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, Itaconic acid, styrene, acrylonitrile, acrylamidopropanesulfonic acid and Vinyl sulfonic acid; particularly preferably from the group comprising n-butyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide and itaconic acid.

In all of the above cases, isobutyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, iso-bornyl acrylate, iso-bornyl methacrylate, 4-tert-butylcyclohexyl acrylate, 4-tert.- Butylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, acrylonitrile, styrene, α-phenylstyrene, α-methylstyrene, methyl methacrylate and mixtures of the aforementioned monomers, which i preferably monomers to be polymerized. This statement is correct also in the case of other polymers 1 too.

According to the invention, polymer 1 is prepared according to the free-radical aqueous emulsion polymerization method, d. that is, in the presence of dispersant and radical poly merization initiator directly in the aqueous medium in disperse Distribution located.

As dispersants come both for carrying out radical aqueous emulsion polymers usually protective colloids used as well as emulsifiers.

Suitable protective colloids are, for example, polyvinyl alcohols, Cellulose derivatives or copolymers containing vinyl pyrrolidone sate. A detailed description of other suitable protection colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag,  Stuttgart, 1961, pp. 411 to 420. Of course you can too Mixtures of emulsifiers and / or protective colloids are used will. Preferably, only dispersants are used Emulsifiers used, the relative molecular weights in Difference to the protective colloids usually below 2000, preferably less than 1000. They can be both anionic, be cationic or nonionic in nature. Of course need to be more surface-active in the case of mixtures Substances the individual components are compatible with each other, which in case of doubt can be checked using a few preliminary tests can. In general, anionic emulsifiers are among themselves and compatible with nonionic emulsifiers. The same applies also for cationic emulsifiers, while anionic and cat ionic emulsifiers are mostly incompatible with one another. Common emulsifiers are e.g. B. ethoxylated mono-, di- and Tri-alkylphenols (EO grade: 3 to 100, alkyl radical: C₄ to C₁₂), ethoxylated fatty alcohols (EO grade: 3 to 100, preferably 6 to 50, alkyl radical: C₆ to C₂₀), and alkali and ammonium salts of Alkyl sulfates (alkyl radical: C₈ to C₁₈), of sulfuric acid semiesters ethoxylated alkanols (EO grade: 1 to 70, especially 2 to 10, Alkyl radical: C₁₀ to C₁₈) and ethoxylated alkylphenols (EO grade: 3 to 100, preferably 6 to 50, alkyl radical: C₄ to C₁₈), of alkyl sulfonic acids (alkyl radical: C₁₀ to C₁₈) and of alkylarylsulfone acids (alkyl radical: C₉ to C₁₈). Other suitable emulsifiers such as Sulfosuccinic acid esters can be found in Houben-Weyl, Methods of organic chemistry, volume XIV / 1, macromolecular substances, Georg- Thieme-Verlag, Stuttgart, 1961, pages 192 to 208.

Other suitable surfactants have also been found Compounds of the general formula I

wherein A¹ and A² are hydrogen or C₄- to C₂₄-alkyl and are not hydrogen at the same time, and X and Y are alkali metals Ions and / or ammonium ions can be proven. In the For mel I A¹ and A² are preferably linear or branched alkyl residues with 6 to 18 carbon atoms or hydrogen, and in particular with 6, 12 and 16 carbon atoms, wherein A¹ and A² are not both at the same time are hydrogen. X and Y are preferably sodium, potassium or Ammonium ions, with sodium being particularly preferred. Especially Compounds 1 in which X and Y are sodium, A 1 are advantageous a branched alkyl radical with 12 C atoms and A² hydrogen or A¹ is. Technical mixtures are often used, some  Share of 50 to 20 wt .-% of the monoalkylated product have, for example Dowfax® 2A1 (trademark of DOW Chemical Company). Frequently, the compounds I alone or in Mixture with ethoxylated fatty alcohols (EO grade: 3 to 50, Alkyl radical: C₈ to C₃₆) used as a dispersant. The Ver bindings I are generally known, e.g. B. from US-A 4,269,749, and commercially available. Usually the amount is one set dispersant 0.5 to 6, preferably 1 to 5 and particularly preferably 2 to 4% by weight, based on that for production of polymer 1 monomers to be polymerized by free radicals.

The triggering of radical polymerization for production of polymer 1 can in principle by all radical Initiators are made who are capable of a radical trigger aqueous emulsion polymerization. It can happen both peroxides, e.g. B. H₂O₂, peroxodisulfuric acid and / or their salts, e.g. B. alkali metal or ammonium peroxodisulfate, as well as azo compounds such as azo-bis-isobutyronitrile or Act 4,4'-azo-bis-cyanvaleric acid.

An initiation of the radical aqueous emulsion polymer sation for the preparation of the polymer 1 by comparison low temperatures enable combined initiator systems that of at least one organic and / or inorganic Reducing agent and at least one peroxide and / or hydro peroxide are composed, e.g. B. tert-butyl hydroperoxide and the sodium metal salt of hydroxymethanesulfinic acid or water peroxide and ascorbic acid. The above applies in particular for combined systems that also have a small amount a metal compound soluble in the polymerization medium, the metallic components occur in several valence levels may contain (often in complex form to prevent precipitation prevent), e.g. B. ascorbic acid / iron (II) sulfate / hydrogen peroxide, instead of ascorbic acid z. B. the sodium metal salt of hydroxymethanesulfinic acid, sodium sulfite or Sodium hydrogen sulfite and instead of hydrogen peroxide too e.g. B. alkali metal peroxodisulfate and / or ammonium peroxodisulfate can be applied. Instead of a water soluble Iron (II) salt can also be a V salt or a combination from water-soluble Fe / V salts can be used. Usually is the amount used to prepare the polymer 1 of radical initiator system, based on the amount of polymerizing monomers, 0.1 to 2 wt .-%.

