WO2004044016A2

WO2004044016A2 - Aqueous polymer dispersion emanating from activated transition metal complexes

Info

Publication number: WO2004044016A2
Application number: PCT/EP2003/012457
Authority: WO
Inventors: Peter PREISHUBER-PFLÜGL; Mubarik Mahmood Chowdhry; Markus Schmid; Xavier Sava; Horst Weiss
Original assignee: Basf Aktiengesellschaft
Priority date: 2002-11-11
Filing date: 2003-11-07
Publication date: 2004-05-27
Also published as: WO2004044016A3; DE10252658A1; AU2003286157A1

Abstract

The invention relates to aqueous polymer dispersions that can be obtained by polymerizing one or more olefins in the aqueous medium in the presence of dispersants and, optionally, in the presence of organic solvents. The polymerization of the olefin(s) ensues with the aid of a catalyst system based on transition metal complexes having neutral ligands and with the aid of an activator. Transition metal complexes of this type are used that, before being activated with the aid of the utilized activator, do not have any metal-carbon bonds.

Description

Aqueous polymer dispersions, based on activated transition metal complexes

description

The present invention relates to aqueous polymer dispersions obtainable by polymerizing one or more olefins in an aqueous medium in the presence of dispersants and, if appropriate, organic solvents, the

Polymerization of the olefin (s) is carried out with the aid of a catalyst system based on transition metal complexes with neutral ligands and with the aid of an activator, and those transition metal complexes are used which have no metal-carbon bond before their activation with the aid of the activator used.

Furthermore, the present invention relates to a process for the preparation of aqueous polymer dispersions and their use for paper applications, paint coatings, adhesive raw materials, molded foams, 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 a technical 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 ÜS-A 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, the 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.

For the metal complex-catalyzed polymerization of olefins in an aqueous medium, the following state of the art can be assumed.

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

10 app. Chem. 1995, 207, pages 1255ff. 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 that water as

15 catalyst poison must be carefully excluded.

There are few reports of transition metal catalyzed reactions of olefins such as ethylene in an aqueous environment. L. Wang et al. in ^" . Am. Chem. Soc. 1993, 20 115, pages 6999ff. on a Rhodiυ -catalyzed polymerization. However, the activity is much too low at around one insertion / hour for technical applications.

The reaction of ethylene with nickel-P, 0-chelate complexes, as described in US-A 3,635,937 and US-A 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 the reaction of 30 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 denotes 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. 45 In US-A 4,698,403 (column 7, lines 13-18) it is disclosed that an excess of water over bidentate Ni chelate complexes acts as a catalyst poison, even if they carry an S0 ₃ ^~ group.

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

10 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

25 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, it should be noted that the temperature of

30 40 ^C C should not be exceeded, otherwise the catalytic converter will be deactivated (page 25, lines 5ff.). However, higher reaction temperatures are generally desirable because this can increase the activity of a catalyst system.

35

A further disadvantage of catalyst systems of the general formula B is that generally highly branched polymers are formed with ethylene (C. Killian, ^" . Am. Chem. Soc. 1996, 118, pages 11664ff.), Which have so far been of less technical importance

40 are.

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

45

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).

Such complexes of nickel or palladium with neutral ligands are also referred to as cationic transition metal complexes. By adding a cocatalyst, the actually active species is formed, which has a positive charge on the metal. The negative charge is carried by a counter ion that is not connected to the neutral ligand. In contrast to the cationic transition metal complexes with neutral ligands, neutral transition metal complexes have at least one ionic ligand, which makes the overall charge of the complex neutral.

To date, neutral transition metal complexes have mostly been described for the catalytic emulsion polymerization of olefins in water (WO 00/20464, WO 01/44325, US-A 4689437, EP-A 177999 'and US-A 3676523).

From the. WO 96/23010 discloses the polymerization of olefins and acrylates with the aid of cationic transition metal complexes of nickel and palladium with neutral diimine ligands.

Further examples of cationic transition metal complexes can be found in WO-A 98/47934 and WO-A 96/37522, where nickel complexes with phosphine ligands are used for the polymerization of olefins. In WO-A 98/47934 the nickel complexes are used together with aluminum alkyl compounds as activators. WO 01/10876 discloses the polymerization of nickel complexes with P-X-P ligands.

In addition, it is known from Chem. Communication 2000.301 and Chem. Eur. J. 2000.6.24.4623 to use cationic palladium complexes for polymerization in an aqueous medium. Alkyl complexes of palladium are used as starter compounds, no cocatalyst being used for activation. In WO 97/17380 and WO 97/48740, cationic complexes of palladium are used for the production of polyolefins in an aqueous medium. The complexes described therein have, inter alia, a metal-carbon bond, the actual active species not being produced in situ. When the palladium complexes described are used, polymers are obtained which are characterized by a gray coloration due to the formation of metallic palladium. If the polymers produced are polyethylenes, they have a high degree of branching.

The present invention was therefore based on the object of remedying the disadvantages described and of developing novel aqueous polymer dispersions based on cationic transition metal complexes with neutral ligands, which are accessible through the simplest possible activation step. Furthermore, the object of the present invention also extends to the development of a new process for the preparation of the aqueous polymer dispersions according to the invention and their use in customary technical fields of application.

