EP1537150A1 - Method for the production of aqueous polymer dispersions - Google Patents

Abstract

The invention relates to a method for the production of aqueous polymer dispersions, by the polymerisation of one or more olefins in aqueous media in the presence of dispersing agents and optionally organic solvents, characterised in that the polymerisation of the olefin(s) is catalysed by means of one or more complex compounds of general formula (I), where at least one of the groups R<1> to R<9> must be in the form of a group of the following general formula (II) where Z = an electron-withdrawing group and n= a whole number from 1 to 5.

Description

Process for the preparation of aqueous polymer dispersions

description

The present invention relates to a process for the preparation of aqueous polymer dispersions by polymerizing one or more olefins in an aqueous medium in the presence of dispersants and, if appropriate, organic solvents, characterized in that the polymerization of the olefin (s) is catalyzed using one or more complex compounds of the general formula I

in which the substituents and indices have the following meaning:

M is a transition metal from groups 7 to 10 of the Periodic Table of the Elements,

L ⁱ phosphines (R ¹⁶ ) _X PH ₃ _ _X or amines (R ¹⁶ ) _X NH ₃ _ _X with identical or different radicals R ¹⁶ , ether (R ¹⁶ ) ₂ 0, H ₂ 0, alcohols (R ¹⁶ ) 0H, Pyridine, pyridine derivatives of the formula C ₅ H ₅ - _X (R ¹⁶ ) _X N, CO, C 1 -C ₂ alkyl nitriles, C ₆ -C ₄ aryl nitriles or ethylenically unsaturated double bond systems, where x is an integer from 0 to 3 means

Eating halide ions, amide ions (R ¹⁵ ) _h NH_ _h , where h is an integer from 0 to 2, and furthermore C 6 -C 6 -alkyl anions, allyl anions, benzyl anions or aryl anions,

where L ¹ and L ² can be linked to one another by one or more covalent bonds,

X: CR, nitrogen atom (N)

R: hydrogen, Ci-Cg-alkyl groups, C -C ₃ aralkyl radicals or

C ₆ -C ₄ aryl groups, optionally substituted by one or more Ci-C ^ alkyl groups, halogens, one or more halogenated C ₁ -C ₁ alkyl groups, C ₁ -C alkoxy groups, silyloxy groups OSiR ¹¹ R ^12th R ¹³ , amino groups NR ¹ R ¹⁵ or C ¹ -C ₂ thio ether groups,

Y: OH group, oxygen, sulfur, NR ¹⁰ or PR ¹⁰ ,

N: nitrogen atom

R ¹ to R ⁹ : independently of one another hydrogen,

Cχ-Cι alkyl, where the alkyl groups can be branched or unbranched,

-CC -alkyl, mono- or polysubstituted, identically or differently, by -CC ₂ -alkyl groups, halogens, -C -CC -alkoxy groups or -CC -thioether- groups, C -Cι ₃ aralkyl, C ₃ - Ci ₂ -cycloal yl, C ₃ -C -cycloalkyl, substituted one or more times identically or differently by -CC -alkyl groups,

Halogens, C 1 -C ₂ alkoxy groups or C 1 -C ₂ thio ether groups, C ₆ -Ci ₄ aryl, C ₆ -C ₄ aryl, substituted identically or differently by one or more Cχ-Ci ₂ alkyl groups, halogens , singly or multiply halogenated Cι _Cι-2 alkyl groups, Cι-Cι ₂ alkoxy groups, silyloxy groups OSiR ¹¹ R ¹² R ^13, amino groups NR ¹⁴ R ¹⁵ or Cχ-C ₁₂ ether groups thio, Cι-Cι ₂ - alkoxy,

Silyloxy groups OSiR ^{1: L} R ¹² R ¹³ , halogens, N0 ₂ groups or amino groups NR ¹ R ¹⁵ , where two adjacent radicals R ¹ to R9 together can form a saturated or unsaturated 5- to 8-membered ring,

R ¹⁰ to R ^{16 are} independently hydrogen,

-C-C o-alkyl groups, which in turn with 0 (C _α -C ₆ alkyl) or N (-C-C ₆ alkyl) ₂ groups can be tuiert, -C -C cycloalkyl groups, C ₇ -Cι ₃ aralkyl radicals or C _ß -C ^ aryl groups,

where at least one of the radicals R ¹ to R ^{9 must be} in the form of a radical of the general formula II below

where Z is an electron-withdrawing group and n is an integer from 1 to 5.

Furthermore, the present invention relates to aqueous dispersions of polyolefins or copolymers of several olefins, and to the use of the aqueous dispersions according to the invention for paper applications such as paper coating or surface sizing, paint coatings, adhesive raw materials, molded foams such as mattresses, textile or leather applications, carpet backing coatings or pharmaceutical applications.

The common processes for the preparation of aqueous polymer dispersions from the olefins ethene, propene and / or 1-butene either use free-radical high-pressure polymerization or else the preparation of secondary dispersions. These methods have disadvantages. The radical polymerization processes require extremely high pressures, they are limited on an industrial scale to ethylene and ethylene copolymers, and the equipment required is very expensive to purchase and maintain (F. Rodriguez, Principles of Polymer Systems, 2nd edition, McGraw-Hill, Singapore 1983, page 384). Another possibility is to first polymerize the aforementioned olefins in any process and then to produce a secondary dispersion, as described, for example, in US Pat. No. 5,574,091. This method is a multi-stage process and therefore very complex.

It was therefore desirable to prepare aqueous polymer dispersions of olefins, such as the industrially available olefins ethylene, propylene, butylene, etc., in one process step by polymerizing the olefins in an aqueous medium. In addition, polymerization in aqueous medium has the general advantage that the heat of polymerization can be easily removed due to the process. After all, polymerization reactions in aqueous systems are quite general interesting because water is a cheap and environmentally friendly solvent.

The following prior art is to be assumed for the metal complex-catalyzed polymerization of olefins.

With electrophilic transition metal compounds such as TiCl ₄ (Ziegler-Natta catalyst) or metallocenes, olefins can be polymerized, as described, for example, by H.-H. Brintzinger et al. in Angew. Chem. 1995, 207, pages 1255ff., Ängew. Chem. , Int. Ed. Engl. 1995, 34, pages 1143ff. is described. However, both TiCl ₄ and metallocenes are sensitive to moisture and are therefore not very suitable for the polymerization of olefins in an aqueous medium. The aluminum alkyls used as cocatalysts are also sensitive to moisture, so water must be carefully excluded as a catalyst poison.

There are few reports of transition metal catalyzed reactions of olefins such as ethylene in an aqueous environment. L. Wang et al. in J. ^" Am. Chem. Soc. 1993, 115, pages 6999ff. on a rhodium-catalyzed polymerization. However, the activity is much too low at around one insertion / hour for technical applications.

The reaction of ethylene with nickel-P, O-chelate complexes, as described in US Pat. Nos. 3,635,937, 3,637,636, 3,661,803 and 3,686,159, appears to be much more promising. The disadvantage is that the reported activities are too low.

EP-A 46331 and EP-A 46328 report on the reaction of ethylene with Ni chelate complexes of the general formula A, the same or different organic groups being used under R.

Substituents are understood, one of which carries a sulfonyl group and F is phosphorus, arsenic or nitrogen. Under the selected reaction conditions in solvents such as methanol or mixtures of methanol and a hydrocarbon, only oligomers were obtained which are unsuitable for the above-mentioned applications. The advantage of the sulfonated derivatives over unsulfonated compounds, as described by W. Keim et al. in Angew. Chem. 1978, 90, pages 493ff .; Angew. Chem. , Int. Ed. Engl. 1978, 6, pages 466ff., Is in their higher activity.

