Method for the production of an aqueous polymer dispersion

Translation of description of equivalent WO 2004108782 A1

A process for preparing an aqueous polymer dispersion

description

The present invention is a method for preparing an aqueous polymer dispersion by polymerizing at least one et hylenisch unsaturated monomer B in an aqueous medium in the presence of particles of at least one polymer A (polymer particles A) and at least one dispersant, which is characterized in that the polymerization of the one ethylenically unsaturated monomer B in the presence of polymer particles a having a weight-average particle diameter> 1 nm occurs at least, wherein the polymer a is either

a) by one initiated with at least one radical initiator polymerization or b) by one initiated with at least one transition metal complex polymerization

of at least one ethylenically unsaturated monomer A (monomer A) was obtained

and the polymerization of at least one ethylenically unsaturated monomer B (monomer B)

i) in case a) by at least one transition metal complex and ii) in the case b) by at least one radical initiator

is initiated.

The present invention also includes the after process of the invention ren aqueous polymer dispersions obtainable, their use as binders in adhesives, sealants, polymer renders, paper coating, paints, for producing nonwovens, and for modifying mineral binders or other plastics, as well as the aqueous from the polymer accessible polymer powders and their respective use.

Aqueous polymer dispersions (latices) are generally known. These are fluid systems which contain as disperse phase in the aqueous dispersion of a plurality of intertwined polymer existing Polymerisatknäuel (so-called polymer) in disperse distribution. The gewichtsmittle- re diameter of the polymer is frequently in the range of 10 to 5000 nm. Like polymer during evaporation of the solvent, aqueous polymer dispersions have on evaporation of the aqueous dispersion medium, the potential for the formation of polymer films, which is why they are used in particular as binders application. Due to its environmentally friendly properties threaded it an increasingly important role.

The preparation of aqueous polymer dispersions is frequently done by radically initiated aqueous emulsion [see FIG. ., For example, Encyclopedia of Polymer Science and Engineering, Vol 8, page 659 ff (1987). . DC Blackley, in High Polymer latexes, Vol 1, page 35 et seq (1966). H. Warson, The Applications of Synthetic Resin Emulsions, page 246 ff, Chapter 5 (1972). D. Diederich, Chemie in unserer Zeit 24, pages 135-142 (1990); Emulsion Polymerization, Interscience Publishers, New York (1965); DE-A 40 03 422, and dispersions of synthetic high polymers, F. Holscher, Springer-Verlag, Berlin 1969]. A characteristic of this method is that so-called polar monomers are used as polymerization onskatalysatoren called radical generator and the main monomers generally.

The production of multi-phase aqueous polymer dispersions by free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated compounds (monomers) is known to the skilled worker. Examples can be found in EP-A 955 323, US-A 4,683,269 and in low-Peters, "core-shell dispersions using polymeric azo initiators", Dissertation University of Bayreuth., 1991

On the other hand a variety of polymerization catalysts are known whose po- lymerisationswirkung not based on mereninsertion radical formation but on a so-called mono. For this polymerization in particular so-called non-polar monomers are suitable. If anything, this polar monomers are used only to a minor extent for modifying the polymer properties. The Polymerisationskatalysa- used for these polymerization factors are particularly catalytically active transition metal complexes or transition metal complexes in combination with compounds that activate the transition metal complexes, called activators. Due to the usually high susceptibility to hydrolysis of the transition metal complexes or transition metal complex / activator combinations, these polymerization reactions are usually carried out in the form of a bulk polymerization, wherein the monomer reactant and solvent is at the same time or in the form of a solution polymerization, wherein a non-aqueous, often aprotic organic solvent for both the transition metal complex or the transition metal complex / activator combination, the monomer and the polymer formed contains dissolved. Examples of these include the documents DE-A 10017660, DE-A 10118633, Le ere et al., Angew. Chem., Int. Ed. Engl. 1998, 37, page th 922ff., Ziegler, Angew. Chem., 1955, 67, pages 541 ff., Natta, J. Am. Chem. Soc. 1962, 84, pages 1488ff. and sense and Kaminsky, Adv. Organornet. Chem. 1980, 18, pp 99ff ..

In recent times, is amplified reports the polymerization of monomers by means of monomer insertion in aqueous medium with hydrolysis-stable transition metal complexes or transition metal complex / activator combinations. Examples which may be mentioned here are the writings of Mecking, Angew. Chem. Int. Ed. 2001, 40, pages 534-540, Bauers and Mecking, Angew. Chem. Int. Ed. 2001, 40, pages 3020-3022, metal cking et al. Chem. Commun. 2000, pages 301 and 302, Tomov et al., Macromol.

Symp. 2000, 150, pages 53 to 58 as well as the publications WO 01/44325, WO 00/20464, DE-A 2,923,206 and DE-A 3,345,785th

Also, the polymerization of monomers having carbon monoxide in an aqueous medium a monomer insertion with hydrolysis-stable transition metal complexes or transition metal complex / activator combinations is known. Examples can be found in Held et al., Macromolecules 2002, 35, pages 3342-3347, Lindner et al., J. Organornet. Chem. 2000, 602, pages 173 ff., Sheldon et al., Angew. Chem. 2000, 112, pages 825ff. and in the publications WO 00/63277, DE-A 19829520, DE-A 19829520, DE-A 19917920 and DE-A 10,061,877th

In addition, can also conjugated dienes such as butadiene, in an aqueous medium are polymerized by means of insertion using hydrolysis-stable transition metal complexes or transition metal complex / activator combinations [see, for example, Ono and Kato, J. Polym. Be. A. 2000, 38, pages 1083-1089, Rinehart, J. Polym. Be. C. 1969, 27, pages 7 to 25 as well as DE-A 2332921 and EP-A 152 175].

Furthermore, the unpublished German application having the reference number DE-A discloses 10322466.1 which carried by a solid polymerization catalyst resulted polymerization of ethylenically unsaturated monomers in an aqueous medium, which likewise unpublished German application having the reference number DE-A 10229977.3 the corresponding polymerization by in wax particles contained polymerization and also unpublished German application having the reference number DE-a 10133042.1 preparing aqueous polymer dispersions by transition metal complex-catalyzed polymerization of ethylenically unsaturated compounds in the presence of carbon monoxide using a Miniemulsionspolymerisationsverfahrens.

The production of multiphase aqueous polymer dispersions by polymerization of ethylenically unsaturated monomers by means of hydrolysis-stable transition- metal complexes or transition metal complex / activator combinations known to the skilled worker. Examples can be found for example in Ono and Kato, J. Polym. Be. A. 2000 38, pages 1083-1089.

The preparation of aqueous polymer dispersions by means of free-radical emulsion has the advantage that the polymer properties, such as the glass transition temperature, are widely variable in a simple manner by appropriate selection of the monomers used for the polymerization and the auxiliaries, such as radical initiators, regulators etc. low tolerant connections depicting - len. A disadvantage is that the ethylenically unsaturated for the polymerization usually used as main monomers compounds such as esters of acrylic or methacrylic acid, styrene, vinyl chloride, vinylidene and vinyl esters of organic monocarboxylic acids due to the reaction steps necessary for their manufacture are relatively expensive, or low available monomers such as ethene, radically often polymerize only slowly. On the other hand low available for preparing aqueous polymer dispersions by means Übergangsmetallkomplex- catalyzed polymerization and rapidly abreagierende nonpolar monomers such as ethylene, propylene, butene, butadiene, etc. can be used as polar monomers, such as esters of acrylic or methacrylic acid, styrene , vinyl chloride, vinylidene and vinyl esters of organic monocarboxylic acids, although may also be used, but often much slower to react. Another disadvantage is that suitable for transition metal complex-catalyzed polymerization metal complexes are generally more expensive than the radical initiators used for the free-radically initiated aqueous emulsion polymerization.

Against this background of prior art, the object of the present invention was to provide a process for preparing aqueous polymer dispersions is available, which combines the advantages of free radical polymerization and the transition metal complex catalyzed polymerization in itself.

Accordingly, the process defined above was found.

is essential to the process that when the polymer A obtained by an initiated with at least one radical initiator, polymerization of at least one ethylenically unsaturated monomer A, the polymerization of at least one ethylenically unsaturated monomer B is initiated by at least one transition metal complex (Method 1) and then, if the polymer a is obtained by one initiated with at least one transition metal complex polymerization of at least one ethylenically unsaturated monomer a, the polymerization of the is initiated at least one ethylenically unsaturated monomer B by at least one radical initiator (method 2).