Polymerization pressure and polymerization temperature are in the frame the production of polymer 1 from a rather minor Be interpretation. In general, temperatures from 0 ° C to  100 ° C, often 20 ° C to 100 ° C, or 50 to 95 ° C, mostly 60 to 90 ° C. In order to obtain particularly long-chain polymers 1, polymerize expediently at temperatures of 40 to 70 ° C. The application of reduced or increased pressure is possible so that the polymerization temperature also exceed 100 ° C and can be up to 130 ° C and more. Preferably be light volatile monomers such as ethylene or butadiene under increased pressure polymerized. To regulate the pH of the polymerization mediums can during the radical aqueous emulsion poly merization for the preparation of the polymer 1 pH buffer as NaHCO₃, Na₂CO₃, Na acetate or Na₂P₂O₅ can be added.

Define to improve reproducibility and setting ter particle diameter can be used in the manufacture of Polymer 1 polymer particle formation phase and polymer Particle growth phase in a manner known per se to the person skilled in the art be decoupled from each other by having a defined Amount of a pre-formed aqueous polymer dispersion (one Seed latex) in the polymerization vessel or in the same one models such in situ. The further course of the radika to aqueous emulsion polymerization added amount Dispersant is then usually dimensioned so that the critical micelle concentration no longer exceeded thus largely avoiding new polymer particle formation becomes. Will a wide distribution of the diameter of the poly targeted polymer particles 1, one will in the Rule the polymerization vessel in a manner known per se during the radical aqueous emulsion polymerisation of latex inflict. Like the process of radical polymerization in general, is both the radical aqueous emulsion poly merization for the preparation of the polymer 1 as well as each Polymerization stage i under an inert gas atmosphere (e.g. N₂, Ar) or in an atmosphere containing oxygen (e.g. air) feasible.

The free radical aqueous can be carried out in a particularly simple manner Emulsion polymerization to produce an aqueous dispersion perform a polymer 1 as follows.

The monomers to be polymerized are in an aqueous medium emulsified and the radical polymerization initiator is in Water dissolved. Water and water are added to the polymerization vessel if a small amount of α, β-monoethylenically unsaturated Carboxylic acid submitted and to the polymerization temperature warmed up. Then part of the aqueous monomer emulsion and part of the aqueous initiator solution of the template at once added and polymerized. After that, the polymerization vessel while maintaining the polymerization, the remaining amount  of the aqueous monomer emulsion and the remaining amount of the aqueous Initiator solution, preferably essentially synchronous, continuous fed slowly. After the initiator and monomers have ended the polymerization mixture is fed upright maintenance of the polymerization temperature expediently still leave yourself to stir for a while. To carry out The subsequent polymerization stages i become the reak tion mixture then expediently cool first. Then you become the monomers to be polymerized in stage i the polymerization vessel, preferably by itself and all at once, admit. The emulsifier content of the aqueous is advantageous Dispersion of the polymer 1 be such that the aqueous dispersion medium essentially no emulsifier micelles having. Then you get the advantageously cooled reactor contents expediently while stirring usually for some time left to favor swelling. After that normally fresh free radical polymerization initiator add and then to the polymerization temperature heat and polymerize as desired. In corresponding If necessary, further polymerization stages i can be closed.

As a radical polymerization initiator for Initiation of the polymerization stages i in principle all the use those who are already involved in the production of the Dispersion of the polymer 1 have been mentioned. Prefers however, such radical initiator systems are used which comprise organic peroxides or organic hydroperoxides. In particular, such organic peroxides and / or hydroperoxides comprehensive redox initiator systems. Especially tert-butyl hydroper free radical initiator comprising oxide and cumene hydroperoxide systems are suitable. But also pinane hydroperoxide, p-mentane hydroperoxide, diisopropylphenyl hydroperoxide, dibenzoyl peroxide, Radicals comprising dilauryl peroxide and diacetyl peroxide Initiator systems are suitable. As a reducing partner come, for example, alkali metal sulfites, ascorbic acid, Acetone bisulfite and the alkali metal salts of hydroxymethane sulfinic acid into consideration. Based on that in a polymerisa tion stage i to be polymerized monomers are usually 0.1 to 2 wt .-% of radical polymerization initiator put. Of course, the in a polymerization stage i before to polymerize monomers in a less preferred embodiment of the present invention also in in aqueous medium pre-emulsified the polymerization vessel be added. All can be used as dispersants in this regard those used to manufacture the aqueous dispersion of polymer 1 were recommended. As a result  the preferred use of organic redox initiator systems in the polymerization stages i the associated polymerisa tion temperature below 80 ° C (usually 40 ° C to  80 ° C). This applies to the polymerization pressure 1 statements regarding the preparation of the polymer.

The films of the aqueous poly resulting according to the invention merisate dispersions (pigmented and / or filled or not pigmented and not filled) show next to those already described advantages also good flexibility, reduced Surface stickiness and a satisfactory hardness. she are u. a. as a binder for coatings on leather and of hydrophobic substrates, such as. B. from with masses Polyurethane base, e.g. B. for reasons of thermal insulation, coating flat roofs. By performing in a manner known per se leading spray drying can be obtained from those obtained according to the invention Lichen aqueous polymer dispersions in an aqueous medium redispersible polymer powder can be prepared. In these Brought dry form can be obtained according to the invention transport aqueous polymer dispersions inexpensively to to be returned to the aqueous dispersion at the place of use. The polymer powders obtainable in this way can also be used for production of dry plaster for sale as well as for the production of with Polymer modified mineral binding materials such as Dry mortar, especially cement-based ones, is used will. The poly obtainable according to the invention are also suitable merisat systems as adhesives, as binders for paper coating masses and as binders for nonwovens. Particularly suitable as already mentioned, it is for crack bridging coating compound (e.g. paints).

Such coating compositions usually contain 40 to 95% by weight, preferably 60 to 90% by weight and in particular 65 to 85% by weight of non-volatile components. Based on their total amount is about 10 to 99.5 wt .-%, preferably 10 to 50 wt .-% and in particular 20 to 40 wt .-% on those in the polymer Binder contained solids, 0 to 60 wt .-%, before preferably 20 to 60% by weight, in particular 30 to 55% by weight Fillers, 0 to 60% by weight, preferably 0 to 20% by weight Pigments and 0.5 to 25% by weight, preferably 1 to 10% by weight Tools.

Suitable fillers are, for example, aluminosilicates, silicates, Alkaline earth carbonates, preferably calcium carbonate in the form of Calcite or chalk, dolomite and aluminum silicates or Magnesium silicates such as talc.  