US Pat. No. 4,698,403 (column 7, lines 13-18) and US Pat. No. 4,716,205 (column 6, lines 59-64) disclose that an excess of water acts as a catalyst poison over bidentate Ni chelate complexes, even if they carry an S0 ₃ ^_ group.

It can be seen from the documents cited above that numerous Ni complexes are not polymerization-active in the presence of water.

On the other hand, it is known from WO 97/17380 that palladium compounds of the formula B

Et = C ₂ H ₅ , Ph = phenyl in which R * is, for example, isopropyl groups, or the analog nickel compounds can polymerize higher olefins such as 1-octene in an aqueous environment. Optionally, an emulsifier can be added to facilitate polymerization. However, please note that the temperature should not exceed 40 ° C, otherwise the catalytic converter will be deactivated (page 25, lines 5ff.). higher

However, reaction temperatures are generally desirable because this can increase the activity of a catalyst system.

A further disadvantage of catalyst systems of the general formula B is that generally highly branched polymers are formed with ethylene (LK Johnson J. Am. Chem. Soc. 1995, 117, pages 6414ff _.; C. Killian, J. Am. Chem. Soc. 1996, 118, pages 11664ff.), Which have so far been of less technical importance, and, with higher α-olefins (LT Nelson Polymer Preprints 1997, 38, pages 133ff.), So-called "chain running" of the active complexes is observed. "Chain running" leads to a large number of l, ω false insertions, and as a result, amorphous polymers are generally produced which are not very suitable as materials.

5 From WO 98/42665 it is also known that complexes of the general formula C,

15 with M = Ni or Pd and n neutral ligands L are polymerization-active in the presence of small amounts of water without the catalytic activity suffering (page 16, line 13). However, these amounts of water must not exceed 100 equivalents, based on the complex (page 16, lines 30 and 31). Under

However, under these conditions, polymerization cannot be carried out in an aqueous medium.

It is also known from WO 98/42664 that complexes of the general formula D,

= Phenyl

" _{with the} same or different radicals R should be able to polymerize ethylene in the presence of small amounts of water (see page 17, lines 14ff.). However, these amounts of water should not exceed 100 equivalents, based on the complex ( Page 17, lines 33 to 35. Under these conditions is

⁴⁰ but no polymerization in an aqueous medium is conceivable.

The object of the present invention was therefore to remedy the disadvantages described and to provide a new process for the preparation of aqueous polymer dispersions by polymerizing one or more olefins in an aqueous medium in the presence of complex compounds, which is easy to carry out and leads to dispersions of olefin polymers with high molecular weights.

Surprisingly, it has now been found that aqueous olefin polymer dispersions, the polymers of which have high molecular weights, are obtained by the process defined at the outset.

Examples of suitable olefins for the preparation of homopolymers for the process according to the invention are: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and

1-eicosen, but also branched olefins such as 4-methyl-1-pentene, norbornene, vinylcyclohexene and vinylcyclohexane and styrene, para-methylstyrene and para-vinylpyridine, ethylene and propylene being preferred. Ethylene is particularly preferred.

The copoly erization of two or more olefins is also possible using the process according to the invention, the coolefins used being able to be selected from the following groups:

* Non-polar 1-olefins, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and 1-eicosen, but also branched olefins, such as 4-methyl -l-pentene, vinylcyclohexene and vinylcyclohexane and styrene, para-methylstyrene and para-vinylpyridine, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene being preferred.

* Olefins which contain polar groups, such as, for example, acrylic acid, C 6 -C 8 -alkyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methacrylic acid, C-Cβ-alkyl methacrylate, Cχ-C ₆ -Alkyl-vinyl ether and vinyl acetate, but also 10-undecenoic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid and styrene-4-sulfonic acid. Acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, ethyl vinyl ether, vinyl acetate, 10-undecenoic acid, 3-butenoic acid and 4-pentenoic acid and 4-pentenoic acid are preferred 5-hexenoic acid.

The proportion of coolefins in the olefin mixture to be polymerized is freely selectable and is usually <50% by weight, frequently <40% by weight and often <30% by weight or <20% by weight. If olefins containing polar groups in particular are used for the copolymerization, their proportion in the olefin to be polymerized is mixture generally> 0.1% by weight,> 0.2% by weight or> 0.5

% By weight, and <2% by weight, <5% by weight or <10% by weight.

Only ethylene is preferably used. If at least two olefins are used for the polymerization, these are often selected from the group comprising ethylene, propylene, 1-butene, 1-hexene and styrene. Ethylene is often used in combination with propylene, 1-butene, 1-hexene or styrene.

The residues in the complex compounds of the general formula I are defined as follows:

M is a transition metal from groups 7 to 10 of the Periodic Table of the Elements, preferably manganese, iron, cobalt, nickel or palladium and particularly preferably nickel or palladium

L ¹ is selected from phosphines of the formula (R ¹⁶ ) _X PH ₃ _ _X or amines of the formula (R ¹⁶ ) _X NH ₃ _ _X , x is an integer between 0 and 3. But also ether (R ¹⁶ ) ₂ 0 such as diethyl ether or tetrahydrofuran, H ₂ 0, alcohols (R ¹⁶ ) OH such as methanol or ethanol, pyridine, pyridine derivatives of the formula C ₅ H ₅ _ _X (R ¹⁶ ) _X N, such as 2 -Picolin, 3-picoline, 4-picoline, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine or 3,5-lutidine, CO, -CC-alkyl nitriles or C ₆ -C ₄ aryl nitriles are suitable, such as acetonitrile, propionitrile, butyronitrile or benzonitrile. Furthermore, single or multiple ethylenically unsaturated double bond systems can serve as ligand, such as ethenyl, propenyl, cis-2-butenyl, trans-2-butenyl, cyclohexenyl or norbornenyl,

L ² is selected from halide ions, such as fluoride, chloride,

Bromide or iodide, preferably chloride or bromide, amide ions (R ¹⁶ ) _h NH ₂ - _h ' ^A where h is an integer between 0 and 2, C ₁ -C ₆ -alkyl anions such as Me ^~ , (C ₂ H ₅ ) -, (C ₃ H ₇ ) ^~ , (nC ₄ H ₉ ) -, (tert-C ₄ H ₉ ) ^~ or (C ₆ Hι ₃ ) ^~ , allyl anions or methallyl anions, benzyl anions or aryl anions, such as (C ₆ H ₅ ) -.

In a particular embodiment, L ¹ and L ² are linked to one another by one or more covalent bonds. Examples of such ligands are 1,5-cyclooctadienyl ligands (“COD”), cyclooct-1-en-4-yl, 1,6-cyclodecenyl ligands or 1,5,9-alI-fcra-πs-cyclododecatrienyl- ligands.

In a further special embodiment, L ^{1 is} tetramethylethylenediamine, only one nitrogen coordinating with the metal. X denotes radicals of the formula CR or a nitrogen atom (N), in particular radicals of the formula CR, where

R for hydrogen,

Ci-C _ß alkyl groups, C ₇ -C ₃ aralkyl radicals or

C6-C- aryl groups, optionally substituted by one or more Cι-alkyl groups, halogens, one or more halogenated Cierte-Cι ₂ alkyl groups, Cι-Cι ₂ alkoxy groups, silyloxy groups OSiR ¹¹ R ¹² R ¹³ , amino groups NR ¹⁴ R ¹⁵ or -C ₂ -C thio ether groups.

Examples of particularly preferred radicals R of the formula CR can be found in the description of the radicals R ¹ to R ⁹ .