As at least one ethylenically unsaturated monomer for the free radical polymerisation (monomers A in process 1 and monomers B in process 2) are in particular readily radically polymerizable ethylenically unsaturated monomers, such as ethylene, vinyl aromatic monomers such as styrene, σ methylstyrene, o-chlorostyrene or vinyltoluenes; vinyl halides such as vinyl chloride or vinylidene chloride, esters of vinyl alcohol and 1 to 18, carbon atoms, monocarboxylic acids such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of preferably 3 to 6 carbon atoms having a, ß-monoethylenically unsaturated mono- and dicarboxylic acids, especially acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, with in general from 1 to 12, preferably nolen 1 to 8 and especially 1 to 4 carbon atoms which are alkali how particular methyl ethyl, n-butyl, iso- butyl, pentyl, hexyl, -heptyl-, octyl, -nonyl-, decyl and -2 -ethylhexylester, fumaric and dimethyl maleate or di-n-butyl maleate, nitriles αr,? -monoethylenically unsaturated carboxylic acids, such as acrylonitrile, methacrylonitrile, fumaronitrile, maleonitrile and C _-8thconjugated dienes such as 1, 3-butadiene and isoprene. Said monomers form the principal monomers, which, based on merenmenge Gesamtmono-, a share of more than 50 wt .-%, preferably more than 80 wt .-% to unite usually. In general, these monomers in water under standard conditions [20 ° C, 1 bar (absolute)] only moderate to low solubility.

Monomers which have increased water solubility under the abovementioned conditions, are those which contain at least one acid group and / or the corresponding anion thereof or at least one amino, amido, ureido or N-heterocyclic group and / or protonated on the nitrogen either or alkylated ammonium derivatives. Examples include σ,? monoethylenically unsaturated mono- and dicarboxylic acids and their amides, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, acrylamide and methacrylamide, also vinylsulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, styrene sulfonic acid and their water-soluble salts and N-vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-diethylamino) ethyl acrylate , 2- (N, N-

Diethylamino) ethyl methacrylate, 2- (N-tert-butylamino) ethyl methacrylate, N- (3-N ', N'-dimethylaminopropyl) methacrylamide and 2- (1-imidazolin-2-onyl) ethyl methacrylate. Normally, the abovementioned monomers are present only as modifying monomers, in amounts, based on the total amount, of less than 10% by weight, preferably less than 5 wt .-%. Monomers which usually increase the internal strength of the films of the polymer matrix normally contain at least one epoxy, hydroxyl, N-methylol or carbonyl group or at least two nonconjugated ethylenically unsaturated double bonds on. Examples include two vinyl radicals, monomers containing two vinylidene radicals monomers containing two alkenyl monomers. The diesters are particularly advantageous, dihydric alcohols with a, ß-monoethylenically unsaturated monocarboxylic acids, among which acrylic and methacrylic acid are preferred. Examples of such two nonconjugated ethylenically unsaturated double bonds are alkylene glycol diacrylates monomers and - dimethacrylates, such as ethylene glycol diacrylate, 1, 2-propylene glycol, 1, 3- propylene glycol, 1, 3-butylene glycol diacrylate, 1, 4-Butylenglykoldiacrylate and ethylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, methylenebisacrylamide, cyclopentene tadienylacrylat, triallyl cyanurate or triallyl isocyanurate. In this context, of particular importance are also the methacrylic and acrylic acid CrC_8th- Hydroxyalkyl as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl acrylate and methacrylate and also compounds such as diacetone and Acetylacetoxyethy- lacrylat or methacrylate. Frequently, the abovementioned monomers in amounts of up to 10 wt .-%, are, however, preferably less than 5 wt .-%, each based on the total amount used.

According to particularly favorable usable monomer mixtures for the radical polymerization are those which

50 to 99.9 wt .-% esters of acrylic and / or methacrylic acid having 1 to 12 carbon alkanols and / or styrene, or

50 to 99.9 wt .-% styrene and / or butadiene, or

50 to 99.9 wt .-% of vinyl chloride and / or vinylidene chloride, or

From 40 to 99.9 wt .-% of vinyl acetate, vinyl propionate, vinyl esters of

Versatic and / or vinyl esters of long chain fatty acids contain.

In particular, such monomer mixtures for the radical polymerization are used according to the invention, the

0.1 to 5 wt .-% of at least one 3 to 6 carbon atoms containing Cr, ß-monoethylenically unsaturated mono- and dicarboxylic acid and / or their amide and

50 to 99.9 wt .-% of at least one ester of acrylic and / or

Methacrylic acid having 1 to 12 carbon alkanols and / or styrene, or

0.1 to 5 wt .-% of at least one 3 to 6 C-atoms which σ,? -monoethylenically Unsaturated mono- and dicarboxylic acid and / or their amide and

50 to 99.9 wt .-% styrene and / or butadiene, or

0.1 to 5 wt .-% of at least one 3 to 6 C-atoms which σ,? -monoethylenically Unsaturated mono- and dicarboxylic acid and / or their amide and

50 to 99.9 wt .-% of vinyl chloride and / or vinylidene chloride, or

0.1 to 5 wt .-% of at least one 3 to 6 C-atoms which σ,? -monoethylenically Unsaturated mono- and dicarboxylic acid and / or their amide and

From 40 to 99.9 wt .-% of vinyl acetate, vinyl propionate, vinyl esters of

Versatic and / or vinyl esters of long chain fatty acids

contain. Polymers are obtained respectively by the free-radical polymerization, which are composed of the abovementioned monomers in copolymerized form.

It is important that the monomers or monomer mixtures can be polymerized in the step or gradient known to the expert. Also it should be noted at this point that in the context of this document, the term is intended to include a monomer and also monomer mixtures and the term polymer also Copo lymerisate.

It is essential that the polymer particles A are commonly used in both methods as stable aqueous dispersions. These can both be in the form of a Primärais also in the form of a secondary dispersion.

The preparation of an aqueous Polymerisatsekundärdispersion in method 1, for example via a radical solution, introducing this solution polymer to remove the solvent in the aqueous medium to form an aqueous dispersion of polymer particles A, is known to the expert (see for example EP-A 467 906, EP A 691 384 or Schiarb et al., Prog. Org. Coat. 1995 (29), pages 201 to 208). the polymer particles A are preferably used, however, in method 1 in the form of an aqueous primary dispersion.

As well as the free radical polymerization of monomer B in Method 2 is also the formation of a primary dispersion of polymer particles A in Process 1 by the method of the skilled worker radically initiated aqueous emulsion polymerization. This is usually carried out such that you. The least distributed a monomer A or B with the addition of at least one dispersing agent in an aqueous medium and polymerized by means of at least one free radical polymerization

Suitable free radical polymerization initiators are all those into consideration, which are capable of initiating a free radical aqueous emulsion polymerization. They may be in principle either be peroxides or azo compounds. Of course, redox initiator systems are also suitable. The peroxides used may in principle be inorganic peroxides such as hydrogen peroxide or peroxy xodisulfate as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric acid, such as its mono- and di-sodium, dipotassium or ammonium salts or organic peroxides, such as alkyl hydroperoxides, for example tert-butyl, p-menthyl or cumyl, and dialkyl or diaryl, such as di- tert-butyl or dicumyl peroxide are used. The azo compounds essen- sentlichen 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (amidinopropyl) dihydrochloride (equivalent to V-50 from Wako Chemicals). Suitable oxidizing agents for redox initiator the abovementioned peroxides are essentially. Corresponding reducing agents, sulfur compounds with a low oxidation state, such as alkali metal sulfites, for example potassium and / or sodium sulfite, alkali metal such as potassium and / or sodium hydrogen sulfite, alkali metal such as potassium and / or sodium metabisulfite, formaldehyde, for example potassium and / or Natriumformal- formaldehyde-sulfoxylate, alkali metal salts, especially potassium and / or sodium salts of aliphatic sulfonic finsäuren and alkali metal hydrogen sulfides, such as potassium and / or sodium umhydrogensulfid, polyvalent metal salts such as iron (II) sulfate, iron (II) - ammonium sulphate, iron (II) phosphate, endiols how dihydroxymaleic, benzoin and / or ascorbic acid, and reducing saccharides, such as sorbose, glucose, fructose and / or dihydroxyacetone. In general, the amount of free radical polymerization initiator is from 0.05 to 5.0 parts by weight, often 0.1 to 3.0 parts by weight, and often 0.2 to 2.0 parts by weight, each based on 100 parts by weight used in the radical polymerization monomers.