Accordingly, novel polymer dispersions have been found, obtainable by polymerizing one or more olefins in an aqueous medium in the presence of dispersants and, if appropriate, organic solvents, the polymerization of the olefin (s) using a catalyst system based on transition metal complexes with neutral ligands and with the aid of a Activator takes place and such transition metal complexes are used which have no metal-carbon bond before their activation with the aid of the activator used.

Suitable olefins for the preparation of aqueous homopolymer dispersions include: ethylene, propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 1-heptene, 1-octene, 1 -Decene and 1-eicosen, but also branched olefins such as 4-methyl-1-pentene, norbornene, vinylcyclohexene and vinylcyclohexane as well as styrene, para-methylstyrene and para-vinylpyridine, ethylene and propylene being preferred. Ethylene is particularly preferred.

In addition to the olefins already mentioned, aqueous copolymer dispersions of two or more olefins also contain coolefins from the following groups: * Nonpolar I-01efins, 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-1-pentene, vinylcyclohexene and vinylcyclohexane and styrene, para -Methylstyrene and para-vinyl pyridine, where

Ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene are preferred.

* Olefins with internal double bonds, for example 2-butene, 2-pentene or 2-hexene.

* Olefins which contain polar groups, such as, for example, acrylic acid, acrylic acid-Ci-Cs-alkyl ester, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methacrylic acid, methacrylic acid-Ci-Cs-alkyl ester, Cχ-Cg- 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. Preferred are acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, acrylonitrile, ethyl vinyl ether, vinyl acetate, 10-undecenoic acid, 3-butenoic acid, 4-butenoic acid, 4-butenoic acid, 4-butenoic acid, Pentenoic acid and 5-hexenoic acid.

Carbon monoxide can also be used as a coolefin.

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 mixture to be polymerized is 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 consisting of ethylene, propylene, 1-tin, 1-hexene and styrene. Ethylene is often used in combination with propylene, 1-butene, 1-hexene or styrene.

The polymers present in the aqueous polymer dispersions according to the invention are produced with the aid of a catalyst system based on transition metals with neutral ligands. In addition to other transition metal complexes, those of the following general formulas (I) to (X) are particularly suitable:

I II III

VII VIII

IX

in which the substituents and indices have the following meaning.

M: a transition metal of groups 7 to 10 of the periodic table

El: nitrogen atom or phosphorus atom for the formulas I, II,

III, VI, VII, IX, X

Oxygen atom or sulfur atom for the formulas IV and

V Substituted nitrogen tom (NR ⁸ ) or substituted Phoεphoratom (PR ⁸ ) for the formula V

E ₂ : nitrogen atom or phosphorus atom for the formulas I, VII, IX and X

Oxygen atom or sulfur atom for the formulas II, III, IV, V, VI

Substituted nitrogen atom (NR ⁸ ) or substituted phosphorus atom (PR ⁸ ) for the formulas III, IV, V, VI

E ₃ : nitrogen atom or phosphorus atom for the formula IX oxygen atom or sulfur atom for the formula X

E ₄ : phosphorus atom for the formula VIII

L (n): halide ions, amide ions (R ¹⁰ ) _h NH ₂ - _h > where h is an integer from 0 to 2, oxy compound OR ⁹ or acetylacetonate and n stands for the valency of the metal M.

R ^l to R ⁸ : independently of one another hydrogen,

C 1 -C ₂ -alkyl, where the alkyl groups may be branched or unbranched, C 1 -C ₂ -alkyl, one or more times the same or differently substituted by C 1 -C ₂ -alkyl groups, halogens, N0 groups, C 1 -C ₂ - Alkoxy groups or C 1 -C ₂ thioether groups, C ~ C ₃ aralkyl, C ₃ -C ₂ cycloalkyl,

C ₃ -C ₂ cycloalkyl, substituted one or more times identically or differently by C ₁ -C ₁₂ alkyl groups, halogens, N0 ₂ groups, C ₁ -C ₂ alkoxy groups or C ₁ -C ₂ thioether groups, C ₆ -C 4 _4- aryl,

C ₆ -Ci ₄ aryl, identically or differently substituted by one or more C 1 -C ₂ alkyl groups, halogens, N0 ₂ groups, one or more halogenated C 1 -C ₂ alkyl groups, C 1 -C ₂ alkoxy groups, silyloxy group - Pen OSiR ^H Ri ² Rl ³ , amino groups NR ⁱ⁴ R ⁵ or C-Cι ₂ thio ether groups, Cι-C ₂ alkoxy groups, silyloxy groups OSiRü ^ R ¹³ , halogens, N0 groups or

Amino groups NR ⁱ⁴ R ⁱ⁵ , two adjacent residues R ¹ to R ⁸ others can form a saturated or unsaturated 5- to 8-membered ring,

R ⁹ to R ^{X5 are} independently hydrogen,

-C-C ₂ o ~ alkyl groups, which in turn can be substituted with 0 (-C-C ₆ alkyl) or N (-C-C ₆ ~ alkyl) groups,

C ₃ -C -cycloalkyl groups,

C -C ₃ aralkyl radicals or C ₆ -C ₄ aryl groups.

It is essential in the transition metal complexes described here that they do not have a metal-carbon bond before they are activated with the aid of the activator used.

Preferred transition metals of groups 7 to 10 of the periodic table include Nickel and palladium.

The substituents Ei, E, and E ₃ in particular represent a nitrogen atom.