Y represents an OH group, oxygen, sulfur, NR ¹⁰ or PR ¹⁰ , the OH group and oxygen being particularly preferred.

N stands for a nitrogen atom.

The radicals R ¹ to R ⁹ are selected independently of one another

Hydrogen, -C-Cχ ₂ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso- Pentyl, sec.-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-A yl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n -Nonyl, n-decyl, and n-dodecyl; preferably Ci-Cg-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferably C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec.-butyl and tert.-butyl,

C 1 -C ₂ alkyl, one or more times the same or differently substituted by C 1 -C alkyl groups, halogens such as fluorine, chlorine, bromine and iodine, preferably chlorine and bromine and

C 1 -C ₂ alkoxy groups or C 1 -C ₂ thioether groups, the alkyl groups of these two groups being defined below, C -C ₃ aralkyl, such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1-methyl-l-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl,

C ₃ -C cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl, preferably cyclopentyl, cyclohexyl and cycloheptyl, - C ₃ -Cι cycloalkyl, one or more times the same or different substituted by Cι-Cι ₂ alkyl groups, halogens, Cι-C _.L2 ^_ Αlkoxygruppen or Cι-Cι ₂ -thioether groups, such as 2-methylcyclopentyl, 3-methylcyclopentyl, cis-2, 4-dimethylcyclopentyl, trans-2, 4 -Dimethylcyclopentyl 2, 2, 4, 4-tetramethylcyclopentyl, 2-methylcyclohexyl, 3-methylcyc1ohexy1, 4-methy1cyc1ohexy1, cis-2, 5-dimethy1cyc1ohexy1, trans-2, 5-dimethylcyclohexyl, 2,2,5, 5- Tetramethylcyclohexyl, 2-methoxycyclopentyl, 2-methoxycyclohexyl, 3-methoxycyclopentyl, 3-methoxycyclohexyl, 2-chlorocyclopentyl, 3-chlorocyclopentyl, 2, 4-dichlorocyclopentyl, 2, 2, 4, 4-tetrachlorocyclopentyl, 2- Chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2, 5-dichlorocyclohe xyl, 2, 2, 5, 5-tetrachlorocyclohexyl, 2-thiomethylcyclopentyl, 2-thiomethylcyclohexyl, 3-thiomethyl-cyclopentyl, 3-thiomethylcyclohexyl and other derivatives, - C ₆ -Ci ₄ -aryl, such as phenyl, 1-naphthyl,

2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, in turn substituted by one or more

* -CC -alkyl groups, as defined above,

* Halogens as defined above,

* one or more halogenated C 1 -C ₂ -alkyl groups, such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, preferably fluoromethyl, difluoromethyl, tri-fluorobutyl .

* Cι-Cι ₂ alkoxy groups, preferably C; _ι. -C ₆ alkoxy groups, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert. -Butoxy, n-pen-toxy, iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy,

* Silyloxy groups OSiR ¹¹ R ¹² R ¹³ , where R ¹¹ to R ¹³ independently of one another are hydrogen, C ₁ -C ₂ -alkyl groups, which in turn have 0 (C ₁ -C ₆ alkyl) or N (C ₁ -C ₆ - Alkyl) ₂ groups can be substituted, C ₃ -C cycloalkyl groups, C -C ₃ aralkyl radicals or C ₆ -Ci ₄ aryl groups, such as for example, the trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert. -Butyldimethylsilyloxy, tert-butyldiphenylsilyloxy, tribenzylsilyloxy, triphenylsilyloxy and the tri-para-xylylsilyloxy group; the trimethylsilyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred,

* Amino groups NR ¹⁴ R ¹⁵ , where R ¹⁴ and R ¹⁵ independently of one another hydrogen, -CC ₂ o -alkyl groups, which in turn with 0 (C _! -C ₆ alkyl) or N (C -C ₆ alkyl) ₂ - Groups can be substituted, are C ₃ -C ₂ cycloalkyl groups, C -C ₃ aryl alkyl radicals or C ₆ -Ci ₄ aryl groups, where R ¹⁴ and R ¹⁵ also form a saturated or unsaturated 5- to 8-membered ring can, such as, for example, dimethylamino, diethylamino, diisopropylamino, methylphenylamino diphenylamino, N-piperidyl, N-pyrrolidinyl, N-pyrryl, N-indoly or JV-carbazolyl, or

* -C 1 -C ₂ thioether groups, as defined above,

- Cχ -CC alkoxy groups, as defined above, preferred

Ci-Cg-alkoxy groups, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec. -Butoxy, tert. -Butoxy, n-pen-toxy, iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy, - silyloxy groups 0SiR ¹¹ R ¹² R ¹³ , as defined above, halogens, as defined above, or

- amino groups ΝR ¹⁴ R ¹⁵ , as defined above, or N0 groups,

where in each case two adjacent radicals R ¹ to R ⁹ can form a saturated or unsaturated 5- to 8-membered ring which is aromatic or aliphatic, such as - (CH ₂ ) ₃ - (trimethylene), - (CH ₂ ) ₄ ~ (Tetramethylene), - (CH ₂ ) ₅ - (pentamethylene), - (CH ₂ ) ₆ - (hexamethylene), -CH ₂ -CH = CH-, -CH ₂ -CH = CH-CH ₂ -, -CH = CH-CH = CH-, -0-CH ₂ -0-, -O-CHMe-O-, -CH- (C ₆ H ₅ ) -0-,

-0-CH ₂ -CH ₂ -0-, -0-CMe ₂ -0-, -NMe-CH ₂ -CH ₂ -NMe-, -NMe-CH ₂ -NMe- or -0-SiMe ₂ -0- ,

R ¹⁰ to R ¹⁶ independently of one another mean:

- hydrogen,

Cι ~ C o-alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl , neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-octyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n- Undecyl, iso-undecyl, n-dodecyl, iso-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-egg cosyl; particularly preferably C] _. -C ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec. -Butyl and tert. - butyl, with 0 _(Cι-C6 alkyl) or N _(Cι-C6 alkyl) ₂ radicals substituted _{Cι-C2o-alkyl} groups, such as CH ₂ -CH ₂ -OCH _3, or

CH ₂ -CH ₂ -N (CH ₃ ) ₂ ,

C ₃ -C 5 -cycloalkyl, as defined above, C ₇ -C ₃ -alkyl radicals, as defined above, C ₆ -C ₄ -aryl groups, as defined above,

where two adjacent radicals R ¹⁰ to R ¹⁵ together with the hetero atom in question can form a saturated or unsaturated aliphatic or aromatic 5- to 8-membered ring.

The complex compounds of the general formula I to be used according to the invention are also characterized in that at least one of the radicals R ¹ to R ^{9 must be} in the form of a radical of the general formula II below

where Z is an electron-withdrawing group and n is an integer from 1 to 5. Particularly preferred aromatic radicals of the general formula II are distinguished, inter alia, by the fact that Z for N0 _{2 /} S0 ₃ , F, C _m F _{2 +} i / it is not an integer from 1 to 10, and for a single or multiple fluorinated aryl stands.

Complex compounds to be used with very particular preference have the CF ₃ radical as an electron-withdrawing group and are characterized by n equal to 2 or 3. Examples include 3,5-bis (trifluoromethyl) phenyl, 2,6-bis (trifluoromethyl) phenyl and 2,4,6-tris (trifluoromethyl) phenyl.

The synthesis of the complexes of the general formula I is known per se. The syntheses of the complexes of the formula I can be analogous to the teachings of the documents EP-A 46331, EP-A 46328 and EP-A 52929 as well as WO 98/30609 and WO 98/42664 and in the publication by C. Wang et al., Organometallics 1998, 17, pages 3149ff. respectively.