The manner in which the polymerization initiator is added to the polymerization is. Regarding the success of the process tends to be of minor importance according to the invention The polymerization initiator may be either completely initially taken in the polymerization when added continuously or stepwise in the course of free radical aqueous emulsion also according to its consumption. Specifically, this depends to a conventional manner from both the chemical nature of the initiator system and on the polymerization and the monomers to be polymerized in itself.

To adjust the molecular weight can optionally also known in the art of molecular weight regulators, for example alcohols such as butenediol or isopropanol, mercapto compounds such as 2-mercaptoethanol or tert

Dodecyl mercaptan or haloform compounds such as bromoform or chloroform, are typically on the total amount of the monomers used in the free radical polymerization, added in amounts of 0.1 to 5 wt .-%, based.

Suitable reaction temperatures for the free-radical aqueous emulsion polymerization of the entire range from 0 to 170 ° C into consideration. Here are usually from 50 ° to 120 ° C, frequently employed 60 to 110 ° C and often> 70 to 100 ° C. The free-radical aqueous emulsion polymerization can be at a pressure less than, equal to or greater than 1 bar (absolute). Preferably, highly volatile monomers such as ethylene, butadiene or vinyl chloride are po- under elevated pressure polymerized. Here, the pressure 1.2, 1, 5, 2, 5, 10, 15 bar or even higher values ​​are taking. Emulsion polymerizations are conducted under pressure, pressures of <950 mbar, frequently of <900 mbar and often <850 mbar (absolute) set. Advantageously, the radical aqueous emulsion polymerization is gas atmosphere under Inertga- as performed for example under nitrogen or argon.

Usually, the monomers are polymerized to a conversion of at least 80%, but usually a monomer conversion of> 90%,> 95% or> 98% is preferred.

As at least one ethylenically unsaturated monomer for the initiated by at least one transition metal complex polymerization (monomers B in process 1 and monomers A in process 2) join the present invention, both pure ethylenically unsaturated nonpolar hydrocarbon compounds and polar heteroatom-containing σ-olefins such as (meth) acrylic acid ester and Homoallyl - or allyl alcohols, ethers or halides into consideration. Among the pure hydrocarbons, non-polar ethylenically unsaturated C₂- To C₂₀-1-Alkenes suitable. Among these, the low molecular weight alkenes such as ethene or σ-alkenes emphasize having 3 to 20 carbon atoms, such as propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene or 1-decene. Of course, also cyclic olefins such as cyclopentene, cyclohexene, dicyclopentadiene or norbornene, conjugated dienes such as 1, 3-butadiene (butadiene), 2-chlorobutadiene, 2-methyl butadiene or 2,3-dimethylbutadiene, aromatic olefin compounds such as styrene, σ-methylstyrene or ortho- meta-, or para-vinyltoluene and vinyl esters such as vinyl acetate or vinyl propionate are used. However, particularly suitable are the C₂- To C₂₀-1-Alkenes. Among these, ethene, propene, 1-butene, 1-pentene, 1-hexene or 1-octene and 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene and compositions olefin fractions of a cracker are to be emphasized. Of course, it is possible according individually the aforementioned monomers or to use a mixture. Said monomers are generally the main monomers which, based on the total, a proportion> 50 wt .-% unite, in particular> 80 wt .-% or> 90 wt .-% in coming. Often made by at least one Ü bergangsmetallkomplexes be polymerized monomer mixture to 100 wt .-% of at least one of the aforementioned monomers.

In addition, however, it is also possible to use the aforementioned monomers in the mixture having such polar ethylenically unsaturated monomers which contain as structural element at least one amide group, an acid group and / or its corresponding anion. Examples include σ, .beta.-monoethylenically unsaturated mono- and dicarboxylic acids and their amides, such as acrylic acid, methacrylic acid, maleic einsäure, fumaric acid, itaconic acid, acrylamide, methacrylamide, and also vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, 10-undecenoic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid and their corresponding alkali metal and ammonium salts. Normally, the amide or acid group-containing mono- mers are present only as modifying monomers in amounts of <50 wt .-%, <10 wt .-%, preferably <5 wt .-%, in each case based on the total.

Of importance is that which may be obtained by polymerization of at least one mono- Neren A with at least one transition metal complex polymer accessible A- particles both in the form of a primary and in the form of a secondary dispersion.

The preparation of an aqueous Polymerisatsekundärdispersion in method 2, for example, a transition metal complex catalyzed solution, introducing this solution polymer to remove the solvent in the aqueous medium to form an aqueous dispersion of polymer particles A, is principle to those skilled in the art (refer, for example, DE-A 19821746 or Echersley et al., Am. Chem. Soc, Div. Polym. Chemistry, 1977 (38) pages 630ff.). the polymer particles A are preferred, however, used in Method 2 in the form of an aqueous primary dispersion.

Like the transition metal complex catalyzed polymerization of the monomer B in method 1, the formation of a primary dispersion of polymer particles A in Process 2 by the method of the skilled worker takes place transition metal complex catalyzed polymerization in an aqueous medium. This is usually carried out in such a way that one one monomer A or B with the addition of at least one dispersant by polymerizing at least at least one suitable transition metal complex in an aqueous medium. It is important that this polymerization can also be carried out in the presence of carbon monoxide.

For the transition metal complex catalyzed polymerization those transition metal complexes are suitable which are capable of initiating polymerization of ethylenically unsaturated monomers in an aqueous medium. For example, mentioned in the prior art complexes for the inventive polymerization are suitable.

As for being mentioned as examples in an aqueous medium for the polymerization of monomer A and monomer B in particular usable transition metal complexes described in DE-A 10133042 disclosed complexes [1, 3-bis (diphenylphosphino) propane] -, , 3-bis (di (2-methoxyphenyl) phosphino) propane] -,

, 3-bis (dimethylphosphino) propane] -,

, 3-bis (dietyhlphosphino) propane] -,

, 3-bis (di (n-propyl) phosphino) propane] -,

, 3-bis (di (iso-propyl) phosphino) propane] -,

, 3-bis (di (n-butyl) phosphino) propane] -

, 3-bis (di (n-pentyl) phosphino) propane] -

, 3-bis (di (n-hexyl) phosphino) propane] -,

, 3-bis (di (iso-hexyl) phosphino) propane] -,

, 3-bis (di (neo-hexyl) phosphino) propane] -,

, 3-bis (di (n-heptyl) phosphino) propane] -,

, 3-bis (di (3- (cyclopentyl) propyl) phosphino) propane] -,

, 3-bis (di (n-octyI) phosphino) propane] -,

, 3-bis (di (n-nonyl) phosphino) propane] -,

, 3-bis (di (n-decyl) phosphino) propane] -,

, 3-bis (di (n-dodecyl) phosphino) propane] -,

, 3-bis (di (n-tetradecyl) phosphino) propane] -,

, 3-bis (di (3- (cyclohexyl) propyl) phosphino) propane] - or

, 3-bis (di (n-hexadecyl) phosphino) propane] palladium (II) acetate, e in DE-A 10061877 disclosed complexes

, 3-bis (di-hydroxyphenyl) phosphinopropane] -,

, 3-bis (d -hydroxybutyl) phosphinopropane] -,

, 3-bis (di-4-methylol-5-hydroxypentyl) phosphinopropane] -

, 3-bis (di-5-hydroxypentyl) phosphinopropane] -,

, 3-bis (di-6-hydroxyhexyl) phosphinopropane] -,

, 3-bis (di (3-hydroxycyclopentyl) propyl) phosphinopropane] -,

, 3-bis (di-8-hydroxyoctyl) phosphinopropane] -,

, 3-bis (di-3-hydroxycyclohexyl) propyl) phosphinopropane] -,

, 3-bis (di-sulfonatophenyl) phosphinopropane] -,

, 3-bis (di-4-sulfonatobutyl) phosphinopropane] -,

, 3-bis (di-4-methylol-5-suIfonatopentyl) phosphinopropane] -,

, 3-bis (di-5-sulfonatopentyl) phosphinopropane] -,

, 3-bis (di-6-sulfonatohexyl) phosphinopropane] -,

, 3-bis (di (3-sulfonatocyclopentyl) propyl) phosphinopropane] -,

, 3-bis (di-8-sulfonatooctyl) phosphinopropane] -,

, 3-bis (di-3-sulfonatocyclohexyl) propyl) phosphinopropane] -,

, 3-bis (di-carboxyphenyl) phospinopropan] -,

, 3-bis (di-4-carboxybutyl) phosphinopropane] -,

, 3-bis (di-4-methylol-5-carboxypentyl) phosphinopropane] -,

, 3-bis (di-5-carboxypentyl) phosphinopropane] -, [1,3-bis (di-6-carboxyhexyl) phosphinopropane] -,