A typical pigment is, for example, titanium dioxide wise in the rutile form. However, the coating compositions can especially when used for decorative purposes, also contain colored pigments, for example iron oxides.

The usual auxiliaries include wetting agents such as sodium or Potassium polyphosphates, polyacrylic acids, their alkali salts, poly vinyl alcohols etc. They also contain coating usually mass substances that modify the viscosity, for example cellulose ethers, such as hydroxyethyl cellulose. Next Dispersants, defoamers, Preservatives or water repellents, biocides, dyes, Fibers or other components are added. Can too the coating compositions to adjust the film formation proper Properties of the binder polymers contain plasticizers.

Of course, this can be done in those obtainable according to the invention polymer containing aqueous polymer dispersions by coagulation to be carried out in a manner known per se isolated and z. B. to modify engineering plastics be used.

The aqueous solutions obtainable according to the invention can also be used Polymer dispersions for modifying other aqueous Polymer dispersions are used. This can be done in simple be done in such a way that the other aqueous Add polymer dispersions. But it can also be done that you can use it as a seed dispersion to make another aqueous polymer dispersion used.  

Examples Bi and comparative examples VB

The following abbreviations are used below:
MMA = methyl methacrylate
nBA = n-butyl acrylate
EHA = 2-ethylhexyl acrylate
tBMA = tert-butyl methacrylate
iBMA = iso-butyl methacrylate
nBMA = n-butyl methacrylate
S = styrene
alMS = α-methylstyrene
BDA2 = butanediol diacrylate
MAA = methacrylic acid
IA = itaconic acid
AM = acrylamide
NaPS = sodium peroxodisulfate
tBHP = tert-butyl hydroperoxide
RC = sodium salt of hydroxymethanesulfinic acid (Rongalit® C)
E1 = ethoxylated alkanol (alkyl radical: C _16-18 ; EO grade: 18)
E2 = sodium salt of dodecylphenoxybenzyl disulfonic acid (active ingredient corresponding to Dowfax 2A1)
AcBS = acetone bisulfite
RF = tensile strength or tensile strength [N / mm²]
RD = elongation at break [%, based on the initial length]
RA = fraction work = RF × RD [% × N / mm²].

The content was in all examples and comparative examples the resulting aqueous polymer dispersion not polymerized monomers (determined by gas chromatography) at <2000 ppm (based on the weight of the aqueous polymer dispersion). That is, the residual monomer content of the polymer dispersions were essentially without influence in all cases the mechanical properties of the associated polymer films.

VB1: From 268 g of water, 14.22 g of a 45% by weight aqueous Solution of E2, 160 g EHA, 520 g nBA, 120 g MMA and 16 g MAA an aqueous monomer emulsion was generated. From 2.4 g Sodium peroxodisulfate (the alkali metal peroxodisulfates are preferred for the preparation of the polymers 1 set) and 75 g of water became an aqueous initiator solution generated. In a stirred polymerization vessel (2 l) 250 g of water and 3.2 g of itaconic acid were placed in glass. After rinsing the template and the polymerization vessel with Nitrogen was heated to 85 ° C. Subsequently the polymerization vessel was initially 54.5 g at a time the aqueous monomer emulsion and then 7.7 g of the aqueous initiator solution added. While maintaining  the 85 ° C was the reactor content for 30 min under Polymeri left to itself. Then were under Maintains the remaining amount at 85 ° C (starting at the same time) the aqueous monomer emulsion (within 3 h) and the remaining amount of the aqueous initiator solution (within 3.5 h) continuously fed to the polymerization vessel. Thereafter, the polymerization mixture was at 85 ° C for 1 h touched. Then, to reduce the rest monomer content successively 1.6 g of a 50 wt .-% aqueous tBHP solution and 0.64 g RC into the polymerization vessel given and the reaction mixture cooled to 25 ° C. After that was the by means of a 10 wt .-% aqueous NaOH solution pH of the aqueous dispersion medium to a value of 9 set. The resulting aqueous polymer disper sion VB1 had a solids content of 56.2% by weight and one using photon correlation spectroscopy (quasi elastic light scattering) determined medium polymer particle diameter of 260 nm.

The dispersed polymer had the following composition:
63.5 wt% nBA
19.5 wt% EHA
14.65 wt% MMA
1.95 wt% MAA
0.40 wt% IA.

To determine the mechanical properties of the film the aqueous polymer dispersion (in all subsequent Examples were followed accordingly) this was based on diluted a solids content of 25 wt .-%. Subsequently became a sample of the aqueous polymer thus diluted dispersion in a 15 cm × 15 cm × 0.6 cm form made of silicone for 2 weeks at 23 ° C and 50% relative humidity dried.

The amount of sample was measured so that the resulting film thickness was about 0.1 cm. The determination of RF, RD and thus RA was based on DIN 53 455 and DIN 53 504. The measurement values given are mean values from 5 measurements on 5 test specimens. For this purpose, after the film had been detached from the silicone mold, the test specimens required for carrying out the tensile test were punched out. The dumbbell format described in DIN 53 504 (see 2.4.11.6) as standard rod S2 was used as the specimen format. The thickness of the samples was checked with the thickness measuring device according to DIN 53 370 with a circular button shape of 10 mm in diameter. The test specimens were clamped in the clamps of a tensile testing machine and torn at a withdrawal speed of 250 mm / min. The elongation at break is the stretch at the moment of tearing. It refers to 23 ° C and 1 atm. They are specified as [(LL _o ) / L _o ] × 100 (%), where:
L _o = the original measuring length,
L = the measuring length when tearing.

Correspondingly, the tear strength is that at the moment force to be applied to the tearing. It is usually based on the cross-section specified.

Furthermore, the glass transition temperature of the film certainly.

The following values were obtained:
RF = 1.80
RD = 844
RA = 1519
Tg = -30 ° C.