The substituent L (n) means in particular fluoride, chloride and bromide, where n symbolizes the valence of the metal.

The radicals R ^x to R ⁸ are selected independently of one another

Hydrogen,

C 1 -C ₂ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec .-Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n -Decyl, and n-dodecyl; preferably Ci-C _δ- 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 -C ₄ alkyl, such as methyl, ethyl, n-propyl, iso- Propyl, n-butyl, isobutyl, sec-butyl and tert-butyl,

C 1 -C ₂ alkyl, substituted one or more times identically or differently by C 1 -C ₂ alkyl groups, N0 ₂ 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 ₂ 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 identical or differently substituted by C 1 -C ₂ -alkyl groups, halogens, NO groups, C 1 -C ₂ -alkoxy groups or C 1 -C ₂ -thioether groups, such as 2-methylcyclopentyl, 3-methylcyclopentyl, cis-2, 4-dirnethylcyclopentyl, trans-2, 4-dimethylcyclopentyl 2, 2, 4, 4-tetramethylcyclopentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, cis-2, 5-dirnethylcyclohexyl, trans-2, 5-dirnethylcyclohexyl, 2.2 , 5, 5-tetramethylcyclohexyl, 2-methoxycyclopentyl, 2-methoxycyclohexyl, 3-methoxycyclopentyl, 3-methoxycyclohexyl, 2-chlorocyclopentyl, 3-chlorocyclopentyl, 2, 4-dichlorocyclopentyl, 2, 2, 4, 4-tetrachlorocyclopen - tyl, 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2, 5-dich lorcyclohexyl, 2, 2, 5, 5-tetrachlorocyclohexyl, 2-thiomethylcyclopentyl, 2-thiomethylcyclohexyl, 3-thiomethyl-cyclopentyl, 3-thioethylcyclohexyl and other derivatives, - C ₆ -Ci ~ 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

* -C-Ci ₂ alkyl groups, as defined above,

* Halogens as defined above,

* NO ₂ groups

* 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, trifluoromethyl, trifluoromethyl, trifluoromethyl, trifluoromethyl,

* -C -CC alkoxy groups, preferably Ci-C _ß 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 ^H R ² R ⁱ³ , where R ^xl to R ⁱ³ independently of one another are hydrogen, C 1 -C 8 -alkyl groups, which in turn contain 0 (C ₁ -C ₆ -alkyl) or N (C ₁ -C ₆ -alkyl) ₂ - Groups can be substituted, C ₃ -C ₂ cycloalkyl groups, C -C ₃ aralkyl radicals or C ₆ -C ₄ aryl groups, such as, for example, the trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert. Butyldimethylsilyloxy, tert.butylsilyloxy, tert.butyldipyl, , Triphenylsilyloxy and the tri-para-xylylsilyloxy group; the trimethylsilyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred,

* Amino groups NR ¹ R ^x5 , where R ^X4 and R ⁱ⁵ independently of one another are hydrogen, C ₁ -C ₂₀ -alkyl groups, which in turn contain 0 (-C-C ₆ -alkyl) or N (-C-C ₆ -alkyl) ₂ Groups can be substituted, C ₃ -C cycloalkyl groups, C -C ₃ aryl alkyl radicals or Cg-Ci ₄ aryl groups, where R ⁱ⁴ and R ^{i5 can} also form a saturated or unsaturated 5- to 8-membered ring , like for example

Dimethylamino, diethylamino, diisopropylamino, methylphenylamino, diphenyamino, JV-piperidyl, iV-pyrrolidinyl, N ~ pyrryl, i \ 7-indoly or JV-carbazolyl, or

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

C 1 -C ₂ -alkoxy groups, as defined above, preferably C ₁ -C 6 -alkoxy groups, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, 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 OSiRHR ⁱ² R ⁱ³ as defined above, halogens as defined above or amino groups NR ¹⁴ R ⁱ⁵ as defined above, or O ₂ groups,

where two adjacent radicals R ⁱ to R ⁸ together can form a saturated or unsaturated 5- to 8-membered ring which is aromatic or aliphatic, such as - (CH ₂ ) ₃ - (trimethylene), - (CH ₂ ) - (Tetramethylene), - (CH ₂ ) s- (pentamethylene), - (CH ₂ ) ₆ - (hexamethylene), -CH ₂ -CH = CH-, -CH ₂ -CH = CH-CH ₂ -, - CH = CH-CH = CH-, -O-CH ₂ -O-, -0-CHMe-O-, -CH- (C ₆ H ₅ ) -0-, -O-CH ₂ -CH ₂ -O- , -0-CMe ₂ -0-, -NMe-CH ₂ -CH ₂ -NMe-, -NMe-CH ₂ -NMe- or -0-SiMe ₂ -0-.

R ⁹ to R ⁱ⁵ mean independently of one another:

Hydrogen,

-C-C ₂ 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 preferred C 1 -C ₄ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, - with 0 (C ₁ -C ₆ -alkyl) or N (-CC ₆ -alkyl) ₂ radicals substituted -CC ₂ o -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 -C ₃ -aryl radicals, as defined above, - C ₆ ~ Ci ₄ aryl groups, as defined above,

where two adjacent radicals R ⁹ to R ⁱ⁵ together with the hetero atom in question can form a saturated or unsaturated aliphatic or aromatic 5- to 8-membered ring.