[1, 3-bis (di (3-carboxycyclopentyl) propyl) phosphinopropane] -,

[1, 3-bis (di-8-carboxyoctyl) phosphinopropane] - or

[1, 3-bis (di-3-carboxycyclohexyl) propyl) phosphinopropane] palladium (II) acetate, disclosed in DE-A 10,107,452 complexes

N, N, N-trimethyl-1-hexadecanaminium- (T-4) - [1- (diphenylphosphino-κP) -2- (hydroxy- κO) -2- (4-methylphenyl) ethylensulfonato] phenyl-nickel (ll) (triphenylphosphine) or

Sodium (T-4) - [1- (diphenyiphosphino-κP) -2- (hydroxy-κO) -2- (4-methylphenyl) ethylensulfonato] phenyl-nickel (II) (triphenylphosphine), which in the non-prepublished German Patent application with the file reference

DE-A 10240577.8 disclosed complexes

[2 - [[[2,6-bis (1-methylethyl) phenyl] imino-N] methyl] -4,6-diiodophenolato-κO] methyl nickel (II) (pyridine),

[2 - [[[2,6-bis (1-methylethyl) phenyl] imino-κN] methyl] -4,6-diiodophenolato-κO] phenyl- nickel (ll) (triphenylphosphine),

[2 - [[[2,6-bis (1-methylethyl) phenyl] imino-κN] methyl] -4,6-diphenylphenolato-κO] phenyl- nickel (ll) (triphenylphosphine),

[2 - [[[2,6-bis (phenyl) phenyl] imino-κN] methyl] -4,6-diphenylphenolato-κO] phenyl- nickel (ll) (triphenylphosphine), or [2 - [[[2,6 bis (phenyl) phenyl] imino-κN] methyi] -4,6-diiodophenolato- O] phenyl nickel (ll) (triphenylphosphine), and in co-unpublished German patent application with the file reference DE-A 10234005.6 disclosed complex systems ,

The specific reaction conditions such as temperature, pressure, catalyst amounts, etc. are disclosed in the relevant prior art. The transition metal complex catalyzed polymerization is often carried out with exclusion of oxygen, for example under an inert gas atmosphere such as nitrogen or argon and under carbon monoxide or Monomerenatmosphäre. The polymerization temperature and the polymerization pressure is strongly dependent on the activity of the transition metal complex used and the reactivity of the monomers to be reacted. It may be the polymerization temperature 0 to 200 ° C, or 20 to 50 ° C and 40 to 120 ° C and the polymerization pressure measured in the gas phase 1 to 300 bar, or 5 to 200 bar and from 10 to 100 bar (respectively absolute values).

It is also significant that the transition metal complex-catalyzed polymerization of ethylenically unsaturated monomers A (method 2) or B (method 1) can be carried out in an aqueous medium in the presence and under copolymerization of carbon monoxide. The transition metal complexes suitable for this purpose and the Conditions under which polymerization is carried out in aqueous medium, are disclosed for example in DE-A 10061877 or DE-A 10,125,238th

In addition, the transition metal complex-catalyzed polymerization can ethylenically unsaturated monomers A (method 2) or B (Method 1) disclosed in an aqueous medium in the form of, for example, in DE-A 19,859,191, carried out so-called ring-opening metathesis polymerization.

In the inventive method, at least one dispersing agent is also used, which holds distributed in the aqueous phase used for the polymerization in disperse the polymer A and the polymer particles formed during the polymerization of the monomer B and thus ensures the stability of the aqueous polymer dispersion. Dispersants both protective colloids and emulsifiers are.

Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polymethacrylic acids, cellulose derivatives, starch derivatives and gelatin derivatives, or acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid co- polymers, and their alkali metal salts but also N-vinylpyrrolidone, N-

Vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amine-group-containing acrylates, methacrylates, acrylamides and / or methacrylamides containing homo- and copolymers. A detailed description of further suitable protective colloids is given in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Ge org-Thieme-Verlag, Stuttgart, 1961, pages 411 to 420th

Of course, mixtures of emulsifiers and / or protective colloids can be used. Often dispersants are exclusively emulsifiers set one whose relative molecular weights, in contrast to the protective colloids, usually below 1500th They may be anionic, cationic or nonionic. Of course, the individual components must be compatible with one another in the case of use of mixtures of surfactants, a few preliminary can be checked in case of doubt by. In general, anionic emulsifiers are compatible with one another and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually not compatible with one another. An overview of suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208th Customary nonionic emulsifiers are ethoxylated mono-, di- and tri-alkylphenols (EO units: 3 to 50, alkyl: C to C₁₂) And ethoxylated fatty alcohols (EO units: 3 to 80; alkyl radical: C_8th to C∞). Examples are the Lutensol^® A grades (C₁₂-C Fatty alcohol ethoxylates, EO units: 3 to 8), Lutensol^® AO brands (C₁₃C₁₅- Oxoalkoholethoxilate, EO units: 3 to 30), Lutensol^® AT-marks (C₁₆C₁₈- Fatty alcohol ethoxylates, EO degree 11 to 80), Lutensol^® ON-marks (C₁₀- Oxoalkoholethoxilate, EO units: 3 to 11) and the Lutensol^® TO brands (C₁₃- Oxoalkoholethoxilate, EO units: 3 to 20) of BASF AG.

Customary anionic emulsifiers are alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C_8th -C₁₂), Of sulfuric monoesters of ethoxylated alkanols (EO units: 4 to 50, alkyl radical: C₁₂ -C₁₈) And ethoxylated alkylphenols (EO units: 3 to 50, alkyl: C₄ -C₁₂), Of alkylsulfonic acids (alkyl: C₁₂ -C₁₈) And kylarylsulfonsäuren of Al (alkyl: C₉ -C-ι_8th).

Further anionic emulsifiers are furthermore compounds of the formula I

<img id="imgf000016_0001" he="25" wi="52" file="imgf000016_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

wherein R and R² H atoms or C₄- To C₂₄-alkyl and are not simultaneously H Ato E, and may be A and B, alkali metal ions and / or ammonium ions. In the general formula I, R¹ and R² preferably linear or branched alkyl radicals having 6 to 18 carbon atoms, in particular having 6, 12 or 16 carbon atoms, or -H, R¹ and R² are not both simultaneously hydrogen atoms. A and B are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Particularly advantageous compounds I in which A and B are sodium, R¹ a branched alkyl group with 2 C-atoms and R² an H atom or R¹ is. Industrial mixtures are used which comprise domestic product containing from 50 to 90 wt .-% of the monoalkylated product, such as Dowfax^® 2A1 (trademark of Dow Chemical Company). The compounds I are generally known, eg from US-A 4,269,749, and are commercially available.

Suitable cationic emulsifiers are usually a C₆- To -C_8thAlkyl, - aralkyl or a heterocyclic radical containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium, pyridinium Imidazolini- umsalze, oxazolinium, morpholinium, thiazolinium and salts of Amine oxides, quinolinium, isoquinolinium, tropylium, sulphonium salts and phosphonium. called Dodecylammonium or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethyl ammonium) ethylparaffinsäureester, N-cetylpyridinium chloride, N Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethyl ammonium bromide, N- dodecyl N, N, N-trimethyIammoniumbromid, N-octyl-N, N, N-trimethlyammoniumbromid, N, N-distearyl-N, N-dimethyl ammonium chloride and the Gemini surfactant N, N (lauryl) ethylendiamindibromid. Numerous other examples can be found in H. Stache, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981, in Mc- Cutcheon's, Emulsifiers &amp; Detergents, MC Publishing Company, Glen Rock., 1989

However, particularly suited are non-ionic and / or anionic emulsifiers.

In general, a total of 0.05 to 20 parts by weight, frequently from 0.1 to 10 parts by weight, and often 1 to 7 parts by weight of dispersant, based on 100 parts by weight of an aqueous medium, formed from the amounts of deionized water and the at least one dispersant is used.

The amount of deionized water is calculated so that the Polymerisat- solids content of the inventive aqueous polymer dispersion obtained 5 to 75 weight .-%, frequently from 10 to 65 wt .-%, and often 20 to 55 wt .-%, each based on the aqueous polymer dispersion is,.