B1: From 249 g of water, 14.22 g of a 45% strength by weight aqueous solution of E2, 20 g of a 20% strength by weight aqueous solution of E1, 150.4 g of EHA, 488.8 g of nBA, 112.8 g of MMA, 16 g of MAA and 8.0 g of a 50% by weight aqueous solution of AM were used to produce an aqueous monomer emulsion. An aqueous initiator solution was prepared from 2.4 g of sodium peroxodisulfate and 75 g of water. 250 g of water and 1.6 g of IA were placed in a stirred glass polymerization vessel (2 l). After purging the template and the polymerization vessel with nitrogen, the template was heated to 85 ° C. Subsequently, 21.2 g of the aqueous monomer emulsion and then 7.7 g of the aqueous initiator solution were added in one portion to the polymerization vessel. While maintaining the 85 ° C, the reactor contents were left to polymerize for 30 minutes. Subsequently, the remaining amount of the aqueous monomer emulsion (within 3 h) and the remaining amount of the aqueous initiator solution (within 4 h) were continuously fed to the polymerization vessel while maintaining the 85 ° C. (starting simultaneously). After the supply of the aqueous initiator solution had ended, the polymerisation vessel contained the aqueous dispersion of a polymer 1, which had the following structure:
63.2 wt% nBA
19.4 wt% EHA
14.6 wt% MMA
2.1 wt% MAA
0.5 wt% AM
0.2 wt% IA.

The glass transition temperature of the associated film was:
Tg 1 = -29 ° C.

The aqueous dispersion of polymer 1 was at 40 ° C. cooled and obtained at one time with 48 g of tBMA (5.8% by weight to the total polymerized monomers). While maintaining the 40 ° C, the reactor contents Stirred for 10 min. Thereafter, 3.2 g were initially suddenly a 50% by weight aqueous solution of tBHP and then 0.8 g RC dissolved in 5 g of water added. Finally, the Temperature of the reaction mixture increased to 60 ° C and the reaction mixture with stirring for 45 min at this Temperature kept (released heat of reaction indicated the ongoing polymerization). In conclusion, that was Cooled reaction mixture to 25 ° C and the pH of the aqueous dispersion medium by means of 10 wt .-% aqueous NaOH solution adjusted to a value of 8.5. Of the Solids content of the resulting aqueous polymer dispersion B1 was 57% by weight and that by means of photons correlation spectroscopy determined medium polymer particle diameter was 480 nm.

The mechanical properties of the associated polymer film were:
RF = 3.65
RD = 1086
RA = 3964
Tg = -27 ° C
Tg ⁱ = 105 ° C.

From 240.5 g of water, 14.22 g of a 45% by weight aqueous solution of E2, 20 g of a 20% by weight aqueous solution of E1, 144 g EHA, 468 g nBA, 108 g MMA, 16 g MAA and 8 g of a 50% by weight aqueous solution of AM, an aqueous monomer emulsion was prepared. An aqueous initiator solution was produced from 2.4 g of sodium peroxodisulfate and 75 g of water. 250 g of water and 1.6 g of IA were placed in a stirred glass polymerization vessel (2 l). After purging the template and the polymerization vessel with nitrogen, the template was heated to 85 ° C. Then 20.55 g of the aqueous monomer emulsion and 7.7 g of the aqueous initiator solution were added in one portion to the polymerization reactor. While maintaining the 85 ° C, the reactor contents were left to polymerize for 30 minutes. Subsequently, the remainder of the aqueous monomer emulsion (within 3 h) and the remainder of the aqueous initiator solution (within 4 h) of the polymerization vessel were continuously fed while maintaining the 85 ° C (starting simultaneously). After the addition of the aqueous initiator solution had ended, the polymerisation vessel contained the aqueous dispersion of a polymer 1, which had the following structure:
63.1 wt% nBA
19.4 wt% EHA
14.6 wt% MMA
2.2 wt% MAA
0.5 wt% AM
0.2 wt% IA.

The glass transition temperature of the associated film was:
Tg 1 = -29 ° C.

The aqueous dispersion of polymer 1 was at 40 ° C. cooled and all at once obtained with 80 g of tBMA (9.7% by weight to the total polymerized monomers). While maintaining the 40 ° C, the reactor contents Stirred for 10 min. Thereafter, 4.8 g were initially suddenly a 50% by weight aqueous solution of tBHP and then 1.2 g RC dissolved in 5 g of water added. Finally, the Temperature of the reaction mixture increased to 60 ° C and that Reaction mixture with stirring for 45 min at this Temperature kept (released heat of reaction indicated the ongoing polymerization). In conclusion, that was Cooled reaction mixture to 25 ° C and the pH of the aqueous dispersion medium by means of 10 wt .-% aqueous NaOH solution adjusted to a value of 8.2. The feast substance content of the resulting aqueous polymer dispersion B2 was 56.2% by weight and that by means of photons correlation spectroscopy determined medium polymer particle diameter was 354 nm.  

The mechanical properties of the associated polymer film were:
RF = 3.71
RD = 708
RA = 2627
Tg = -25 ° C
Tg ⁱ = 105 ° C.

Like B1, but in polymerization stage i was used instead used by tBMA nBMA. Furthermore, the pH of the aqueous dispersion medium to a value of 8.1 posed. The solids content of the resulting aqueous Polymer dispersion B3 was 55.6% by weight and that of Mean poly determined by photon correlation spectroscopy Merisate particle diameter was 330 nm.

The mechanical properties of the associated polymer film were:
RF = 2.52
RD = 1222
RA = 3079
Tg = -28 ° C
Tg ⁱ = 20 ° C.

Like B1, but instead of tBMA iBMA was used in the poly merization level i used. The solids content of the resulting aqueous polymer dispersion B4 56.8% by weight and that by means of photon correlation spectroscopy determined medium polymer particles diameter was 390 nm.

The mechanical properties of the associated polymer film were:
RF = 2.84
RD = 1188
RA = 3374
Tg = -29 ° C
Tg ⁱ = 53 ° C.

Like B1, but instead of tBMA, styrene was used in the Polymerization stage i used. The solids content the resulting aqueous polymer dispersion B5 was 56.1% by weight and that by means of photon correlation  spectroscopy determined medium polymer particles diameter was 350 nm.

The mechanical properties of the associated polymer film were:
RF = 3.05
RD = 864
RA = 2580
Tg = -27 ° C
Tg ⁱ = 100 ° C.

B6: Like B1, but instead of tBMA, alMS was used in the poly merization level i used. The solids content of the resulting aqueous polymer dispersion was 53.4 wt .-% and that by means of photon correlation spectroscopy determined medium polymer particles diameter was 320 nm.