The synthex of such complexes of the general formulas I to X is generally known and can be carried out analogously to the teachings of EP-A 46331, EP-A 46328 and WO-A 98/30609.

Suitable activators for the preparation of the aqueous polymer dispersions according to the invention include organometallic compounds. In general, activators in the case of organometallic-catalyzed polymerization of olefins are compounds which can transfer a hydride or an alkyl radical or an aryl radical.

Preferred activators are also compounds of boron, in particular complexes or salt-like borohydrides, boralkyls or boraryls.

Organometallic compounds of tin, zinc, Cadmis, mercury, silicon, germanium, copper, cobalt, iron, lead, nickel, ruthenium, iridium, platinum or rhenium can also be used as activators.

Sodium borohydride is particularly preferred as the activator. The activators used can also serve as molecular weight regulators for the polymers produced.

Weakly coordinating anions can be used as anionic counterions to the cationic transition metal complexes. Preferred counterions are borates, alkyl or aryl sulfates and alkyl or aryl sulfonyl compounds, and also phosphates, antimonates and arsenates. Examples include: BF ₄ ^" , B (C ₆ F ₅ ) ₄ -, B ((3,5-CF ₃ ) ₂ C ₆ H ₃ ) ₄ -, CF ₃ S0 ₃ ^" , C ₄ F ₉ S0 ₃ -, (CF ₃ S0 ₂ ) ₂ N ^~ , (CF ₃ S0 ₂ ) ₃ C-, PF ₆ ^" , SbF ₆ ^~ , AεF ₆ -. Such compounds are Usually added in the form of salts of suitable metals, preferably in the form of their sodium, lithium, potassium or silver salts.

The total amount of wagered. Transition metal complex 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, each based on the total amount of water , olefinically unsaturated compounds and optionally organic solvents. Accordingly, the amount of anionic counterions is in these ranges.

The molar ratio of activator to transition metal complex is generally in the range from 10 ⁵ to 10 ^{~ 2} , often from 10 ³ to 1 and in particular from 10 ⁱ to 1.

The dispersants likewise used to prepare the polymer dispersions 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 poly ethacrylic acids, gelatin derivatives or acrylic acid, acid methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid copolymers and their alkali metal salts as well as 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 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. Frequently, 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 anionic, cationic or nonionic in 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, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pages 192 to 208.

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-al ylphenols (EO grade: 3 to 50, alkyl radical: C ₄ to Cι ₂ ) and ethoxylated fatty alcohols (EO degree: 3 to 80; alkyl radical: Ce to

• Examples include the Lutensol ^® A brands (Cι ₂ Ci ₄ fatty alcohol ethoxylates, EO grade: 3 to 8), Lutensol ^® AO brands (CιCι ₅ oxo alcohol ethoxylates, EO grade: 3 to 30), Lutensol ^® AT Brands (Ci _δ Cis fatty alcohol ethoxylates, EO grade: 11 to

80), Lutensol (5) ON brands (Cio-Oxoalkoholethoxylate, EO grade: 3 to 11) and the Lutensol ^® TO brands (Cι ₃ -Oxoalkoholethoxylate, EO grade: 3 to 20) from BASF AG.

Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: Cs to Cie), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C ₁₂ to Cis) and ethoxylated alkylphenols (EO degree: 3 to 50 , Alkyl radical: C ₄ to Cι ₂ ) of alkyl sulfonic acids (alkyl radical: C ₁₂ to Cis) and of alkylarylsulfonic acids (alkyl radical:

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

wherein R ^X7 and R ^{X8 are} H atoms or C ₄ - to C ₂₄ -alkyl and are not simultaneously H atoms, and Dl and D ^{2 can be} alkali metal ions and / or ammonium ions. In the general formula XI, R ¹⁷ and R ^{18 are} preferably linear or branched alkyl radicals having 6 to 18 carbon atoms, in particular having 6, 12 and 16 carbon atoms or hydrogen, where R ⁱ⁷ and R ^{i8 are} not both H atoms at the same time , D and D ² are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Compounds XI in which D ¹ and D ² Sodium, R ^{17 is} a branched alkyl radical with 12 C atoms and R ^{i8 is} an H atom or R ¹⁷ . 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 the Dow Chemical Company). The compounds XI are generally known, for example from US Pat. No. 4,269,749, and are commercially available.

Suitable cationic emulsifiers are generally a primary, secondary, tertiary or quaternary ammonium salt, alkanolammonium salt, pyridinium salt, imidazolinium salt, oxazolinium salt, and morpholinium salt, and a Cς to Ci ₈ alkyl, alkylaryl or heterocyclic radical 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-trimeth-- lyammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate and the gemini surfactant N, N'- (lauryl) ethylendiamindisulfat, ethoxylated tallow alkyl-N-methyl ammonium sulfate and ethoxylated oleylamine (for example Uniperol.RTM ^® AC from. BASF AG, about 12 ethylene oxide). Numerous other examples can be found in H. St che, 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 Anionic counter groups are as low as possible nucleophilic, such as perchlorate, sulfate, phosphate, nitrate and carboxylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, such as methyl sulfonate, trifluoromethyl sulfonate para-toluenesulfonate, furthermore tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3, 5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.