In the inventive process at least a portion of the deionized water and the at least one dispersant is submitted together with at least a subset of polymer particles A in the polymerization and any remaining amounts of polymer particles A, deionized water and the at least one dispersing agent during the polymerization of the monomer B continuously or discontinuously. As a rule, the monomers B is supplied to the polymerization vessel in accordance with its abreaction during polymerization continuously or intermittently. Often, the total amount of the polymer A is introduced in the polymerization vessel before the polymerization of the monomer B. According to method 1, the total amount of merisationsgefäß least one dispersing agent and / or the deionized water in the polymer is often presented before the polymerization of the monomer B, while method 2 is often a subset of at least one dispersing agent and / or the deionized water together with the monomers B is supplied in the form of an aqueous monomer under polymerization the aqueous dispersion of polymer particles a. The weight average particle size of the polymer particles A is&gt; 1 nm and often &lt;1000 nm. Often the weight average particle diameter is&gt; 5 nm,&gt; 10 nm,&gt; 20 nm,&gt; 30 nm,&gt; 40 nm,&gt; 50 nm,&gt; 60 nm&gt; 70nm,&gt; 80 nm,&gt; 90 nm or&gt; 100 nm and all values ​​in between and &lt;700 nm, &lt;500 nm, &lt;400 nm, &lt;350 nm, &lt;300 nm, &lt;250 nm, &lt;200 nm, &lt;150 nm , &lt;100 nm, &lt;90 nm, &lt;80 nm, &lt;70 nm, &lt;60 nm, &lt;50 nm or &lt;40 nm and all values ​​in between. The determination of the weight average particle diameter is known in the art and for example, via the method of the analytical ultracentrifuge. By weight-particle diameter is in this document, as determined by the method of analytical ultracentrifugation weight average D_w50understood value (see. this SE Harding et al., analytical ultracentrifugation tical in Biochemistry and Polymer Science, Royal Society of Chemistry, Cambridge, Great Britain, 1992, Chapter 10, Analysis of Polymer Dispersions with at Eight-Cell-AUC multiplexer: high resolution Particle Size distribution and density gradient Techniques, W. Mächtle, pages 147-175).

It can be advantageous if the polymer particles A are monomodal and have a narrow particle size distribution. Under narrow particle size distribution is in the context of this document be understood if the ratio of the determined by the method of analytical ultracentrifugation weight average particle diameter D_W50 and number average particle diameter D_N50 [D_w5o / D_N5O] &lt;2.0, preferably &lt;1, 5, and especially preferably &lt;1, 2 or &lt;1, ​​1.

Essentially depending on the emulsifier during the polymerization process of the invention can be controlled so that during the polymerization of a monomer B, are practically at least in addition to the existing polymer particles A no new polymer particles and thus two-phase, of polymer A and polymer B , obtained by the polymerization of monomers B, constructed, forming polymer. This is particularly the case when the emulsifier concentration is controlled during polymerization so that no new Emulgatormicellen be formed. The relevant measures are known to the expert. The case obtained, composed of polymer A and polymer B polymer, different particle morphologies, as have, for example, core / shell, raspberry or crescent structure etc.. Often the weight average particle diameter of the formed two-phase polymer particles be 50 to 1000 nm, often 70 to 700 nm or 80 to 500 nm or 90 to 400 nm or 100 to 300 nm.

however, the emulsifier is controlled so as to form new Emulgatormicellen, including particles of the polymer B can be formed in addition to the polymer A (polymer B). The formation of aqueous Polymer containing (composed of polymer A and B) polymer A, polymer B and two-phase polymer, is also possible. The actions to be taken for this purpose are known to the expert or can be determined from this in a few preliminary.

In general, the amount ratio of polymer A is, for at least one ethylenically unsaturated monomer B 1: 1000 to 1000: 1, but it can also be 1: 500 to 500: 1, 1: 200 to 200: 1, 1: 100 to 100: 1, 1: 50 to 50: 1, 1: 20 to 20: 1 or 1: 10 to 10: 1. Preferred is a ratio of 1: 100 to 100: 1, 1: 50 to 50: 1, 1: 20 to 20: 1 and 1: 10 to 10: 1.

What is important is that the inventive method can also be carried out in the presence of an organic solvent. This occurs particularly when the transition metal complexes to be used for the polymerization, which are sparingly soluble in an aqueous medium. Often in such a case, the complex is taken up in an organic solvent and fed to the aqueous medium in the form of an organic solution. Lying here already polymer radical generated A before (method 1), the solvent and the transition metal complex diffuses frequently in the present polymer particles A, which allows them to swell up. In this case can be used as organic solvents, polar protic or polar aprotic organic compounds having a molecular weight &lt;200 g / mol. Examples of these are polar aprotic organic solvents such as halogenated hydrocarbons, for example dichloromethane, dichloroethane or chloroform, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, or chlorobenzene, or aliphatic ethers, such as tetrahydrofuran or mixtures of these compounds. Furthermore, acetonitrile or acetone are used as liquid polar aprotic solvent or as a component among several used. Polar protic organic solvents include C_r -C₁₀Alkanols, especially C to C₆Alkanols such as methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-propanol-2, as well as the corresponding isomeric pentanols, hexanols, heptanols or.

Also it is possible to receive a solvent sparingly soluble in aqueous media transition metal complex in a likewise sparingly soluble in aqueous media organ Sichen solution. This is done particularly when there is no polymer particles A radical generated are present (method 2). In this case, the transition metal complex is taken at a slightly soluble in aqueous medium organic solvent and stirred into the aqueous medium in the presence of at least one dispersant to form droplets of solvent &lt;1000 nm, &lt;500 nm or &lt;300 nm. The necessary measures and bodies gen, such as ultrasonic or Hochdruckhomegenisatoren such as pressure column or other homogenizers such as Zahnkranzdispergato- reindeer etc. are known in the art (see. for example, GB-A 2,250,930, US-A 5,108,654 and PL Tang, ED Sudol, CA. Silebi and MS El-Aasser in Journal of Applied polymer Science, 1991 (43), pages 1059-1066). Subsequently, the preparation of the Polymeriatteilchen A is carried out by polymerization of corresponding monomers A. As in aqueous medium sparingly soluble organic solvents are liquid aliphatic and aromatic hydrocarbons having 5 to 30 carbon atoms, such as n-pentane and isomers, cyclopentane, n-hexane and isomers , cyclohexane, n-heptane and isomers, n-octane and isomers, n-nonane and isomers, n-decane and i-bond isomers, n-dodecane and isomers thereof, n-tetradecane and isomers, n-hexadecane and isomers, n-octadecane and isomers, eicosane, docosane, benzene, toluene, ethylbenzene, cumene, o-, m- or p-xylene, mesitylene, and generally hydrocarbon mixtures boiling in the range of 30 to 250 ° C using. Also employable are hydroxy compounds, such as saturated and unsaturated fatty alcohols having 10 to 28 carbon atoms, for example, n-dodecanol, n-tetradecanol, n-hexadecanol and isomers thereof or cetyl alcohol, esters such as fatty acid esters having 10 to 28 carbon atoms in the acid moiety and from 1 to 10 carbon atoms in the alcohol part or part esters of carboxylic acids and fatty alcohols with 1 to 10 C atoms in the carboxylic acid moiety and from 10 to 28 carbon atoms in the alcohol. Naturally, it is also possible to use mixtures of the abovementioned solvents.

The amount of organic solvent, based on the aqueous medium consisting of water and dispersing agents, is often &lt;20 wt .-%, &lt;10 wt .-%, &lt;5 wt .-%, or &lt;3 wt .-% or &lt; 1 wt .-%. Frequently the polymerization reaction is carried out without the addition of organic solvent.

Furthermore it may be advantageous that is present having a hydrophobic cavity and a hydrophilic shell during the polymerization of monomer A and / or monomer B in an aqueous medium at least one water-soluble macro- ular host compound. Common effects only the polymerization of monomer B in the presence of a corresponding water-soluble macromolecular host compound. Under a water-soluble macromolecular host compound to in this document, such host compounds are understood which. At 25 ° C and 1 bar (absolute) have a solubility of&gt; 10 g per liter of water It is advantageous if the solubility of the macromolecular host compounds is under the aforementioned conditions&gt; 25 g / l,&gt; 50 g / l,&gt; 100 g / l,&gt; 200 g / L or&gt; 300 g / l. As water-soluble macromolecular Wirtsverbindugen are advantageous, for example calixarenes, cyclic oligosaccharides, noncyclic oligosaccharides and / or derivatives thereof can be used.

Applicable according to invention calixarenes are described in US Patent 4,699,966, the international patent application WO 89/08092 and Japanese Patent Publications 1988/197544 and 1989/007837.