The mechanical properties of the associated polymer film were:
RF = 2.46
RD = 885
RA = 2177
Tg = -28 ° C
Tg ⁱ = 136 ° C.

VB2: From 160 g of water, 14.22 g of a 45% by weight aqueous solution of E2, 40 g of a 20% by weight solution of E1, 160 g of EHA, 520 g of nBA, 120 g of MMA and 16 g of a 50% by weight .-% aqueous solution of AM, an aqueous monomer emulsion was prepared. An aqueous solution of a reducing agent was prepared from 70 g of water and 3.2 g of RC. An aqueous hydroperoxide solution was prepared from 13.6 g of a 50% by weight aqueous solution of tBHP and 70 g of water. 250 g of water and 0.002 g of the Fe ²⁺ / 2Na⁺ salt of ethylenediaminetetraacetic acid were placed in a stirred polymerization vessel (2 l) made of glass. After purging the template and the polymerization vessel with nitrogen, the template was heated to 60 ° C. Subsequently, 20.6 g of the aqueous monomer emulsion and then 7.32 g of the aqueous reducing agent solution and 8.36 of the aqueous hydroperoxide solution were added to the polymerization vessel all at once. While maintaining the 60 ° C, the reactor contents were left to polymerize for 30 minutes. Then the remaining amount of the aqueous monomer emulsion (within 3 h), the remaining amount of the aqueous reducing agent solution (within 4 h) and the remaining amount of the aqueous hydroperoxide solution (while starting at 60 ° C (starting simultaneously and as always via separate feeds) continuously fed to the polymerization vessel within 4 h). The polymerization mixture was then stirred at 60 ° C. for 1 h. The pH of the aqueous dispersing medium was then adjusted to 8.5 using a 10% strength by weight aqueous NaOH solution. The resulting aqueous polymer dispersion VB2 had a solids content of 58.0% by weight and an average polymer particle diameter of 230 nm, determined by means of photon correlation spectroscopy.

The dispersed polymer had the following composition:
64.4 wt% nBA
19.8 wt% EHA
14.8 wt% MMA
1.0 wt% AM.

The mechanical properties of the associated polymer film were:
RF = 0.28
RD = 674
RA = 188
Tg = -36 ° C.

B7: From 200 g of water, 14.22 g of a 45% strength by weight aqueous solution of E2, 40 g of a 20% strength by weight solution of E1, 156.8 g of EHA, 509.6 g of nBA, 117.6 g MMA and 16 g of a 50 wt .-% aqueous solution of AM, an aqueous monomer emulsion was prepared. An aqueous solution of a reducing agent was prepared from 3.2 g of RC and 70 g of water. An aqueous hydroperoxide solution was prepared from 13.6 g of a 50% by weight aqueous solution of tBHP in 70 g water. 200 g of water and 0.002 g of the Fe ²⁺ + / 2Na⁺ salt of ethylenediaminetetraacetic acid were placed in a stirred polymerization vessel (2 l) made of glass. After purging the template and the polymerization vessel with nitrogen, the template was heated to 60 ° C. Then 21.08 g of the aqueous monomer emulsion and then 7.32 g of the aqueous reducing agent solution and 8.36 of the aqueous hydroperoxide solution were added to the polymerization vessel all at once. While maintaining the 60 ° C, the reactor contents were left to polymerize for 30 minutes. The remaining amount of the aqueous monomer emulsion (within 3 hours), the remaining amount of the aqueous reducing agent solution (within 4 hours) and the remaining amount of the aqueous hydroperoxide solution (within 4 hours) were then added to the polymerization vessel while maintaining the 60 ° C. (starting at the same time) fed continuously. After the feed had ended, the polymerisation vessel contained an aqueous dispersion of a polymer 1, which was structured as follows:
64.3 wt% nBA
19.8 wt% EHA
14.9 wt% MMA
1.0 wt% AM.

The glass transition temperature of the associated film was:
Tg 1 = -32 ° C.

The aqueous dispersion of polymer 1 was at 40 ° C. cooled and obtained at one time with 16 g of tBMA (2% by weight to the total polymerized monomers). While maintaining the 40 ° C, the reactor contents Stirred for 10 min. Thereafter, 3.2 g were initially suddenly a 50% by weight aqueous solution of tBHP and then 0.8 g RC dissolved in 10 g of water added. Finally was the temperature of the reaction mixture increased to 60 ° C and the reaction mixture with stirring for 45 min at this Temperature kept (released heat of reaction indicated the ongoing polymerization). In conclusion, that was Cooled reaction mixture to 25 ° C and the pH of the aqueous dispersion medium by means of 10 wt .-% aqueous NaOH solution adjusted to a value of 9.2. The feast substance content of the resulting aqueous polymer dispersion B7 was 56.6% by weight and that by means of photons correlation spectroscopy determined medium polymer particle diameter was 230 nm.

The mechanical properties of the associated polymer film were:
RF = 0.47
RD = 653
RA = 307
Tg = -28 ° C
Tg ⁱ = 105 ° C.

B8: From 200 g of water, 14.22 g of a 45% strength by weight aqueous solution of E2, 40 g of a 20% strength by weight solution of E1, 150.4 g of EHA, 488.8 g of nBA, 112.8 g MMA and 16 g of a 50 wt .-% aqueous solution of AM, an aqueous monomer emulsion was prepared. An aqueous solution of a reducing agent was prepared from 3.2 g of RC and 70 g of water. An aqueous hydroperoxide solution was prepared from 13.6 g of a 50% by weight aqueous tBHP solution and 70 g of water. 200 g of water and 0.002 g of the Fe ²⁺ / 2Na⁺ salt of ethylenediaminetetraacetic acid were placed in a polymerization vessel (2 l) made of glass. After purging the template and the polymerization vessel with nitrogen, the template was heated to 60 ° C. Then 21.08 g of the aqueous monomer emulsion and then 7.32 g of the aqueous reducing agent solution and 8.36 g of the aqueous hydroperoxide solution were added to the polymerisation vessel all at once. While maintaining the 60 ° C, the reactor contents were left to polymerize for 30 minutes. The remaining amount of the aqueous monomer emulsion (within 3 h), the remaining amount of the aqueous reducing agent solution (within 4 h) and the remaining amount of the aqueous hydroperoxide solution (within 4 h) were then the polymerization vessel while maintaining the 60 ° C (starting at the same time) fed continuously. After the feed had ended, the polymerization vessel contained an aqueous dispersion of a polymer 1, which had the following structure:
64.3 wt% nBA
19.8 wt% EHA
14.9 wt% MMA
1.0 wt% AM.