The emulsifiers 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, based in each case on 100 parts by weight of water. Depending on the polymerization system, it is also possible to choose the amount of emulsifiers so that their critical micelle 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. 5

In addition to water, organic solvents that are slightly soluble in water can also be used. Suitable solvents are liquid aliphatic and aromatic hydrocarbons with 5 to 30 carbon atoms, such as n-pentane and isomers, cyclopentane, n-

10 hexane and isomers, cyclohexane, n-heptane and isomers, n-octane and isomers, n-nonane and isomers, n-decane and isomers, n-dodecane and isomers, n-tetradecane and isomers, n-hexadecane and isomers, n Octadecane and isomers, eicosane, benzene, toluene, ethylbenzene, cumene, o-, m- or p-xylene, mesitylene, and generally carbon

15 hydrogen 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, for example fatty acid esters with 10 to

20 28 carbon atoms in the acid part and 1 to 10 carbon atoms in the alcohol part or esters from carboxylic acids and fatty alcohols with 1 to 10 carbon atoms in the carboxylic acid part and 10 to 28 carbon atoms in the alcohol part. Of course, it is also possible to use mixtures of the aforementioned solvents.

25

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, based in each case on the total amount of solvent.

35

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.

40

The present invention also extends to a process for the preparation of aqueous polymer dispersions by polymerization of one or more olefins in the aqueous medium in the presence of dispersants and, if appropriate, 45 organic solvents, which is characterized in that the polymerization of the olefin (s) using a Catalyst system based on transition metal complexes with Neutral ligands and an activator are used, and such transition metal complexes are used which have no metal-carbon bond before their activation with the aid of the activator used.

The polymerization of the olefin (s) is preferably carried out with the aid of a catalyst system based on transition metal complexes of the general formulas (I) to (X). Furthermore, it is advisable to design the polymerization of the olefin (s) with the aid of the activators mentioned above.

The transition metal complexes used can, on the one hand, be prepared by complexing metal salts in organic solvents before dispersing them in an aqueous medium. On the other hand, it is also possible for the transition metal complexes to be accessible by adding the respective ligands to aqueous metal salt solutions (in-situ preparation).

The process according to the invention can also be carried out by continuously adding the activator used during the polymerization. It may also be advisable to introduce the activator into the aqueous dispersion only after the monomers have been added.

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 and the activators used are dissolved in some or all of the olefins and / or the slightly water-soluble organic solvents. This solution is then mixed with the dispersants in an aqueous medium to form oil-in-water dispersions with an average droplet diameter> 1000 μm; the so-called macro emulsions. These macroemulsions are then converted, using known measures, into oil-in-water emulsions with an average droplet diameter of <1000 nm, the so-called mini-emulsions, and the remaining or total amount of the compounds and / or the small amount are added to them at the reaction temperature Water soluble organic solvent.

The average size of the droplets of the disperse phase of the aqueous oil-in-water emulsions can be determined according to the principle of uasielastic dynamic light scattering (the so-called z-average droplet diameter d _{z of} the unimodal analysis of the auto-correlation function), for example with a Coulter N4 Plus Particle Analyzer from Coulter Scientific Instruments. The measurements are diluted at 25 ° C and atmospheric pressure aqueous mini emulsions made, the content of non-aqueous components is 0.01 wt .-%. 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 the thinning from changing the droplet diameter.

The values for d _z determined in this way for the so-called mini emulsions are normally <700 nm, frequently <500 µm. According to the invention, the d _z range from 100 nm to 400 nm or from 100 nm to 300 nm is favorable. In the normal case, d _z for an aqueous miniemulsion is> 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 macroemulsion 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. 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 pressures of up to 1200 bar by means of a pneumatically operated piston pump and removed via a so-called "interaction chamber". stressed. In the "interaction chamber", the emulsion beam is divided into two beams in a microchannel system, which are brought together at an angle of 180 °. Another example for a person working according to this type of homogenization. The homogenizer is the Nanojet Type Expo from Nanojet Engineering GmbH. However, with the Nanojet instead of a fixed channel Systems installed two homogenizing valves that 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, inter alia on the concentration of emulsifier and on the energy introduced during homogenization and is therefore for example be specifically adjusted by appropriate change in the homogenization or the corresponding ^• ultrasonic energy.

The device described in DE 197 56 874 has proven particularly useful for producing an aqueous mini-emulsion from conventional macroemulsions by means of ultrasound. Here- in, it is a device having a reaction chamber or a through-flow reaction channel, and at least one means ^• comprising the through-flow reaction channel to 'be transferred, ultrasonic waves to the reaction space and wherein the means is configured for transmitting ultrasonic waves so 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 such that it essentially corresponds to the surface of the reaction space or, if the reaction space is a section of a flow-through reaction channel, extends essentially over the entire width of the Extends 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. The reaction In principle, rooms can also have a very small depth, but in view of the lowest possible risk of clogging and easy cleaning and a high product throughput, reaction chamber depths are preferred, which are much larger 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 batch-wise production of the mini-emulsions used. 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 flow direction, 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 medium with corresponding dimensions is installed in one side of the rectangle, a particularly effective and uniform 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. This case, both ^'the emitting surfaces and the depth of the reaction space, i.e. the distance between the emitting surface and the bottom of the flow channel vary. The means for transmitting ultrasound waves is particularly advantageously designed as a sonotrode, whose end 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 in the sound to be sonicated 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, for example, such that the total amounts of the metal complex and the activators added 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. In these are metered in at reaction temperature and with constant stirring, the total amount of olefins and, if appropriate, the remaining amounts of organic solvents or dispersants. 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 activators added are dissolved in a part or the total amount of the olefins. This organic metal complex solution is then dispersed together with a part or the total amount of the dispersing agent in water to form a macroemulsion. The macroemulsion is converted into a mini emulsion by means of one of the aforementioned homogenizing devices. In this mini emulsions at reaction temperature and with constant stirring, the optionally remaining amounts of olefins or Diεpergier metered edium and optionally the total amount of low löεlichen in Waεεer organic ^'see solvent. 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, can contain, in addition to the abovementioned compounds, ie the complex compounds, optionally the activators and the solvent and the olefins, and other components. Formulation aids, antioxidants; Light stabilizers, but also dyes, pigments and / or waxes for hydrophobization in question. If the solubility of the other components in the organic phase forming the droplets is greater than in the aqueous medium, they remain in the droplets during the polymerization reaction. Since the droplets of olefins and / or solvents which are slightly soluble in water ultimately contain the metal complexes and ultimately represent the sites of the polymerization, the polymer particles formed generally contain these additional components in copolymerized form. The actual polymerization usually runs at a minimum pressure of 1 bar, below this pressure the polymerization rate is too low. 2 bar are preferred and a minimum pressure of 10 bar is particularly preferred. 5