Cyclic oligosaccharides can, for example, by Takai et al. xose in the Journal of Organic Chemistry, 1994, 59 (11), pages 2967-2975, Cycloinulohe- and described but also -heptose cyclodextrins and / or their derivatives are used.

Particularly suitable cyclodextrins are α-cyclodextrin,? -cyclodextrin Or y cyclodextrin and their methyl, triacetyl, hydroxypropyl or Hydroxyethylderiva- te. Particularly preferred are the commercially available underivatized compounds are Cavamax^® W6, Cavamax^® W7 or Cavamax^® W8, the partially methylated compounds Cavasol.RTM^® W6M, Cavasol.RTM^® W7M or Cavasol.RTM^® W8M and teilhydro- xypropylierten compounds Cavasol.RTM^® W6HP, Cavasol.RTM^® W7HP or Cavasol.RTM^® W8HP (trademarks of Wacker-Chemie GmbH).

When non-cyclic oligosaccharides are for example starches and / or their degradation products.

The water-soluble starches or starch degradation products are frequently to native starches that have been made water-soluble by boiling with water or starch degradation products obtained by hydrolysis, in particular by acid-catalyzed hydrolysis, enzymatically catalyzed hydrolysis or oxidation of the native starches will. Such degradation products are also referred to as dextrins, roasted dextrins or saccharified starches. Their production of native starches is known to the expert and 173ff example in G. Tegge, starch and starch derivatives, EAS Verlag, Hamburg 1984, pp. and pages 220ff. and described in EP-A 0441 197th As native starches can be used practically all starches of plant origin, such as starches from corn, wheat, potato, tapioca, rice, sago and sorghum.

According to the invention can also chemically modified starches or starch degradation products. Chemically modified starches or starch degradation products are starches or starch degradation products are to be understood, in which the OH groups at least partly in derivatized, eg, in etherified or esterified present form. The chemical modification can be carried out both on the native starches as well as on the degradation products. It is also possible to convert the chemically modified starches afterwards into their chemically modified degradation products.

The esterification of starch or starch degradation products can be used both with inorganic and organic acids, carried their anhydrides or their chlorides. Customary esterified starches are phosphated and / or acetylated starches or starch degradation products. Etherification of the OH groups, for example, with organic halogen compounds see, epoxides or sulfates in aqueous alkaline solution carried out. Examples of suitable ethers are alkyl ethers, hydroxyalkyl, carboxyalkyl alkyl ethers, allyl ethers and cationically modified ethers, eg (Trisalkylammoni- to) alkyl and (trisalkylammonio) hydroxyalkyl ethers. Depending on the type of chemical modification, the starches or starch degradation products may be neutral, cationic, anionic or amphiphilic. The production of modified starches and starch degradation products is the most skilled (see. Ullmann's Encyclopedia of Industrial Chemistry, 5^th ed., Vol. 25, pages 12 to 21 and references therein).

In one embodiment of the present invention, water-soluble starch degradation products are and their chemically modified derivatives, which are obtainable by hydrolysis, oxidation on or enzymatic degradation of native starches or chemically modified starch derivatives, used. Such starch degradation products are also referred to as saccharified starches (see. G. Tegge, starch and starch derivatives, EAS Verlag, Hamburg 1984, pp 220ff.). Saccharified starches and their derivatives as such are commercially available (eg, C * Pur^®Products 01906, 01908, 01910, 01912, 01915, 01921, 01924, 01932 or 01934 of Cerestar Germany GmbH, Krefeld) or can be prepared by degradation of commercial starches by known methods, for example by oxidative hydrolysis with peroxides or enzymatic hydrolysis of the starches or chemically modified starches are produced. Favourable are hydrolytically accessible starch degradation products which are not chemically modified further.

Within the aforementioned embodiment, starch degradation products or chemically modified starch degradation products with a weight average molecular weight M_w in the range of 1000 to 30,000 Daltons and most preferably in the range of 3000 to 10,000 daltons used. Such strengths are bar completely soluble at 25 ° C and 1 in water, the solubility limit generally being above 50 wt .-% is what proves to be particularly favorable for the production of the novel copolymers in an aqueous medium. Advantageously, in particular C * Pur^® 01906 (M_w about 20,000) and C * Pur^® 01934 (M_w ca. 3000) are used. Information on the molecular weight of the aforementioned starch degradation products or chemically modified starch degradation products are based on determinations by means of gel permeation chromatography under the following conditions:

Columns: 3 pieces 7.5 x 600 mm steel filled with TSK gel G 2000 PW and

G 4000 PW. Pore ​​width 5 m.

Eluent: deionized water

Temperature: 20 to 25 ° C (room temperature) Detection: differential refractometer (eg ERC 7511)

Fleeds: 0.8 ml / min. Pump: (eg ERC 64.00)

Injection valve: 20 μ \ valve: (eg VICI 6-way valve)

Evaluation: Bruker ChromStar GPC software

Calibration: Calibration was carried out in the low molecular weight range with glucose se, raffinose, maltose and maltopentose. For the higher molecular weight range pullulan standards having a polydispersity &lt;1, used. 2

The amount of water soluble macromolecular rer host compound used in the present process is generally from 0.1 to 50 parts by weight, often from 0.2 to 20 parts by weight and frequently from 0.5 to 10 parts by weight, based in each case to 100 parts by weight of monomer A and / or monomer B.

Through targeted variation of the monomers A and / or B, it is inventively possible to fabricate aqueous polymer dispersions whose polymers have a glass transition temperature or a melting point in the range from -60 to 270 ° C.

With the glass transition temperature T_G, The limit of the glass transition temperature is meant according to G. Kanig (colloid Magazine &amp; Journal of Polymers, vol. 190, p 1, equation 1) tends with increasing molecular weight. The glass transition temperature or the melting point is after the DSC method (differential scanning calorimetry, 20 K min, midpoint measurement, DIN 53765).

According to Fox (TG Fox, Bull. Am. Phys. Soc. 1956 [Ser. II] 1, page 123 and man according to Ullmann's Encyclopedia of Industrial Chemistry, Vol. 19, page 18, 4th edition, Verlag Chemie, Weinheim, 1980), the glass transition temperature of at most weakly crosslinked copolymers in good approximation:

1 / Tg = X¹/ Tg¹ + X²/ Tg² + .... XTL^" " where x¹, x² xⁿ the mass fractions of the monomers 1, 2 n and T_G¹, T_G².... T_Gⁿ the

Glass transition temperatures of the mass fractions of the monomers 1, 2 n polymers synthesized in degrees Kelvin. The T_GValues ​​for Homopolymeri- sate of most monomers are known and for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol 5, Vol A21, page 169, VCH Weinheim, 1992, listed..; further sources of glass transition temperatures of homopolymers are, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1^st Ed., J. Wiley, New York 1966 2^nd Ed. J. Wiley, New York 1975, and 3^rd Ed. J. Wiley, New York 1989).

The accessible by the novel aqueous polymer dispersions often exhibit polymers whose minimum film formation temperature MFT often is &lt;80 ° C &lt;50 ° C or &lt;30 ° C. Because the MFT is no longer measurable below 0 ° C, the lower limit of the MFT can only by the T_GValues ​​are given. The MFT is determined according to DIN 53787th

in the aqueous polymer dispersions obtained are frequently the residual contents of unreacted monomers is also known by the person skilled in chemical and / or physical methods [see for example EP-A 771328, DE-A 19624299, DE-A 19621027, DE-A 19741184, DE-A 19741187, DE-A 19805122, DE-A 19828183, DE-A 19839199, DE-A 19840586 and 19847115] reduced.

The invention resulting aqueous polymer dispersions are often stable for several weeks or months and show during this time is usually virtually no phase separation, precipitation or coagulate. They are excellent in particular as binders in the production of adhesives, such as pressure-sensitive adhesives, building adhesives or industrial adhesives, sealants, polymer renders and paints, such as for paper, emulsion paints or for printing inks and varnishes for printing plastic films and for the production of nonwovens or for the production of protective layers and water vapor barriers, such as in the primer. Also, these aqueous polymer dispersions for modifying mineral binders or other plastics can be used.

It should also be noted that the invention available aqueous polymer dispersions in a simple manner can be dried to give redispersible polymer powders (eg freeze-drying or spray drying). This is especially true when the glass transition temperature of the aqueous polymer dispersion quantitatively predominant polymer A or B is usually&gt; 50 ° C, often&gt; 60 ° C or&gt; 70 ° C, often&gt; 80 ° C or&gt; 90 ° C or is&gt; 100 ° C. The polymer powders are also as a binder in adhesives, sealants, polymer renders and paints, and for producing nonwovens or for modifying mineral binders such as mortar or cement, or as modifying additives in other plastics.