The glass transition temperature of the associated film was:
Tg 1 = -33 ° C.

The aqueous dispersion of polymer 1 was at 40 ° C. cooled and obtained at one time with 48 g of tBMA (5.9% by weight to the total polymerized monomers). While maintaining the 40 ° C, the reactor contents Stirred for 10 min. Thereafter, 3.2 g were initially suddenly a 50% by weight aqueous solution of tBHP and then 0.8 g RC dissolved in 10 g of water added. Finally was the temperature of the reaction mixture increased to 60 ° C and the reaction mixture with stirring for 45 min at this Temperature kept (released heat of reaction indicated the ongoing polymerization). In conclusion, that was  Cooled reaction mixture to 25 ° C and the pH of the aqueous dispersion medium using 10% by weight NaOH Solution set to a value of 9.2. The solid content of the resulting aqueous polymer dispersion B8 was 56.7% by weight and that by means of photon correlation spectroscopy determined medium polymer particles diameter was 330 nm.

The mechanical properties of the associated polymer film were:
RF = 0.83
RD = 898
RA = 745
5 Tg = - 33 ° C
Tg ⁱ = 105 ° C.

B9: From 200 g of water, 14.22 g of a 45% strength by weight aqueous solution of E2, 40 g of a 20% strength by weight solution of E1, 144 g of EHA, 468 g of nBA, 108 g of MMA and 16 g of a 50% strength .-% aqueous solution of AM, an aqueous monomer emulsion was prepared. An aqueous solution of a reducing agent was prepared from 3.2 g of RC and 70 g of water. An aqueous hydroperoxide solution was prepared from 13.6 g of a 50% by weight aqueous tBHP solution and 70 g of water. 200 g of water and 0.002 g of the Fe ²⁺ / Na⁺ salt of ethylenediaminetetraacetic acid were placed in a polymerization vessel (2 l) made of glass. After purging the template and the polymerization vessel with nitrogen, the template was heated to 60 ° C. Subsequently, the polymerization vessel was first added to 21.08 g of the aqueous monomer emulsion and then 7.32 g of the aqueous reducing agent solution and 8.36 of the aqueous hydroperoxide solution. While maintaining the 60 ° C, the reactor contents were left to polymerize for 30 minutes. The remaining amount of the aqueous monomer emulsion (within 3 h), the remaining amount of the aqueous reducing agent solution (within 4 h) and the remaining amount of the aqueous hydroperoxide solution (within 4 h) were then the polymerization vessel while maintaining the 60 ° C (starting at the same time) fed continuously. After the feed had ended, the polymerization vessel contained an aqueous dispersion of a polymer 1, which had the following structure:
64.3 wt% nBA
19.8 wt% EHA
14.8 wt% MMA
1.1 wt% AM.

The glass transition temperature of the associated film was:
Tg 1 = -33 ° C.

The aqueous dispersion of polymer 1 was at 40 ° C. cooled and at one time based on 80 g of tBMA (9.9% by weight to the total polymerized monomers). While maintaining the 40 ° C, the reactor contents Stirred for 10 min. Thereafter, 3.2 g were initially suddenly a 50% by weight aqueous solution of tBHP and then 0.8 g RC dissolved in 10 g of water added. Finally, the Temperature of the reaction mixture increased to 60 ° C and that Reaction mixture with stirring for 45 min at this Temperature kept (released heat of reaction indicated the ongoing polymerization). In conclusion, that was Cooled reaction mixture to 25 ° C and the pH of the aqueous dispersion medium by means of 10 wt .-% aqueous NaOH solution adjusted to a value of 9.2. Of the Solids content of the resulting aqueous polymer dispersion B9 was 56.9% by weight and that by means of photons correlation spectroscopy determined medium polymer particle diameter was 310 nm.

The mechanical properties of the associated polymer film were:
RF = 1.55
RD = 565
RA = 876
Tg = -32 ° C
Tg ⁱ = 105 ° C.

B10: Like B8, but instead of tBMA, nBMA was used in the poly merization level i used. The resulting aqueous Polymer dispersion had a solids content of 56.8% by weight. The pH of the aqueous dispersion medium was set to a value of 9.5. The means Mean photon correlation spectroscopy Polymer particle diameter was 250 nm.

The mechanical properties of the associated polymer film were:
RF = 0.60
RD = 958
RA = 575
Tg = -34 ° C
Tg ⁱ = 20 ° C.

B11: Like B8, but instead of tBMA iBMA was used in the poly merization level i used. The resulting aqueous Polymer dispersion had a solids content of 57% by weight. The pH of the aqueous dispersion medium was set to a value of 10.0. The means Mean photon correlation spectroscopy Polymer particle diameter was 340 nm.

The mechanical properties of the associated polymer film were:
RF = 0.90
RD = 562
RA = 506
Tg = -34 ° C
Tg ⁱ = 53 ° C.

B12: Like B8, but instead of tBMA, MMA was used in the poly merization level i used. The resulting aqueous Polymer dispersion had a solids content of 56.7% by weight. The pH of the aqueous dispersion medium was set to a value of 9.0. The means Mean photon correlation spectroscopy Polymer particle diameter was 320 nm.

The mechanical properties of the associated polymer film were:
RF = 1.15
RD = 704
RA = 810
Tg = -34 ° C
Tg ⁱ = 105 ° C.

B13: Like B8, but instead of tBMA, styrene was used in the poly merization level i used. The resulting aqueous Polymer dispersion had a solids content of 55.2% by weight. The pH of the aqueous dispersion medium was set to 8.5. The means Mean photon correlation spectroscopy Polymer particle diameter was 280 nm.  

The mechanical properties of the associated polymer film were:
RF = 0.40
RD = 819
RA = 328
Tg = -34 ° C
Tg ⁱ = 100 ° C.