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

10

The polymerization temperature can be varied within a wide range. The minimum temperature is 0 ° C, because at. low temperatures reduce the rate of polymerization. goes. A minimum temperature of 10 ° C. is preferred and particularly

15 preferably 30 ° C. 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 20 3000 nm, preferably between 50 and 500 nm and particularly preferably between 70 and 350 nm (quasi-elastic light scattering; ISO standard 13321). The distribution of the particle diameter is generally narrow and monomodal.

25 The particle diameter 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.

30 The weight-average molecular weights M _{w of} the polymers obtained, determined as standard by means of gel permeation chromatography with polystyrene or with polymethyl methacrylate, 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

Molecular weight distribution D (with D = M _w / M _n ) is usually narrow with D values of <4, <3, but also <2.5 or ε even <2.

Through targeted variation of the olefinically unsaturated compounds, it is possible according to the invention to produce polymers whose glass transition temperature or melting point is in the range from -100 to +270 ° C.

With the glass transition temperature T _g , the limit value of the glass transition temperature is meant, which, according to G. Kanig (Kolloid- 45 Zeitschrift für Polymer, vol. 190, page 1, equation 1), strives with increasing molecular weight. The glass transition temperature is determined using the DSC method (diff rential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53765).

After Fox (TG Fox, Bull. Am. Phys. Soc. 1956 [Ser. II] 1, page 5 123 and according to Ulimann's Encyclopedia of Industrial Chemistry, vol. 19, page 18, 4th edition, Verlag Chemie, Weinheim , 1980) applies to the glass transition temperature of highly weakly cross-linked copolymers in a good approximation:

0 1 / T _g = l / _g l + X ² / T _g ² + X ¹¹ / T _g ¹¹ ,

where χ, x ² , .... x ^{n are} the fractions of the monomers 1, 2, .... n and T _g ⁱ , T _g ² , .... Tg ¹¹ 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 for glass transition temperatures of homopolymers are eg J. Brandrup, EH. 0 Immergut, Polymer Handbook, l ^Ξt 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. 5. Since the MFT is no longer measurable below 0 ° C, the lower limit of the MFT can only be given by the Tg values. The MFT is determined in accordance with DIN 53787.

The process according to the invention also makes it possible to obtain aqueous polymer dispersions whose solids content is 0.1 to 70% by weight, frequently 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 completion 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 of the polymers present in the aqueous medium being adversely affected. 0

The aqueous polymer dispersions obtainable according to the invention are frequently stable over several weeks or months and generally do not show any phase separation, separations or coagulum formation during this time. 5 The aqueous polymer dispersions accessible according to the invention can advantageously be used in numerous applications, such as paper applications such as paper coating or surface sizing, and also paints and varnishes, construction chemicals and plastic plasters, adhesive raw materials, sealants, molded foams, textile and leather applications, carpet backing coatings, mattresses or pharmaceuticals preparations. They can also be used as additives in polymer blends or in building materials.

Paper coating is understood to mean coating the paper surface with aqueous pigmented dispersions. The polymer dispersions according to the invention are advantageous here on account of their favorable prices. 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. Another 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 ter. -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 UN stability. Furthermore, aqueous polyethylene dispersions are particularly suitable because they are resistant to basic materials such as cement, for example, which are common in construction chemistry.

In adhesives, insbeεondere in Klebεtoffen for εelbεtklebende labels or sheets εowie Pflaεtern, but also fen ^'in Bauklebstof- or Induεtrieklebstoffen have dispersions of the invention economic benefits. In construction adhesives in particular, they are particularly advantageous because they are resistant to basic materials that are common in construction chemistry.

In molded foams which are produced from the polymer 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 vulcanization pastes. Molded foams are processed into mattresses, for example.

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

Carpet back coatings serve to glue the carpet fibers on the back, 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. Another advantage is that during the preparation of the dispersions for carpet back coatings according to the invention no molecular weight regulators such as, for example, tert. Dodecyl. must be added, which can be badly separated on one side but smell unpleasant on the other. Finally, carpets containing the carpet back coatings according to the invention can be recycled well.