A preferred synthetic route for introducing the radicals of the formula II into the ligands or the ligand precursors is the so-called Suzuki coupling. Boric acid is preferably used, which contains a radical of formula II instead of an OH function. Electrically neutral nickel complex compounds are preferably used.

The total amount of complex compound used is generally 10 ^-7 to 10 ^-2 mol / 1, often 10 ^{~ 5} to 10 ^{~ 3} mol / 1 and often 10 ^-5 to 10 ^-4 mol / 1, based in each case on the total amount of water, olefinically unsaturated compounds and optionally organic solvents.

Metal complex compounds of the general formula I which can be used particularly advantageously are those whose ligands are derived from the derivatives of salicylaldimine. The following representatives of the general formulas Iχ to I ₄ are preferred

II with RAH, -CH ₃ -isoPropyl

I ₃ 14 with RA -H, -CH ₃ , -isoPropyl

The complex compounds of formula I to be used according to the invention can be used either by first isolating them after reaction of the ligands with the metal compound and then introducing them into the polymerization system, or by using them as a so-called in-situ system, focusing on the iso- Complex compound dispensed with.

The aforementioned metal complexes can also be used in combination with an activator. In particular, the activators can be olefin complexes of rhodium or nickel.

Preferred, readily available activators are nickel (olefin) _y complexes, such as Ni (C ₂ H ₄ ) ₃ , Ni (1, 5-cyclooctadiene) ₂ "Ni (C0D) ₂ ", Ni (1, 6-cyclodecadiene) ₂ , or Ni (1, 5, 9-all-trans-cyclododecatriene) ₂ . Ni (COD) ₂ - is particularly preferred. Mixed ethylene / 1,3-dicarbonyl complexes of rhodium, such as, for example, rhodium-acetylacetonate-ethylene Rh (acac) (CH ₂ = CH ₂ ) ₂ , rhodium-benzoylacetonate-ethylene Rh (C ₆ H ₅ -CO-CH- CO-CH ₃ ) (CH ₂ = CH ₂ ) ₂ or Rh (C ₆ H ₅ -CO-CH-CO-C ₆ H ₅ ) (CH ₂ = CH ₂ ) ₂ . Rh (acac) (CH ₂ = CH) is well suited. This connection can be made according to the recipe by R. Cramer from Inorg. Synth. 1974, 15, pages 14ff. synthesize.

The molar ratio of activator to metal complex is usually in the range from 0.1 to 10, often from 0.2 to 5 and often from 0.5 to 2.

The dispersants likewise used in the process according to the invention can be emulsifiers or protective colloids.

Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polyethacrylic acids, gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid and also alkali metal acetates and copolymers of these also containing alkali metal salts Vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amine group-bearing acrylates, methacrylates, acrylamides and / or methacrylamides containing homo- and copolymers. A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pages 411 to 420.

Mixtures of protective colloids and / or emulsifiers can of course also be used. Often only emulsifiers are used as dispersants, the relative molecular weights of which, in contrast to the protective colloids, are usually below 1000. They can be of anionic, cationic or nonionic nature. Of course, if mixtures of surface-active substances are used, the individual components must be compatible with one another, which can be checked in the case of doubt using a few preliminary tests. 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, Macromolecules

Fabrics, Georg-Thieme-Verlag, Stuttgart, 1961, pages 192 to 208. According to the invention, in particular anionic, cationic and / or nonionic emulsifiers, preferably anionic and / or nonionic emulsifiers, are used as dispersants.

Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO grade: 3 to 50, alkyl radical: C ₄ to Cι ₂ ) and ethoxylated fatty alcohols (EO degree: 3 to 80; alkyl radical: C ₈ to C) ₃₆ ). Examples of these are the Lutensol A brands (C ₂ -C ₄ fatty alcohol ethoxylates, EO grade: 3 to 8), Lutensol ^® AO brands (C ₃ Ci ₅ ~ oxo alcohol ethoxylates, EO grade: 3 to 30),

Lutensol® AT brands (Cι ₆ C ₁₈ fatty alcohol ethoxylates, EO grade: 11 to 80), Lutensol ^® ON brands (Cι ₀ -oxo alcohol ethoxylates, EO grade: 3 to 11) and the Lutensol® TO brands (Cι _3- oxo alcohol ethoxylates, EO degree: 3 to 20) from BASF AG.

Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: Cs to C ₆ >, of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: Cχ ₂ to Cι ₈ ) and ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ to Cχ), of alkyl sulfonic acids

(Alkyl radical: C ₁₂ to Cis) and of alkylarylsulfonic acids (alkyl radical: C ₉ to Cι ₈ ).

Compounds of the general formula III have also been found to be further anionic emulsifiers

_R 17 _R 18

SOsD ¹ S0 ₃ D ²

wherein R ¹⁷ and R ^{18 are} H atoms or C ₄ - to C ₄ alkyl and are not simultaneously H atoms, and D ¹ and D ^{2 may be} alkali metal ions and / or ammonium ions. In the general formula III, R ¹⁷ and R ^{18 are} preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or hydrogen, where R ¹⁷ and R ^{18 are} not both H atoms at the same time , D ¹ and D ² are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Compounds III in which D ¹ and D ^{2 are} sodium, R ^{17 is} a branched alkyl radical having 12 C atoms and R ^{18 is} an H atom or R ¹⁷ are particularly advantageous. Technical mixtures are frequently used which have a proportion of 50 to 90% by weight of the monoalkylated product, such as Dowfax® 2A1 (trademark of Dow Chemical Company). The compounds III are generally known, for example from US Pat. No. 4,269,749, and are commercially available.

Suitable cationic emulsifiers are generally a Cξ, - to Ci ₈ ~ alkyl, alkylaryl or heterocyclic radical containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, and morpholinium salts, and morpholinium salts Salts of amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding sulfate, the sulfates or acetates of the various 2- (N, N, N-trimethylammonium) ethyl paraffinates, N-cetylpyridinium sulfate, N-laurylpyridinium sulfate and N-cetyl-N, N, N- trimethylammonium sulfate, N-dodecyl-N, N, N-trimethylammonium sulfate, N-octyl-N, N, N-trimethlyammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate and the mini-surfactant N, N'- (Lauryldimethyl) ethylenediamine disulfate, ethoxylated tallow fatty alkyl N-methylammonium sulfate and ethoxylated oleylamine (for example Uniperol AC from BASF AG, approx. 12 ethylene oxide units). Numerous other examples can be found in H. Stächen, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981 and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989. It is essential that the - Ionic counter groups are as low as possible nucleophilic, such as perchlorate, sulfate, phosphate, nitrate and

Carboxylates, such as, for example, acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, such as, for example, methylsulfonate, trifluoromethylsulfonate and para-toluenesulfonate, furthermore tetrafluoroborate, tetafetrakenophenyl) borate, tetrakis [bis (3, 5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.

The emulsifiers which are preferably used as dispersants are advantageously used in a total amount of 0.005 to 10 parts by weight, preferably 0.01 to 7 parts by weight, in particular 0.1 to 5 parts by weight, in each case based on 100 parts by weight. Parts of water. Depending on the polymerization system, it is also possible to choose the amount of emulsifiers so that their critical micelle formation concentration in the water is not exceeded.