B14: Like B8, but instead of tBMA, alMS was used in the poly merization level i used. The resulting aqueous Polymer dispersion had a solids content of 53.6% by weight. The pH of the aqueous dispersion medium was set to a value of 9.4. The means Mean photon correlation spectroscopy Polymer particle diameter was 310 nm.

The mechanical properties of the associated polymer film were:
RF = 0.41
RD = 795
RA = 326
Tg = -35 ° C
Tg ⁱ = 136 ° C.

VB3: Like B8, but instead of tBMA, BDA2 was used in the poly merization level i used. The resulting aqueous Polymer dispersion had a solids content of 56.2% by weight. The pH of the aqueous dispersion medium was set to a value of 9.5. The means Mean photon correlation spectroscopy Polymer particle diameter was 250 nm.

The mechanical properties of the associated polymer film were:
RF = 0.95
RD = 501
RA = 475
Tg = -36 ° C
Tg ⁱ = -.

VB4: Like B8, but instead of 48 g tBMA a mixture was used standing from 24 g tBMA and 24 g BDA2 in the polymerization stage i used. The resulting aqueous polymer dispersion had a solids content of 57.5% by weight.  

The one determined by means of photon correlation spectroscopy Polymer particle diameter was 186 nm.

The mechanical properties of the associated polymer film were:
RF = 0.35
RD = 375
RA = 131
Tg = -31.7 ° C.

VB5: Like B11, but instead of 48 g iBMA was a mixture consisting of 34 g iBMA and 24 g BDA2 in the poly merization level i used. The resulting aqueous Polymer dispersion had a solids content of 57.5% by weight. The one using photon correlation Spectroscopy determined polymer particle diameter was 212 nm.

The mechanical properties of the associated polymer film were:
RF = 0.46
RD = 315
RA = 145
Tg = -31 ° C.

VB6: Like B8, but the polymerization stage i was omitted. Instead of the 48 g of tBMA were in the aqueous monomers Emulsion for the preparation of the polymer 1 incorporated. The redox initiator system of polymerization stage i was used for post-polymerization. The resulting aqueous Polymer dispersion had a solids content of 56.8% by weight. The one using photon correlation Spectroscopy determined polymer particle diameter was 354 nm.

The mechanical properties of the associated polymer film were:
RF = 0.47
RD = 829
RA = 381
Tg = -27 ° C.

VB7: Like B1, but polymerization stage i was omitted. Instead of the 48 g of tBMA were in the aqueous monomers Emulsion for the preparation of the polymer 1 incorporated.

The redox initiator system of polymerization stage i was used for post-polymerization. The resulting aqueous Polymer dispersion had a solids content of 56.5% by weight. The one using photon correlation Spectroscopy determined polymer particle diameter was 363 nm.

The mechanical properties of the associated polymer film were:
RF = 1.03
RD = 947
RA = 975
Tg = -20.5 ° C.

VB8: Like B1, but the polymerization stage i was so stalt that the 48 g tBMA in the polymerization vessel constant polymerization temperature of 60 ° C within 1 h as a pure monomer feed continuously fed were. In a corresponding manner, the redox initiator System starting within 70 min of the poly merization vessel fed continuously. The polymerisa tion conversion of any in the polymerization stage i Monomers already supplied at a time were thus at any time at <80 mol%. The resulting aqueous Polymer dispersion had a solids content of 55.3% by weight. The one using photon correlation Spectroscopy determined polymer particle diameter was 368 nm.

The mechanical properties of the associated polymer film were:
RF = 2.99
RD = 740
RA = 2212
Tg = -23.8 ° C.

VB9: Like B8, but the polymerization stage i was so stalt that the 48 g tBMA in the polymerization vessel constant polymerization temperature within 1 h as pure monomer feed were fed continuously. In the redox initiator system was correspondingly time starting within 70 min of the polymerization  vessel fed continuously. The polymerization conversion that in polymerization stage i at any time monomers already supplied were included at all times <80 mol%. The resulting aqueous polymer dispersion had a solids content of 55.9% by weight. The means Polymer determined using photon correlation spectroscopy particle diameter was 369 nm.

The mechanical properties of the associated polymer film were:
RF = 1.19
RD = 385
RA = 458.2
Tg = -29.3 ° C.

VB10: Like VB2, but instead of 13.6 g aqueous tBHP solution only 4.8 g used. Also used as a reducing agent instead of 3.2 g RC 2.4 g AcBS used. In addition, fraud the polymerization temperature 70 ° C. The resulting one aqueous polymer dispersion had a solids content from 57.8% by weight. The one using photon correlation Spectroscopy determined polymer particle diameter was 259 nm.

The mechanical properties of the associated polymer film were:
RF = 0.27
RD = 866
RA = 234
Tg = -32.2 ° C.

B15: Like B8, but instead of 13.6 g of aqueous tBHP solution only 4.8 g used. Furthermore, for the production of Polymer 1 used instead of 3.2 g RC 2.4 g AcBS and the polymerization was carried out at 70 ° C. In the poly merisation stage i was 4.8 g of aqueous tBHP solution used and instead of 0.8 g RC 1.6 g AcBS. Furthermore was stirred at 40 ° C. for 12 h instead of 10 min. The resul Aqueous polymer dispersion showed a solid content of 59.7% by weight. The one with photons polymer particles determined by correlation spectroscopy diameter was 333 nm.  

The mechanical properties of the associated polymer film were:
RF = 0.89
RD = 1035
RA = 921
Tg = -30.7 ° C.

B16: Like B9, but instead of 13.6 g of aqueous tBHP solution only 4.8 g used. Furthermore, for the production of Polymer 1 used instead of 3.2 g RC 2.4 g AcBS and the polymerization was carried out at 70 ° C. In the poly merisation stage i was 4.8 g of aqueous tBMP solution used and instead of 0.8 g RC 1.6 g AcBS. Furthermore was stirred at 40 ° C. for 12 h instead of 10 min. The resul Aqueous polymer dispersion showed a solid content of 58.7% by weight. The one with photons polymer particles determined by correlation spectroscopy diameter was 345 nm.

The mechanical properties of the associated polymer film were:
RF = 1.26
RD = 788
RA = 993
Tg = -30.2 ° C.