Pharmaceutical preparations are understood to mean dispersions as carriers of medicaments. Dispersions as carriers of medicines 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, preparatively simple and safety-technically 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 minimal amounts of organic solvents. However, if the process according to the invention is carried out in the presence of solvents which are sparingly soluble in water, it is possible to avoid odor pollution when polymer films are formed by selecting high-boiling solvents. On the other hand, the optionally used solvents often act as coalescing agents and thus promote film formation. Show due to procedure 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, separation or coagulum formation during this time. After erfindungεgemäßen method also provides aqueous polymer dispersions εind also accessible, whose polymer εtoffe next to the polymer further ^'additives such as Formulierungεhilfsmittel, anti-oxidants, light stabilizers, however, also contain dyes, pigments and / or waxes.

The aqueous polymer dispersions according to the invention are distinguished, inter alia, by: also characterized by the fact that they have polyolefins with a high molar mass.

Beiεpiele:

Degassed solvents were always used for the polymerization in the individual examples. In Example 1, the polymerization was carried out using a transition metal compound of the general formula (I), nickel being used as the metal and the individual substituents having the following meaning.

L ( _Z ): bromide; n = 2

E, E ₂ : each nitrogen atom

R ⁱ , R ² : each a 2, 6-iso-propylphenylreεt

R ³ , R ⁴ : each naphthyl

The transition metal compound characterized in this way is referred to below as follows:

[R ^l N = CR ³ CR = NR ^2] NiBr ₂

They were produced in accordance with the regulation which is disclosed in WO 96/23010.

Example 1

0.03 mmol [R ⁱ N = CR ³ CR = NR] NiBr ₂ , 0.15 mmol sodium borohydride and 0.04 mmol Na [((3, 5-CF ₃ ) ₂ Ph) B] were initially in 0.5 ml of 1-octene suspended. Then 19 ml of water and 10 mmol / 1 were added Sodium dodecyl sulfate added. The mixture was stirred at 20 ° C. for 120 minutes. The polyoctene obtained was then precipitated by adding 20 ml of methanol and separated (yield: 2x10 ¹ mol of octene / mol of nickel).

Example 2

0.045 mol [ArN = CRCR = NAr] NiBr ₂ [R = naphthyl, Ar = 2, 6-iso-propylphenyl] and 0.045 mmol Na [((3, 5-CF ₃ ) ₂ Ph) ₄ B] were found in 2 ml of toluene dissolved. Then 100 ml of water and 10 mmol / 1 sodium dodecyl sulfate were added. A mini emulsion was made using an ultrasonic wand. The solution was then transferred to a steel autoclave and rinsed with ethylene. Then 0.68 mmol sodium borohydride were added. An ethylene pressure of 15 bar was set and kept at 30 ° C. for 60 minutes. A stable dispersion of polyethylene was obtained ^' (solids content: 1.5% by weight; glass transition temperature of the polyethylene = 54 ° C; melting point of the polyethylene 114 ° C).

Example 3

0.09 mmol [ArN = CRCR = NAr] NiBr ₂ [R = naphthyl, Ar = 2, 6-iεo-propylphenyl] and 0.09 mmol Na [(3, 5-CF ₃ ) ₂ PI1) ₄ B ] were dissolved in 2 ml of toluene. 100 ml of water with sodium dodecyl sulfate (10 mmol / 1) were added. A mini emulsion was produced using an ultrasound rod. The solution was transferred to a steel autoclave and rinsed with ethylene. Then 1.45 mmol sodium borohydride were added. An ethylene pressure of 15 bar was set and kept at 5 ° C. for 60 minutes. A stable dispersion of polyethylene was obtained (solids content 0.9% by weight, glass transition temperature of the polyethylene -40 ° C., melting point of the polyethylene 118 ° C.).

Example 4

0.03 mmol [ArN = CRCR = NAr] NiBr ₂ [R = naphthyl, Ar = 2, 6-iso-propylphenyl] and 0.04 mmol Na [((3, 5-CF ₃ ) ₂ Ph) ₄ B] were dissolved in 2 ml of toluene. 19 ml of water with sodium dodecyl sulfate (10 mmol / 1) and 1 ml of 1-octene were added. A mini emulsion was made using an ultrasonic wand. Then were

0.15 mmol sodium borohydride added as an aqueous solution. After 2 hours, a stable dispersion of polyoctene was obtained (solids content 3.1% by weight, glass transition temperature of the polymer -60 ° C., molar mass (weight average Mw) 8.3 * 10 ⁵ , molecular weight (number average Mn) 4.5 -10 ⁴ .

Claims

claims

1. Aqueous polymer dispersions, obtainable by polymerizing one or more olefins in an aqueous medium in the presence of dispersants and, if appropriate, organic solvents, the polymerization of the or the olefins using a catalyst system based on transition metal complexes with neutral ligands and using an activator takes place and such transition metal complexes are used which have no metal-carbon bond before their activation with the aid of the activator used.

2. Aqueous Polymeriεatdiεperεionen according to claim 1, wherein transition metal complexes of the general formulas (I) to (X) below are used.

(n) (n) L (n)

I II III

IV ^{■ •} V VI

VII VIII

IX X

in which the substituents and indices have the following meaning.