The total amount of protective colloids additionally or instead used as a dispersant is often 0.1 to 10 parts by weight and often 0.2 to 7 parts by weight, based in each case on 100 parts by weight of water. According to the invention, it is optionally also possible to use slightly water-soluble organic solvents. Suitable solvents are liquid aliphatic and aromatic hydrocarbons with 5 to 30 carbon atoms, such as, for example, n-pentane and isomers, cyclopentane, n-hexane and isomers, cyclohexane, n-heptane and isomers, n-ocane and isomers, n-nonane and isomers, n-decane and isomers, n-dodecane and isomers, n-tetradecane and isomers, n-hexadecan and isomers, n-octadecane and isomers, eicosane, benzene, toluene, ethylbenzene, cumene, o-, m- or p-xylene, mesitylene, and generally hydrocarbon mixtures in the boiling range from 30 to 250 ° C. Hydroxy compounds, such as saturated and unsaturated fatty alcohols with 10 to 28 carbon atoms, for example n-dodecanol, n-tetradecanol, n-hexadecanol and their isomers or cetyl alcohol, esters, such as, for example, fatty acid esters with 10 to 28 carbon atoms, can also be used in the acid part and 1 to 10 C atoms in the alcohol part or esters from carboxylic acids and fatty alcohols with 1 to 10 C atoms in the carboxylic acid part and 10 to 28 C atoms in the alcohol part. Of course, it is also possible to use mixtures of the aforementioned solvents.

The total amount of solvent is up to 15 parts by weight, preferably 0.001 to 10 parts by weight and particularly preferably 0.01 to 5 parts by weight, in each case based on 100 parts by weight of water.

It is advantageous if the solubility of the solvent or of the solvent mixture under reaction conditions in the aqueous reaction medium is preferably <50% by weight, <40% by weight, <30% by weight, <20% by weight or <10% by weight. -%, in each case based on the total amount of solvent.

Solvents are used in particular when the olefinically unsaturated compounds are gaseous under reaction conditions (pressure / temperature), as is the case, for example, with ethene, propene, 1-butene and / or isobutene.

The process according to the invention can be carried out in such a way that, in a first step, the total amount of the metal complexes, that is to say the complex compound of the formula I and the optionally used activators, in a part or the total amount of the olefins and / or the slightly water-soluble organic ones Solvent dissolves. This solution is then dispersed together with the dispersants in an aqueous medium with the formation of oil-in-water dispersions with an average droplet diameter> 1000 nm, the so-called macroemulsions. Then, using known measures, these macroemulsions are converted into oil-in-water emulsions with an average droplet diameter <1000 nm, the so-called mini-emulsions, and these are added Reaction temperature with the remaining or total amount of the compounds and / or the slightly water-soluble organic solvents.

The mean size of the droplets of the disperse phase of the aqueous oil-in-water emulsions can be determined according to the principle of quasi-elastic dynamic light scattering (the so-called z-mean droplet diameter d _{z of} the unimodal analysis of the autocorrelation function), for example with a Coulter N4 Plus Particle Analyzer from Coulter Scientific Instruments. The measurements are carried out at 25 ° C. and atmospheric pressure on dilute aqueous mini-emulsions whose content of non-aqueous components is 0.01% by weight. The dilution is carried out using water which has previously been saturated with the olefins contained in the aqueous emulsion and / or organic solvents which are slightly soluble in water. The latter measure is intended to prevent a change in the droplet diameter with the dilution.

The thus determined for the miniemulsions values for d ₂ are usually ≤ 700 nm, frequently <500 nm. It is favorable according to the invention the d _z range from 100 nm to 400 nm or nm of 100 nm to 300. In the normal case d _{is, for} for an aqueous miniemulsion> 40 nm.

The general production of aqueous mini-emulsions from aqueous macroemulsions is known to the person skilled in the art (cf. P.L. Tang, E.D. Sudol, CA. Silebi and M.S. El-Aasser in Journal of Applied Polymer Science, Vol. 43, pages 1059 to 1066 [1991]).

High-pressure homogenizers, for example, can be used for this purpose. The fine distribution of the components in these machines is achieved through a high local energy input. Two variants have proven particularly useful in this regard.

In the first variant, the aqueous macroemulsion is compressed to over 1000 bar using a piston pump and then expanded through a narrow gap. The effect here is based on an interaction of high shear and pressure gradients and cavitation in the gap. An example of a high pressure homogenizer that works on this principle is the Niro-Soavi high pressure homogenizer type NS1001L Panda.

In the second variant, the compressed aqueous macro-emulsion is expanded into a mixing chamber via two opposing nozzles. The fine distribution effect is primarily dependent on the hydrodynamic conditions in the mixing chamber. gig. An example of this type of homogenizer is the M 120 E microfluidizer from Microfluidics Corp. In this high-pressure homogenizer, the aqueous macroemulsion is compressed to a pressure of up to 1200 bar by means of a pneumatically operated piston pump and expanded via a so-called "interaction chamber". In the "interaction chamber", the emulsion jet is divided into two jets in a microchannel system, which are brought together at an angle of 180 °. Another example of a homogenizer working according to this type of homogenization is the Nanojet type Expo from Nanojet Engineering GmbH. However, instead of a fixed duct system, two homogenizing valves are installed in the Nanojet, which can be adjusted mechanically.

In addition to the principles explained above, homogenization can e.g. also by using ultrasound (e.g. Branson Sonifier II 450). The fine distribution here is based on cavitation mechanisms. In principle, the devices described in GB-A 22 50 930 and US-A 5,108,654 are also suitable for homogenization by means of ultrasound. The quality of the aqueous miniemulsion generated in the sound field depends not only on the sound power introduced, but also on other factors such as e.g. B. the intensity distribution of ultrasound in the mixing chamber, the residence time, the temperature and the physical properties of the substances to be emulsified, for example on the toughness, the interfacial tension and the vapor pressure. The resulting droplet size depends, among other things. on the concentration of the emulsifier and on the energy introduced during the homogenization and is therefore e.g. selectively adjustable by changing the homogenization pressure or the corresponding ultrasonic energy.

The device described in the older German patent application DE 197 56 874 has proven particularly useful for producing an aqueous mini emulsion from conventional macroemulsions by means of ultrasound. This is a device which has a reaction space or a flow reaction channel and at least one means for transmitting ultrasound waves to the reaction space or the flow reaction channel, the means for transmitting ultrasound waves being designed such that the entire reaction space , or the flow-through reaction channel in one section, can be irradiated uniformly with ultrasonic waves. For this purpose, the radiation surface of the means for transmitting ultrasound waves is designed in such a way that it essentially corresponds to the surface of the reaction space or, if the reaction space is a partial section of a flow-through reaction channel, essentially Chen extends over the entire width of the channel, and that the depth of the reaction space substantially perpendicular to the radiation surface is less than the maximum depth of action of the ultrasound transmission means.

The term “depth of the reaction space” here essentially means the distance between the radiation surface of the ultrasound transmission means and the bottom of the reaction space.

Reaction chamber depths of up to 100 mm are preferred. The depth of the reaction space should advantageously not be more than 70 mm and particularly advantageously not more than 50 mm. In principle, the reaction spaces can also have a very small depth, but in view of the lowest possible risk of clogging and easy cleanability and a high product throughput, reaction space depths are preferred which are substantially greater than the usual gap heights for high-pressure homogenizers and are usually over 10 mm , The depth of the reaction space can advantageously be changed, for example by means of ultrasound transmission means immersed in the housing at different depths.

According to a first embodiment of this device, the radiation area of the means for transmitting ultrasound corresponds essentially to the surface of the reaction space. This embodiment serves for the batchwise production of the mini-emulsions used according to the invention. With this device, ultrasound can act on the entire reaction space. A turbulent flow is generated in the reaction chamber by the axial sound radiation pressure, which causes intensive cross-mixing.