Claims (24)

1. A process for the preparation of aqueous polymer dispersions, in which firstly from at least one ethylenically unsaturated group-containing compounds (monomers) according to the radical aqueous emulsion polymerization method, a polymer 1 which is in disperse distribution in an aqueous medium is produced and then in one or more successive Polymerization stages i further monomers in the presence of the polymer 1 in disperse distribution in the aqueous medium with the proviso that radical polymerization

• a) the polymer 1 has a glass transition temperature Tg¹;
• b) the monomers polymerized in each of the polymerization stages are such that, in the case of isolated statistical copolymerization of these monomers, a polymer i sat would be obtained, the glass transition temperature of which tends towards the limit value Tg ⁱ with increasing molecular weight;
• c) for each Tg ⁱ the difference Tg ⁱ -Tg¹ is 10 ° C;
• d) the amount of the monomers polymerized to produce the dispersed polymer 1, based on the amount of the total polymerized monomers in the process, is <85% by weight and 99.9% by weight;
• e) the total amount of the monomers polymerized in all polymerization stages i, based on the total amount of the total monomers polymerized in the process, is 0.1% by weight and <15% by weight;
• f) in each of the polymerization stages i, the monomers to be polymerized in this polymerization stage i are added to the polymerization vessel in such a way that, at the end of the addition, the polymerization conversion U ⁱ of monomers to be polymerized in stage i and the polymerization vessel already added to the polymerization at no time Exceeds 50 mol%;
• g) the total amount of the monomers polymerized in all polymerization stages i, apart from two monomers having conjugated ethylenically unsaturated groups, does not include monomers which have more than one ethylenically unsaturated group and
• h) the total amount of the monomers polymerized for the preparation of the polymer 1, apart from two monomers having conjugated ethylenically unsaturated groups, does not comprise more than 5% by weight of monomers which have more than one ethylenically unsaturated group.

2. The method according to claim 1, characterized in that in each of the polymerization stages i, the addition of the monomers to be polymerized in this polymerization stage i into the polymerization vessel is carried out in such a way that until the addition of the polymerization conversion U ⁱ of the stage i to be polymerized and the Polymerization already added monomers never exceeds 30 mol%. 3. The method according to claim 1, characterized in that in each of the polymerization stages i the addition of those in this Polymerization stage i monomers to be polymerized Polymerization vessel takes place so that the polymerization in essentially interrupted, the addition carried out that the resulting mixtures, if appropriate, stirred for some time, and then the polymerization is continued. 4. The method according to any one of claims 1 to 3, characterized records that in each of the polymerization stages i the addition the one to be polymerized in this polymerization stage i Monomers in the polymerization vessel as a pure addition of monomers he follows. 5. The method according to any one of claims 1 to 4, characterized records that the polymer 1 no monomers einpolymeri contains contains more than one ethylenically unsaturated Have group. 6. The method according to any one of claims 1 to 5, characterized records that in none of the polymerization stages i monomers be polymerized in, more than an ethylenically unung have saturated group.   7. The method according to any one of claims 1 to 5, characterized records that there is only one polymerization stage i sums up. 8. The method according to any one of claims 1 to 7, characterized records that Tg¹ is -60 ° C to 110 ° C. 9. The method according to any one of claims 1 to 7, characterized records that Tg¹ is -50 ° C to 0 ° C. 10. The method according to any one of claims 1 to 9, characterized in that the difference Tg ⁱ -Tg¹ is 60 to 190 ° C for each Tg ⁱ . 11. The method according to any one of claims 1 to 10, characterized characterized in that the weight average diameter of the disperse in an aqueous medium Polymer 1 is 200 nm to 500 nm. 12. The method according to any one of claims 1 to 11, characterized records that the total amount of all polymerization stages i polymerized monomers, based on the total amount of the total monomers polymerized in the process, 1% to 8% by weight. 13. The method according to any one of claims 1 to 12, characterized characterized in that the polymer 1 to at least 75 wt .-% from esters of acrylic and / or methacrylic acid with C₁- bis C₈-alkanols or their mixture with styrene and / or acrylic nitrile is built up. 14. The method according to any one of claims 1 to 13, characterized records that in the polymerization stages i polymeri based monomers are selected from the group comprising iso-butyl methacrylate, n-butyl methacrylate, tert-butyl meth acrylate, iso-bornyl acrylate, iso-bornyl methacrylate, 4-tert.- Butylcyclohexyl acrylate, 4-tert-butylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, acrylonitrile, styrene, α-methylstyrene, α-phenyl styrene and methyl methacrylate. 15. The method according to any one of claims 1 to 14, characterized records that the polymer 1 building monomers are selected from the group comprising ethyl acrylate, Methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, acrylic acid, methacrylic acid, acrylamide,  Methacrylamide, itaconic acid, styrene, acrylonitrile, acrylamido propane sulfonic acid and vinyl sulfonic acid. 16. The method according to any one of claims 1 to 15, characterized characterized in that the radical aqueous emulsion polymerization to produce polymer 1 a temperature of 60 to 90 ° C takes place. 17. The method according to any one of claims 1 to 16, characterized characterized in that the polymerization temperature in the Polymerization levels i 40 ° C to 80 ° C. 18. The method according to any one of claims 1 to 17, characterized characterized in that the radical aqueous emulsion poly merization for the preparation of the polymer 1 under With use of peroxodisulfuric acid and / or its salts is initiated. 19. The method according to any one of claims 1 to 18, characterized records that the radical polymerization in the poly merization stages i with the use of tert-butylhydro peroxide or cumene hydroperoxide is initiated. 20. Aqueous polymer dispersions, obtainable after a ver drive according to one of claims 1 to 19. 21. Polymer powder, obtainable by spray drying one aqueous polymer dispersion according to claim 20. 22. Use of aqueous polymer dispersions according to claim 19 as adhesives or as binders for paper coating slips, or as a binder for nonwovens, or as a binder for leather coatings, or as a binder for filled and / or pigmented paints, or as a binder for synthetic resin plasters, or as a binder for coatings of masses based on polyurethane. 23. Polymers obtainable by a process according to one of the Claims 1 to 19. 24. Aqueous polymer dispersions containing a polymer according to claim 23.