It is also possible, according to the invention aqueous polymer dispersions obtainable to undergo the skilled worker coagulation, thereby coagulate the polymer and can be separated by simple filtration from the aqueous medium. Subsequent drying yields a polymer which re particular for modifying other plastic materials as well as to the production of moldings, in particular by injection molding or extrusion and can be used for coating surfaces.

The novel process opens up an economic, environmental, preparative-operatively simple and safety largely acceptable access to novel aqueous Polymerisatsystemen, which combines the advantages of free radical polymerization and the transition metal complex-catalyzed polymerization in itself.

The present invention is further illustrated by the following examples.

Examples

example 1

Preparation of [1, 3-bis (di (n-hydroxypentyl) phosphino) propane] palladium (II) diacetate (173ff according to Lindner et al., J. Organomet. Chem. 2000, 602, pp.)

642 mg (1, 25 mmol) 1, 3-bis (di (n-hydroxypentyl) phosphino) (room temperature) propane at 20 to 25 ° C weighed under an argon atmosphere in a Schlenk tube and anhydrous in 20 ml, degassed dichloromethane (Aldrich GmbH ) dissolved. In a second Schlenk tube, 286 mg (1, 27 mmol) palladium (II) acetate (99 wt .-%, Aldrich GmbH) dissolved in 20 mi of anhydrous, degassed dichloromethane at room temperature with stirring. The 1, 3-bis (di (n-hydroxypentyl) phosphino) propane solution was added diumacetatlösung at room temperature and under an argon atmosphere within 10 minutes to palladium, followed by stirring for 30 minutes and then the solvent in a vacuum (ca. 1 mbar absolute ) away. There was obtained 925 mg (yield: 99%) of [1, 3-bis (di (n-hydroxypentyl) phosphino) propane] palladium (II) diacetate in the form of a yellow-brown oil. example 2

a) transition metal complex catalyzed polymerization of 1-butene / carbon monoxide in an aqueous medium

In 2000 ml of deionized water, 200 mg [1, 3-bis (di (n-hydroxypentyl) phosphino) propane] palladium (II) 25.6 g of a 1 wt .- was treated sequentially at room temperature diacetate of Example 1, aqueous% strength solution of tetrafluoroboric (Aldrich GmbH) and 10 g sodium dodecyl sulfate (99 wt .-%, Aldrich GmbH) were dissolved with stirring and nitrogen gas atmosphere. The mixture was transferred to a 9 I-steel autoclave equipped with mechanical stirrer and electrically heated jacket. Then passed at room temperature, 1600 g of 1-butene in the autoclave. Thereafter, as long as you pressed under stirring at room temperature carbon monoxide into the autoclave, until a pressure of 50 bar was reached. With stirring, the autoclave was heated to 60 ° C and the carbon monoxide pressure 60 bar regulated and stirred while maintaining this kept constant pressure carbon monoxide for 10 hours. After cooling the autoclave to a temperature of about 40 ° C and relax to 4 bar (absolute) of the autoclave were transferred to a 5 l glass container with a mechanical stirrer, gas inlet and exhaust pipe and thereby to atmospheric pressure. Then removed unreacted 1-butene and carbon monoxide by one hour in a nitrogen flow at about 40 ° C. This resulted in a 2580 g of an aqueous polymer dispersion. The solids content of the polymer was after filtration through a 60 micron filter to 23 wt .-%, based on the aqueous polymer dispersion obtained after filtration is determined. The content of the remaining on the sieve was coagulum to 0.7 wt .-%, based on the aqueous polymer dispersion, is determined. The weight average particle size D_W5o the obtained polymer particles was 112 nm. The aqueous polymer dispersion obtained was stable and showed within 10 weeks no Phasense- are groomed or sedimentation.

The coagulate was generally determined by filtering the aqueous polymer dispersion through a 60 micron filter fabric. The filter cloth was then rinsed with 100 ml deionized water and dried in an oven at 100 ° C and atmospheric pressure to constant weight. From the weight difference of the filter cloth prior to filtration and the filter cloth after the filtration and drying of the coagulate the aqueous polymer dispersion was, in each case based on the aqueous polymer dispersion prior to filtration, is determined. The solids content was generally determined by drying approximately 1 g of the obtained after filtration aqueous polymer dispersion was dried in an open aluminum crucible having an internal diameter of approximately 3 cm in a drying oven at 100 ° C and atmospheric pressure to constant weight. salary to determine the solids, two separate measurements were each carried out and formed the corresponding average. the solids content is in each case based on the aqueous polymer dispersion after filtration.

The particle sizes were either after the method of the analytical ultracentrifuges fugue (W. Mächtle, Macromolecular Chemistry 1984 (185), pages 1025-1039) or by dynamic light scattering determines (autosizer MC Fa. Malvern Instruments, England) where the average diameter of the cumulant [cumulant z-average] of the measured autocorrelation function according to ISO standard is indicated 13,321th

10 ml of the aqueous polymer dispersion obtained was placed in a polyethylene tray with an inner diameter of about 5 cm and dried at 23 ° C and 50% relative humidity for 24 hours. This gave a rough, cracked polymer film. The glass transition temperature of the polymer was about 9 ° C contributing factors. In addition, the polymer still had a wide melting point range from 80 to 120 ° C. The determination of the glass transition temperature or the melting point (melting range) was generally in accordance with DIN 53765 using a DSC 820 instrument, series TA 8000, Messrs. Mettler-Toledo.

The molecular weight of the dried polymer film was permeation chromatography by gel permeation (GPC) (hexafluoroisopropanol with 0.05 wt .-% trifluoroacetic acid-potassium salt; the calibration was carried out with narrow distribution polymethacrylate standards from PSS having molecular weights of M = 505 to. M = 2740000; lying outside this interval were estimated Elution completed by extrapolation; detection was with a differential refractometer HP 1100 Fa Hewlett Packard).. The number-average molecular weight was M_n 9000 g / mol and the weight average molecular weight M_w 21000 g / mol.

b) radical emulsion polymerization in the presence of Polyketondispersion a)

In a glass reactor which is thermostatically controlled in a heating bath and is equipped with a mechanical stirrer, reflux condenser and two feed vessels, stirred, 265.5 g of aqueous Polyketondispersion a) were placed under nitrogen atmosphere. The feed vessel 1 was charged with an emulsion consisting of 119 g deionized water, 4.8 g of a 15 wt .-% aqueous solution of n-Dodecylbenzolsulfonat- Sodium salt, 119 g of n-butyl acrylate and 1.2 g of acrylic acid charged. The feed vessel 2 was treated with a solution consisting of 0.84 g sodium and 40 g of deionized water, filled.

The contents of the initial charge was heated with stirring and nitrogen atmosphere to 80 ° C, 4 g of feed 2 and stirred for 10 minutes. Thereafter, feed 1 was added continuously over one hour and the remainder of feed 2 continuously within one and a half hours at the aforementioned temperature and then cooled to room temperature.

The aqueous polymer dispersion obtained had a coagulum content of 0.5 wt .-% and the solids content was determined to be 33 wt .-%. The weight average particle size D_w50 the obtained polymer was 188 nm.

10 ml of the aqueous polymer dispersion obtained was placed in a polyethylene tray with an inner diameter of about 5 cm and dried at 23 ° C and 50% relative humidity for 24 hours. This gave a closed, flexible and transparent polymeric film. The glass transition temperature of the polymer was determined to be 40 ° C. In addition, the polymer still had a wide melting point range of about 80 to 120 ° C.

example 3

A composition prepared by radical emulsion polymerization of polystyrene dispersion having a weight average particle diameter D_w50 of 30 nm and a polydispersity tätsindex of &lt;1, 5 was diluted with deionized water to a solids content of 10 wt .-%.

100 ml of this aqueous dispersion of polystyrene were placed in a Schlenk tube with 10 ml of a 10 wt .-% solution of [1,3-bis (di (n-hexyl) phosphino) propane] - palladium (II) diacetate (prepared analogously to Example 1) styrene added in and stirred at room temperature under nitrogen atmosphere for 24 hours. Thereafter, the polystyrene particles were swollen with styrenic catalyst solution and no separate styrene roltröpfchen longer visible (light microscope; magnification: 40x).