According to a second embodiment, such a device has a flow cell. The housing is designed as a flow-through reaction channel which has an inflow and an outflow, the reaction space being a partial section of the flow-through reaction channel. The width of the channel is the channel extension which is essentially perpendicular to the direction of flow. The radiation area covers the entire width of the flow channel transverse to the direction of flow. The length of the radiation surface perpendicular to this width, that is to say the length of the radiation surface in the direction of flow, defines the effective range of the ultrasound. According to an advantageous variant of this first embodiment, the flow-through reaction channel has an essentially rectangular cross section. If a likewise rectangular ultrasound transmission means with corresponding dimensions is installed in one side of the rectangle, so a particularly effective and even sound system is guaranteed. Due to the turbulent flow conditions prevailing in the ultrasonic field, however, a round transmission means can also be used without disadvantages, for example. In addition, instead of a single ultrasound transmission means, a plurality of separate transmission means can be arranged, which are connected in series as seen in the flow direction. Both the radiation surfaces and the depth of the reaction space, that is to say the distance between the radiation surface and the bottom of the flow channel, can vary.

The means for transmitting ultrasound waves is particularly advantageously designed as a sonotrode, the end of which facing away from the free radiation surface is coupled to an ultrasound transducer. The ultrasonic waves can be generated, for example, by utilizing the reverse piezoelectric effect. With the help of generators, high-frequency electrical vibrations (usually in the range from 10 to 100 kHz, preferably between 20 and 40 kHz) are generated, converted into mechanical vibrations of the same frequency by means of a piezoelectric transducer, and with the sonotrode as a transmission element into the sound to be irradiated Medium coupled.

The sonotrode is particularly preferably designed as a rod-shaped, axially radiating λ / 2 (or multiple of λ / 2) longitudinal oscillators. Such a sonotrode can be fastened in an opening of the housing, for example, by means of a flange provided on one of its vibration nodes. The lead-through of the sonotrode into the housing can thus be made pressure-tight, so that the sonication can also be carried out under increased pressure in the reaction space. The oscillation amplitude of the sonotrode can preferably be regulated, that is to say the respectively set oscillation amplitude is checked online and, if necessary, automatically readjusted. The current vibration amplitude can be checked, for example, by a piezoelectric transducer mounted on the sonotrode or a strain gauge with downstream evaluation electronics.

According to a further advantageous embodiment of such devices, baffles are provided in the reaction space to improve the flow and mixing behavior. These internals can be, for example, simple deflection plates or a wide variety of porous bodies. If necessary, the mixing can also be further intensified by an additional agitator. The reaction space can advantageously be temperature-controlled.

One embodiment of the method according to the invention is such that the total amounts of the metal complex and the optionally added activators are dissolved in a part or the total amount of the slightly water-soluble organic solvents. This organic metal complex solution is then dispersed together with some or all of the dispersants in water to form a macroemulsion. The macroemulsion is converted into a mini emulsion by means of one of the aforementioned homogenizing devices. The total amount of olefins and, if appropriate, the remaining amounts of organic solvents or dispersants are metered into these at reaction temperature and with constant stirring. This process variant is chosen in particular when the olefins used are gaseous under reaction conditions, as is the case, for example, with ethene, propene, 1-butene and / or isobutene.

In a further embodiment, the total amount of the metal complex and the optionally added activators is dissolved in a part or the total amount of the olefins. This organic metal complex solution is then dispersed together with some or all of the dispersants in water to form a macroemulsion. The macroemulsion is converted into a mini emulsion by means of one of the aforementioned homogenizing devices. The remaining amounts of olefins or dispersing agents, as well as the total amount of the slightly water-soluble organic solvents, are metered into these mini-emulsions at the reaction temperature and with constant stirring. This process variant is chosen in particular when the olefinically unsaturated compounds used are liquid under reaction conditions, as is the case, for example, with 1-pentene, cyclopentene, 1-hexene, cyclohexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and / or 1-hexadecene is the case.

It is important that the liquid droplets with a diameter of <1000 nm, which are present as a separate phase in the aqueous medium, may contain other components in addition to the aforementioned compounds, ie the complex compounds, optionally the activators and the solvent and the olefins. Additional components include, for example, formulation auxiliaries, antioxidants, light stabilizers, but also dyes, pigments and / or waxes for water repellency. Is the Solubility of the other components in the organic phase forming the droplets is greater than in the aqueous medium, so they remain in the droplets during the polymerization reaction. Since the droplets of olefins and / or slightly water-soluble solvents containing the metal complexes ultimately represent the locations of the polymerization, the polymer particles formed generally contain these additional components in copolymerized form.

The actual polymerization usually takes place at a minimum pressure of 1 bar, below this pressure the polymerization rate is too slow. 2 bar are preferred and a minimum pressure of 10 bar is particularly preferred.

The maximum pressure is 4000 bar; at higher pressures, the requirements for the material of the polymerization reactor are very high and the process becomes uneconomical. <100 bar are preferred and <50 bar are particularly preferred.

The polymerization temperature can be varied within a wide range. The minimum temperature to be mentioned is 10 ° C, since the rate of polymerization drops at low temperatures. A minimum temperature of 20 ° C. and particularly preferably 30 ° C. is preferred. The maximum sensible temperature is 350 ° C. and preferably 150 ° C., particularly preferably 100 ° C.

The number average particle diameters of the polymer particles in the dispersions according to the invention are between 10 and 3000 nm, preferably between 50 and 500 nm and particularly preferably between 70 and 350 nm (quasi-elastic light scattering; ISO standard 13321). The particle diameter distribution is usually narrow and monomodal.

The particle diameters can be determined using customary methods. An overview of these methods can be found, for example, in D. Distler (editor) "Aqueous polymer dispersions", Wiley-VCH Verlag, 1st edition, 1999, chapter 4.

The weight-average molecular weights M _{w of} the polymers obtainable according to the invention, determined by means of gel permeation chromatography with polymethyl methacrylate as the standard, are generally in the range from 10,000 to 10,000,000, frequently in the range from 15,000 to 1,000,000 and often in the range from 20,000 to 1,000,000. The molecular weight distribution D (with D = M _w / M _n ) is usually narrow with D values of <4, <3, but also <2.5 or even <2. By specifically varying the olefinically unsaturated compounds, it is possible according to the invention to prepare copolymers whose glass transition temperature or melting point is in the range from -60 to +270 ° C.

The glass transition temperature T _{g means} the limit value of the glass transition temperature which, according to G. Kanig (Colloid Journal & Journal for Polymers, Vol. 190, page 1, equation 1), strives with increasing molecular weight. The glass transition temperature is determined by the DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53765).

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

1 / T _g = x T _g ¹ + X ² / T _g ² +. , , , X / T _g ⁿ ,

where x ¹ , x ² , .... x ^{n are} the mass fractions of the monomers 1, 2, .... n and T _g ¹ , T _g ² , .... T _g ^{n are} the glass transition temperatures of only one of the Monomers 1, 2, ... n mean polymers in degrees Kelvin. The T _g values for the homopolymers of most monomers are known and are listed, for example, in Ullmann's Ecyclopedia of Industrial Chemistry, Vol. 5, Vol. A21, page 169, VCH Weinheim, 1992; further sources of glass transition temperatures of homopolymers are, for example, J. Brandrup, EH Immergut, Polymer Handbook, l ^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 polymer dispersions according to the invention often have minimum film-forming temperatures MFT <80 ° C, often <50 ° C or <30 ° C. Since the MFT is no longer measurable below 0 ° C, the lower limit of the MFT can only be specified by the T _g values. The MFT is determined in accordance with DIN 53787.