M. a transition metal of groups 7 to 10 of the periodic system

Egg: nitrogen atom or phosphorus atom for the formulas I, II, III, VI, VII, IX, X

Oxygen atom or sulfur atom for the formulas IV and V

Substituted nitrogen atom (NR ⁸ ) or substituted phosphorus atom (PR ⁸ ) for the formula V

E ₂ : nitrogen atom or phosphorus atom for the formulas

I, VII, IX and X

Oxygen atom or sulfur atom for the formulas

II, III, IV, V, VI

E ₄ : phosphorus atom for the formula VIII L (n): halide ions, amide ions (R ¹⁰ ) NH_j-, where h is an integer from 0 to 2, oxy compound OR ⁹ or acetylacetonate and n stands for the valency of the metal M.

R ⁱ to R ⁸ : independently of one another hydrogen

C 1 -C ₂ -alkyl, where the alkyl groups may be branched or unbranched, C 1 -C ₂ -alkyl, one or more times identical or differently substituted by C ₂ -C ₂ -alkyl groups, halogens, N0 groups, C ₁ -C ₂ - Alkoxy groups or -C ₂ -C thioether groups, C ₇ -C ₃ aralkyl, C ₃ -C ₂ cycloalkyl,

C ₃ -Ci ₂ cycloalkyl, substituted one or more times identically or differently by C ₁ -C ₄ -alkyl groups, halogens, NÜ ₂ groups, C 1 -C ₂ alkoxy groups or C ₁ -C ₃ thioether groups, C ₆ -Ci ₄ aryl .

C ₆ -Ci ₄ aryl, identical or differently substituted by one or more C ₁ -C ₄ alkyl groups, halogens, N0 ₂ groups, mono- or polyhalogenated C ₁ -C ₄ alkyl groups, C 1 -C ₂ alkoxy groups, silyloxy groups 0SiR ^H R ^l2 R ¹³ , amino groups NR ⁱ⁴ R ^l5 or

Cι -Cι thioether groups, Cι-Ci ₂ ~ alkoxy groups, silyloxy groups OSiR ^lx R ⁱ² R ¹³ , halogens, N0 groups or

Amino groups NR ⁱ R ⁱ⁵ , where in each case two adjacent radicals R ⁱ to R ⁸ can form a saturated or unsaturated 5- to 8-membered ring with one another,

R ⁹ to R ⁱ⁵ independently of one another,

-C ~ C o -alkyl groups, which can be substituted on their side with 0 (C ₁ -C ₆ -alkyl) or N (C ₁ -C ₆ -alkyl) ₂ groups,

C ₃ -C ₂ cycloalkyl groups, C ₇ -C ₃ aralkyl groups or Cg-Ci ₄ aryl groups.

3. Aqueous polymer dispersions according to claim 2, wherein in the general formula (I) the substituents and indices have the following meaning: M: nickel or palladium

Egg: nitrogen atom

5 E _2: nitrogen atom

L (n): fluoride, chloride, bromide,

n: valence of the metal M 10

R ^l to R ⁴ : C ₆ -C aryl

C ₇ -Cι ₃ aralkyl

4. Aqueous polymer dispersions according to any one of claims 1 15 to 3, wherein organometallic compounds are used as activator.

5. Aqueous polymer dispersions according to one of claims 1 to 3, wherein boron compounds are used as the activator.

6. Aqueous polymer dispersions according to claim 5, wherein complex borohydrides, boraryls or boron alkyls are used as the activator.

25

7. Aqueous polymer dispersions according to one of claims 1 to 6, the olefin being exclusively an olefin from the group consisting of ethylene, propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 1 -Octen is used.

30

8.- Aqueous polymer dispersions according to one of claims 1. to 6, at least two olefins selected from the group comprising ethylene, propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 1-octene, styrene and

35 acrylic acid or its derivatives are used.

9. Aqueous polymer dispersions according to claims 1 to 8, these being in the form of a mini emulsion.

40 10. A process for the preparation of aqueous polymer dispersions by polymerizing one or more olefins in the aqueous medium in the presence of dispersants and, if appropriate, organic solvents, characterized in that the polymerization of the or

45 olefins with the aid of a catalyst system based on

Transition metal complexes with neutral ligands and with the help of an activator and where such transition metal complexes are used which have no metal-carbon bond before their activation with the aid of the activator used.

11. The method according to claim 10, characterized in that the polymerization of the olefin (s) is carried out with the aid of a catalyst system based on transition metal complexes of the general formulas (I) to (X) according to claims 2 or 3. 10

12. The method according to claims 10 or 11, characterized in that the polymerization of the olefin or olefins with the aid of an activator according to claims 4 to 6

- follows. 15

13. The method according to claims 10 to 12, characterized daεs that Practice ^{'rgangsmetallkomplexe} before their dispersion in aqueous media by complexation of metal salts in organic solvents can be prepared.

20

14. The method according to claims 10 to 12, characterized in that the transition metal complexes are produced by adding the respective ligands to aqueous metal salt solutions.

25

15. The method according to claims 10 to 14, characterized in that the activator used is continuously added during the polymerization.

30 16 .. Method according to claims 10 to 15, characterized in that the activator is introduced into the aqueous dispersion only after the addition of the monomers.

17. Use of the aqueous dispersions according to claims 35 1 to 9 for paper applications such as paper coating or

Surface sizing, paint, adhesive raw materials, molded foams such as mattresses, textile and leather applications, carpet backing or pharmaceutical applications, as well as additives in polymer blends or in building materials. 40

45