10 g of the aforementioned "swollen" polystyrene dispersion were stirred under nitrogen in 2000 g of deionized water and treated successively at room temperature with 12 g of a 1 wt .-% solution of tetrafluoroboric acid in entionisierem water, 10 g of sodium dodecyl sulfate (Fa. Aldrich GmbH) and 20 g cyclodextrin cava sol^® W7 M (Fa. Wacker-Chemie GmbH). The aqueous mixture was in one NEN 9 I steel autoclave transferred with mechanic stirrer and electrically heated jacket. Followed by the metered the autoclave also at room temperature 100 g of 1-hexene to, led to a to a pressure of 50 bar of carbon monoxide and heated the autoclave at 60 ° C on. Here you regulated the carbon monoxide pressure at a constant 60 a bar. With stirring and a constant pressure of carbon monoxide were 1-hexene added via an HPLC pump for 10 hours, 900 g. Then allowed to the reaction mixture for 2 hours at this temperature, the autoclave was vented to 4 bar and transferred to the autoclave in a 5 l glass container equipped with a mechanical stirrer and a gas inlet and exhaust Röhr. unreacted 1-hexene was removed by passing hour of gaseous nitrogen through the aqueous dispersion heated to 70 ° C. This gave 2830 g of an aqueous polymer dispersion. The aqueous polymer dispersion obtained had a coagulum content of 0.1 wt .-%. The solids content was determined to be 28 wt .-%. The means of dynamic Lichtstreύung determined medium-re particle size of the obtained polymer particles was 260 nm.

10 ml of the aqueous polymer dispersion obtained was placed in a polyethylene tray with an inner diameter of about 5 cm and dried at 23 ° C and 50% relative humidity for 24 hours. This gave a brittle, closed film. The glass transition temperature of the polymer was determined to be -10 ° C.

From the obtained polymer film, the molecular weight was determined by means of gel permeation chromatography. The number-average molecular weight was M_n 8600 g / mol and the weight average molecular weight M_w 20000 g / mol.

example 4

a) transition metal complex-catalyzed preparation of a polyethylene dispersion

19 mg Tetrachlorobenzochinon (Fa. Aldrich GmbH) were dissolved under an argon atmosphere in a Schlenk tube in an anhydrous and degassed mixture of 4 g of toluene, 0.2 g of hexadecane and 1 ml of methanol, the solution after stirring at room temperature 18 mg of triphenylphosphine and 20 mg bis (cyelooctadien) Niekel (0) (Fa. Strem Chemicals Inc.) was added and the resulting solution stirred for 30 minutes. This solution is then placed under stirring 95 ml of a 1 wt .-% solution of sodium dodecyl sulfate in deionized water to give a trained oil-in-water macroemulsion. Using a Microfluidizer (type 120 from the company. Microfluidics Corp.) was prepared therefrom by high-pressure homogenization at 750 bar a so-called mini-emulsion. The average droplet size of the emulsion droplets was by means of quasielastic dynamic light scattering with a Coulter N4 Plus Particle Analyzer determines the Fa. Coulter Scientific Instruments to 150 nm. The aqueous mini-emulsion was added under argon atmosphere, into a 300 ml autoclave equipped with mechanical stirrer, electric heating, as well as two separate feeds, via leads. Then passed under stirring ethene up to a pressure of 50 bar and the reaction mixture heated under constant ethylene pressure at 50 ° C and left under stirring at this temperature for two hours. Thereafter, a 5 ml sample was removed via a diptube. The solids content of the resulting polymer was determined to be 19 wt .-%.

The aqueous polymer dispersion obtained was placed in a polyethylene tray with an inner diameter of about 5 cm and dried for 24 hours at 23 ° C and 50% relative humidity. This gave a colorless, cracked polymer film with no detectable glass transition temperature. However, the polymer had a melting point of about 126 ° C.

From obtained polymer film, the molecular weight was determined by GPC (o-xylene; the calibration was carried out with narrow distribution polystyrene from PSS having molecular weights of M = 400 to M = 2.5 million g / mol;. Outside this interval were Elution by extrapolation estimated and the detection was carried out with a differential refractometer HP 1100 Fa Hewlett Packard).. The number-average molecular weight was M_n 6000 g / mol and the weight average molecular weight M_w 16000 g / mol.

b) radical emulsion polymerization in the presence of polyethylene dispersion a)

The temperature of the product obtained under a) the autoclave was elevated while maintaining the Ethendrucks from 50 to 85 ° C. Followed by the metered stirring 5 g of a feed 1, consisting of an emulsion of 60 g of vinyl acetate, 40 g of deionized water, 0.2 g Mowiol 4088 (polyvinyl Fa. Clariant) and 0.5 g sodium dodecyl sulfate (Fa . Aldrich GmbH) in the autoclave. After 5 minutes, were metered simultaneously starting two separate feeds the remainder of feed 1 and the total amount of feed 2, consisting of a solution of 1 g of sodium in 5 g of deionized water over 1, 5 hours. After a reaction time of half an hour, the autoclave was cooled to room temperature and depressurized to atmospheric pressure.

The aqueous polymer dispersion was filtered through a 60 micron filter cloth, with only traces of coagulum was found. The solids content of the resulting aqueous polymer dispersion was 38 wt .-% and the determined by dynamic light scattering average particle size of the polymer particles was 210 nm.

10 ml of the aqueous polymer dispersion obtained was placed in a polyethylene tray with an inner diameter of about 5 cm and dried at 23 ° C and 50% relative humidity for 24 hours. This gave a clear flexible film. The glass transition temperature of the polymer was determined to be 5 ° C. In addition, the polymer still had a melting point of about 120 ° C.

example 5

a) transition metal complex-catalyzed preparation of a polybutadiene

In a Schlenk tube with magnetic stirring 82 mg of cobalt (II) under argon atmosphere octanoate weighed (Fa. Strem Chemicals Inc.), followed by cooling the Schlenk tube with a cryostat to -10 ° C. Thereafter, the Schlenk tube and then 470 mg of a 30 wt .-% solution of triisobutylaluminum in toluene (Aldrich GmbH Fa.) Were 300 mg 1, 3-butadiene condensed (short butadiene), weight is added and the resulting mixture for 10 minutes at -10 C. stirred. The mixture was poured into a nitrogen-inertized, heated to 50 ° C autoclave transferred with 300 ml volume, in the previous 100 ml of deionized and degassed water, 1 g of sodium dodecyl sulfate, 18 mg of carbon disulfide and 30 g of butadiene were charged. This reaction mixture was allowed to react at 50 ° C with stirring for 2 hours. Subsequently, a via a riser tube a 5 ml sample was taken.

The solids content of the resulting aqueous polymer dispersion was 18 wt .-% and the determined by dynamic light scattering average particle size of the polymer particles was 230 nm.

1 ml of the resulting aqueous polymer dispersion was placed in a polyethylene tray with an inner diameter of about 5 cm and dried for 24 hours at 23 ° C and 50% relative humidity. This gave a white powder. The glass transition temperature of the polymer was determined to be -17 ° C. In addition, the polymer still had a melting point of about 175 ° C. b) radical emulsion polymerization in the presence of polybutadiene a)

The autoclave contents are obtained from a) was heated with stirring to 90 ° C, this sem added then 1 g of a feed stream 3, and the mixture was stirred at the aforementioned reaction temperature for 10 minutes. Thereafter, the total amounts of feed 1 and feed 2 over 2 hours and the remaining amount of feed 3 over 2.5 hours were added continuously, beginning simultaneously. After completion of addition of feed 3 was at reaction temperature for 15 minutes more, then cooled to about 30 to 35 ° C and the reactor was content to atmospheric pressure. For depletion unreacted butadiene is then introduced still for about an hour nitrogen gas through the resultant aqueous polymer dispersion.

Feed 1: 50 g of butadiene

Feed 2: aqueous emulsion composed of 50 g of styrene, 1 g of acrylic acid, 0.2 g tert-

Xapón Dodecyimercaptan, 3.0 g of a 28 wt .-% aqueous solution of tele-^® NSO (Fa. Cognis) and 40 g of deionized water

Feed 3: 0.5 g of sodium dissolved in 10 g of deionized water

The aqueous polymer dispersion obtained had a coagulum content of 0.4 wt .-% and the solids content was determined to be 46 wt .-%. The means of dynamic light scattering particle size of the resulting determined average Polymeriatteil- chen was 303 nm.

10 ml of the aqueous polymer dispersion obtained was placed in a polyethylene tray with an inner diameter of about 5 cm and dried for 24 hours at 23 ° C and 50% relative humidity. There was obtained th a clear flexible film. The glass transition temperature of the polymer was determined to be -5 ° C. In addition, the polymer still had a melting point of about 170 ° C.