The process according to the invention makes it possible to obtain aqueous copolymer dispersions whose solids content is 0.1 to 70% by weight, often 1 to 65% by weight and often 5 to 60% by weight and all values in between.

Of course, the residual monomers remaining in the aqueous polymer system after the end of the main polymerization reaction can be removed by steam and / or inert gas stripping familiar to the person skilled in the art without the polymer properties create disadvantageously change the polymers present in the aqueous medium.

The aqueous polymer dispersions obtainable according to the invention are often stable over several weeks or months and generally show virtually no phase separation, deposition or coagulum formation during this time. The aqueous polymer dispersions accessible according to the invention can advantageously be used in numerous applications, such as, for example, paper applications such as paper coating or surface sizing, paints and lacquers, construction chemicals and plastic plasters, adhesive raw materials, sealing compounds, molded foams, textile and leather applications, carpet backing coatings, mattresses or pharmaceutical preparations.

Paper coating is the coating of the paper surface with aqueous pigmented dispersions. The polymer dispersions according to the invention are advantageous because of their low price. Surface sizing is the pigment-free application of hydrophobic substances. The polyolefin dispersions which have hitherto been difficult to access under economic conditions are particularly advantageous as a particularly hydrophobic substance. A further advantage is that during the production of the dispersions according to the invention for paper coating or surface sizing, no molecular weight regulators such as, for example, tert. -Dodecyl mercaptan must be added, which are difficult to separate on the one hand, but smell unpleasant on the other.

The polymer dispersions accessible according to the invention are particularly suitable in paints and varnishes because they are very inexpensive. Aqueous polyethylene dispersions are particularly advantageous because they also have special UV stability. Furthermore, aqueous polyethylene dispersions are particularly suitable because they are resistant to basic materials, such as cement, which are common in construction chemistry.

In adhesives, in particular in adhesives for self-adhesive labels or films and plasters, but also in construction adhesives or industrial adhesives, the dispersions according to the invention have economic advantages. They are particularly favorable in construction adhesives because they are resistant to basic materials that are common in construction chemistry. In molded foams which are produced from the dispersions according to the invention by processes known per se, such as the Dunlop process or the Talalay process, the low price of the dispersions according to the invention is again advantageous. Gelling agents, soaps, thickeners and vulcanizing pastes serve as further components. Molded foams are processed into mattresses, for example.

Textile and leather applications serve to preserve and finish textile or leather. Among the effects, the impregnation and the further finishing of the textiles are exemplary. An advantage of the dispersions according to the invention as a constituent in textile and leather applications is, in addition to the low price, the absence of odor, since olefins as residual monomers can be easily removed.

Carpet back coatings are used to glue the carpet fibers on the back, and they also have the task of giving the carpet the necessary rigidity and evenly distributing additives such as flame retardants or antistatic agents. An advantage of the dispersions according to the invention, in addition to the low price, is their insensitivity to the common additives. In particular, the polyethylene dispersions according to the invention have proven to be particularly chemically inert. It is also advantageous that no molecular weight regulators such as, for example, tert. -Dodecyl mercaptan must be added, which are difficult to separate on the one hand, but smell unpleasant on the other. Finally, carpets containing the carpet backing coatings according to the invention can be recycled well.

Pharmaceutical preparations are understood to mean dispersions as carriers of medicaments. Dispersions as carriers of medication are known per se. An advantage of the dispersions according to the invention as carriers of medicaments is the economically favorable price and the resistance to body influences such as gastric juice or enzymes.

The process according to the invention opens up an economical, ecological, preparative simple and, in terms of safety, largely harmless access to aqueous polymer dispersions of inexpensive olefins. Because of their preparation, the aqueous polymer dispersions accessible according to the invention have polymer particles which contain no or only very small amounts of organic solvents. However, the process of the invention is present in the presence of low Water-soluble solvents carried out, so an odor pollution in the formation of polymer films can be avoided by selecting high-boiling solvents. On the other hand, the optionally used solvents often act as coalescing agents and thus promote film formation. Due to the process, the polymer dispersions accessible according to the invention have polymer particles with a narrow, monomodal particle size distribution. The aqueous polymer dispersions obtained are moreover stable for weeks and months even with small amounts of dispersant and generally show virtually no phase separation, deposition or coagulum formation during this time. The process according to the invention also provides access to aqueous polymer dispersions whose polymer particles contain, in addition to the polymer, other additives, such as formulation auxiliaries, antioxidants, light stabilizers, but also dyes, pigments and / or waxes.

The aqueous dispersions also according to the invention are distinguished, inter alia, by also in that they have polyolefins with a high molecular weight.

Examples

All reactions were carried out under an argon atmosphere. Toluene was over sodium / ether and demineralized water was distilled under argon. The water was degassed three more times. Pyridine and pentane were distilled over KOH.

I. Preparation of 2, 6-diphenylaniline

1.10 g (9.0 mmol) of phenylboric acid in 6 ml of ethanol were added to a solution of 0.75 g (3.0 mmol) of 2,6-dibromoaniline in 30 ml of toluene. The mixture thus obtained was mixed with a 2 molar solution of NaCO ₃ (24 mmol) in water (2 ml). The resulting two-phase mixture was then flushed with argon and then 0.42 g (0.36 mmol) of Pd (PPh ₃ > _{4) was} added. The mixture thus obtained was stirred overnight at 90 ° C. The organic phase was then separated from the aqueous phase and extracted the aqueous phase three times with diethyl ether, the combined organic phases obtained were dried over Na S0, the organic solvent was evaporated off and the compound obtained was purified by means of column chromatography (over silica gel / with toluene) and the compound obtained then by means of ¹ H-NMR, ¹³ -C-NMR, mass spectroscopy and Elemental analysis identified as 2, 6-diphenylaniline. The yield was 80%.

Analogously, 2,6-bis (3,5-bis (trifluoromethyl) phenyl) aniline was prepared starting from 3,5-bis (trifluoromethyl) phenyl boric acid. The yield of this compound was 80%. It was determined by means of ^ H-NMR, ¹³ CN R (nuclear magnetic resonance spectroscopy), mass spectroscopy and elemental analysis.

2,6-bis (3,5-bis (trifluoromethyl) phenyl) aniline: yield 80%. ^! H-NMR (300 MHz, CDC1 ₃ ): 8.01 (CH, s, 4H), 7.94 (CH, s, 2H), 7.21 (CHCHCH, d, ³ J _HH = 7.5 Hz, 2H), 7.01 (CHCHCH, t , ³ J _HH = 7.5 Hz, 1H). ¹³ C-NMR (75.4 MHz, CDC1 ₃ ): 141.3 (CNH ₂ , s), 140.4 (Ph, s), 132.4 (CCF ₃ , quartet, J _CF = 33 Hz), 131.0 (Ph, s),

129.6 (CCCF ₃ , quartet, ³ J _CF = 3 Hz), 125.5 (Ph, s) 123.2 (CF ₃ , quartet, ⁱ Jcp = 273 Hz), 121.5 (CCCF ₃ , septet, ³ J _CF = 3 Hz), 119.3 (Ph, s). Elemental Analysis: (C ₂₂ HnF ₁₂ N): C, 51.08; H, 2.14; N, 2.71. found: C, 51.07; H, 1.99; N, 2.65. Mass: 517.3 g / mol- ⁱ .

II. Preparation of the corresponding salicylaldimine ligand is based on the aniline compound from Section I

5 ml of a methanol solution of 3,5-diiodo-2-hydroxybenzaldehyde (166 mg; 0.61 mmol) were mixed with a catalytic amount of formic acid and 2,6-bis (3,5-bis (trifluoromethyl) phenyl) aniline (0.55 mmol) was added. The reaction mixture was then mixed for 6 hours at room temperature. A yellow solid precipitated out, which was first filtered, then washed with cold methanol and finally dried. The salicylaldimine ligand obtained was determined by means of ^X H-NMR, ¹³ C-NMR, mass spectroscopy and elemental analysis. The yield was 85%.

III. Preparation of the corresponding metal complex starting from the ligand from Section II

A solution of 100 mg (0.49 mmol) Ni (CH ₃ ) ₂ (TMEDA) - TMEDA stands for tetramethylethylenediamine - in 10 ml ether was treated with 0.49 mmol of the salicylaldimine ligand obtained from Section II at -30 ° C added. 0.5 ml of pyridine was further added to this reaction mixture. The temperature was then raised to 0 ° C and the resulting orange-red mixture was stirred for 2 hours. The solvent was then removed in vacuo and the residue with cold Washed pentane. The orange-red nickel complex compound was obtained in a yield of more than 90%.

IV. Polymerization of ethylene using the nickel complex obtained from Section III

A Schlenk tube was filled with a solution of 20 μn-iol of the nickel complex obtained from Section III in 2 ml of toluene and 0.3 ml of hexadecane. The solution thus obtained was then added to a solution of 0.75 g of sodium dodecyl sulfate in 98 ml of water. The resulting mixture was then treated with an ultrasonic homogenizer (120 W, 2 minutes), whereby a mini emulsion was obtained. The mini emulsion was then placed in a 150 ml steel autoclave which was filled with ethylene under a pressure of 40 bar. The temperature in the autoclave was then raised to 50 ° C and after 1 hour the autoclave was rapidly cooled and degassed. The aqueous emulsion obtained was filtered through glass wool. It contained an ethylene homopolymer, which was identified by the fact that it was obtained from the emulsion by precipitation with 3 times the volume of acetone.

Claims

claims

Process for the preparation of aqueous polymer dispersions by polymerizing one or more olefins in an aqueous medium in the presence of dispersants and, if appropriate, organic solvents, characterized in that the polymerization of the olefin (s) is catalyzed using one or more complex compounds of the general formula I

in which the substituents and indices have the following meaning:

M is a transition metal from groups 7 to 10 of the Periodic Table of the Elements,

L ⁱ phosphines (R ¹⁶ ) _X PH ₃ _ _X or amines (R ¹⁶ ) _X NH ₃ _ _X with identical or different radicals R ¹⁶ , ether (R ¹⁶ ) ₂ 0, H ₂ 0, alcohols (R ¹⁵ ) 0H, Pyridine, pyridine derivatives of the formula C ₅ H ₅ _ _X (R ¹⁶ ) _X N, CO, -C -CC alkyl nitriles, C ₆ -Ci ₄ aryl nitriles or ethylenically unsaturated double bond systems, where x is an integer from 0 to 3,

L ² halide ions, amide ions (R ¹⁶ ) _h H ₂ _ _h , where h is an integer from 0 to 2, and further C ₁ -C ₆ -alkyl anions, allyl anions, benzyl anions or aryl anions,

where L ¹ and L ² can be linked to one another by one or more covalent bonds,

X: CR, nitrogen atom (N)

R: hydrogen, Ci-C _δ alkyl groups, C ₇ -Cι ₃ aralkyl radicals or

Cg-C ^ aryl groups, optionally substituted by one or more Cι-Cι-alkyl groups, halogens, one or more halogenated

C 1 -C 4 alkyl groups, C ¹ -C 4 alkoxy groups, silyloxy groups OSiR ^{1: L} R ¹² R ¹³ , amino groups NR ¹ R ¹⁵ or C ¹ -C ₂ thioether groups,

Y: OH group, oxygen, sulfur, NR ¹⁰ or

PR ¹⁰ ,

N: nitrogen atom

R ¹ to R ⁹ : independently of one another

Hydrogen,

C 1 -C ₂ alkyl, where the alkyl groups may be branched or unbranched, C 1 -C 4 alkyl, one or more times the same or differently substituted by C 1 -C 4 alkyl groups, halogens, C 1 -C 4 alkoxy groups or C 1 -C 4 ₂ -Thioethergruppen, C ₇ -C ₁₃ aralkyl, C ₃ -Ci ₂ cycloalkyl, C ₃ -Cι ₂ cycloalkyl, one or more identical or differently substituted by C ₁ -C ₁₂ alkyl groups, halogens, -Cι -CC Groups ₂ alkoxy or Cι-Cι ₂ -thioether, C ₆ -C ₁₄ aryl, C ₆ -C ₄ aryl, identical or different substituted by one or more Cι-Cι groups ₂ alkyl, halogens, mono- or multi-halogenated C 1 -C ₂ alkyl groups, C 1 -C alkoxy groups, silyloxy groups OSiR ¹¹ R ¹² R ¹³ , amino groups NR ¹⁴ R ¹⁵ or Cχ-C thioether groups,

C 1 -C ₂ alkoxy groups, silyloxy groups OSiR ¹¹ R ¹² R ¹³ , halogens, N0 ₂ groups or amino groups NR ¹ R ¹⁵ , where two adjacent radicals R ¹ to R9 together form a saturated or unsaturated 5- to 8-membered ring can,

R ¹⁰ to R ^{16 are} independently hydrogen, _{Cι-C2o-alkyl} groups, in turn, with 0 _(Cι-C5 alkyl) or N _(Cι-C6 alkyl) ₂ groups may be substituted, _C3-Ci2 cycloalkyl, C ₇ -Cι ₃ Aralkyl radicals or C ₆ -Ci ₄ aryl groups,

where at least one of the radicals R ¹ to R ^{9 must be} in the form of a radical of the general formula II below

where Z is an electron-withdrawing group and n is an integer from 1 to 5.

2. The method according to claim 1, characterized in that in the general formula II Z stands for one of the following electron-withdrawing radicals:

N0 ₂ , S0 ₃ , F, C _m F _{2m +} ι where m is an integer from

1 to 10 and one or more fluorinated aryl

3. The method according to any one of claims 1 or 2, characterized in that in the general formula II Z is CF ₃ and n is 2 or 3.

4. The method according to any one of claims 1 to 3, characterized in that the complex compound is still used in combination with an activator.

5. The method according to any one of claims 1 to 4, characterized in that in the general formula I M stands for nickel or for palladium.

6. The method according to any one of claims 1 to 5, characterized in that only ethylene is used as olefin.

7. The method according to any one of claims 1 to 5, characterized in that at least two olefins selected from the

Group comprising ethylene, propylene, 1-butene, 1-hexene and styrene, can be used.

8. The method according to claim 6, characterized in that ethylene is used in combination with propylene, 1-butene, 1-hexene or styrene.

9. The method according to any one of claims 1 to 8, characterized in that anionic, cationic and / or nonionic emulsifiers are used as dispersants.

5 10. The method according to any one of claims 1 to 9, characterized in that aliphatic and aromatic hydrocarbons, fatty alcohols or fatty acids are used as organic solvents.

10 11. Aqueous dispersions of polyolefins or copolymers of several olefins, obtainable by a process according to claims 1 to 10.

12. Aqueous dispersions of polyethylene or copolymers 15 of ethylene, obtainable by a process according to claims 1 to 10.

13. Aqueous dispersions according to claims 11 or 12, which are in the form of a mini emulsion.

20

14. Use of the aqueous dispersions according to claims 11 to 13 for paper applications such as paper coating or surface sizing, paints, adhesive raw materials, molded foams such as mattresses, textile and leather applications,

25 carpet backing or pharmaceutical applications.

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