EP1322417A2

EP1322417A2 - Amino acid complexes and the use thereof in producing olefin polymers

Info

Publication number: EP1322417A2
Application number: EP01982318A
Authority: EP
Inventors: Shahram Mihan; Wolfgang Beck; Walter Ponikwar
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2000-09-21
Filing date: 2001-09-19
Publication date: 2003-07-02
Also published as: WO2002024330A2; WO2002024330A3; JP2004509153A; DE10047461A1; US6858688B2; US20040024150A1

Abstract

The invention relates to an amino acid complex of the general formula (1), wherein M is selected from Fe, Co, Ni, Pd, Pt or Ir, and preferably represents Ni. The invention further relates to a method for producing the same and to the use thereof for polymerizing olefins.

Description

Amino acid complexes and their use in the production of olefin polymers

The present invention relates to amino acid complexes of the general formula I,

where the variables are defined as follows:

M selected from Fe, Co, Ni, Pd, Pt or Ir,

X selected from 0 or S;

R ¹ and R ^{2 are the} same or different and selected from

Hydrogen, -CC ₈ alkyl, substituted or unsubstituted,

C ₃ -C 5 -cycloalkyl, substituted or unsubstituted,

C 1 -C aralkyl,

C ₆ -Ci ₄ aryl, unsubstituted or singly or multiply identical or differently substituted with Ci-Cβ-alkyl, substituted or unsubstituted,

C-Ci ₂ cycloalkyl,

C-Ci ₃ aralkyl,

C ₆ -C ₄ aryl,

Halogen, -CC ₆ alkoxy,

C ₆ -Ci ₄ aryloxy,

SiR ⁴ R ⁵ R ⁶ or 0-SiR R ⁵ R ⁶ , where R ⁴ -R ^{6 are} selected from Ci-Cs-alkyl, C ₃ -Cι ₂ cycloalkyl, C ₇ -Cι ₃ aralkyl or

C ₆ -Cι ₄ aryl; five- to six-membered nitrogen-containing hetero-aryl radicals Y, unsubstituted or mono- or polysubstituted by the same or different substitution

Cι-C ₈ - alkyl, substituted or unsubstituted,

C ₃ -Cι cycloalkyl, C ₇ -Cι ₃ aralkyl,

C ₆ -Ci ₄ aryl,

Halogen,

Ci-Cg-alkoxy, ^c s ~ -C ₄ aryloxy, SiR ⁴ R ⁵ R ⁶ or 0-SiR ⁴ R ⁵ R ⁶ , where R ⁴ -R ^{6 are} selected from Ci-Cs-alkyl, C ₃ -Cι ₂ Cycloalkyl, C ₇ -C ₃ aralkyl or 'C ₆ -C ₁₄ aryl, CH ₂ -Y, where Y is as defined above; y is an integer from 0 to 4; ¹ an inorganic or organic neutral ligand; L ^{2 is} an inorganic or organic anionic ligand, where L ¹ and L ² can be linked to one another by one or more covalent bonds, z an integer from 0 to 3; x is an integer from 0 to 3.

Furthermore, the present invention relates to a process for the preparation of the amino acid complexes of the general formula I according to the invention and catalyst systems for the polymerization or copolymerization of olefins, containing one or more amino acid complexes of the general formula I and optionally an activator, and a process for the polymerization or copolymerization of olefins using the catalyst system according to the invention.

Polymers and copolymers of olefins are of great economic importance because the monomers are easily accessible in large amounts and because the polymers can be varied within a wide range by varying the production process or the processing parameters. Particular attention is paid to the catalyst used in the manufacturing process.

The systems presented in the literature are not free from disadvantages. For the cyclopentadienyl ligands of most metallocenes, complex syntheses are necessary, which can comprise 4 or more stages, as described, for example, in H.-H. Brintzinger et al. , Appl. Chem. 1995, 107, 1255, in EP-A 0 549 900 or EP-A 0 576 970. However, the catalysts are made more expensive by multi-stage syntheses.

After activation with methylaluminoxane ("MAO"), the systems presented in WO 96/23010 provide highly branched polymers which, however, do not have a sufficiently high molecular weight for numerous material applications.

The complex systems presented by Brookhart and Gibson (e.g. WO 98/27124) are easily accessible synthetically, but they only incorporate comonomers in very small quantities. In the polymerization of ethylene, for example, highly linear, brittle polymers are obtained whose suitability for materials is only limited.

From K. Severin et al. , Ciiem. SSSR. 1995, 128, 1127 are Rh-Co - complexes of ^'general formula A known in which R = methyl or benzyl and which are easily accessible synthetically from the natural amino acids. They are suitable as chiral catalysts for hydrogenation, as cytostatics or as labeling reagents in biochemistry. However, they are unsuitable as polymerization catalysts.

It was therefore the task

to provide new complexes which are active in polymerization against olefins, the ligands of which are accessible by simple syntheses or are commercially available and which provide high molecular weight polyethylene; To provide catalyst systems for the polymerization or copolymerization of olefins from the new complexes and suitable activators, to provide a process for the polymerization or copolymerization of olefins using these catalyst systems, - to provide a process for the preparation of the complexes, a solid catalyst which is suitable for gas phase polymerization, the Suspension polymerization or bulk polymerization is to be provided, containing a complex compound, a suitable activator and a solid support, a process for preparing a solid catalyst from the new complexes and to be used for the polymerization or copolymerization of olefins.

Accordingly, the amino acid complexes defined at the outset were found.

In Formula I are

M selected from elements of the 6th to 10th group of the Periodic Table of the Elements, for example Fe, Co, Ni, Pd, Pt or Ir, preferred is Ni or Pd and particularly preferably Ni; X selected from oxygen or sulfur; Sauers is preferred; R ¹ to R ^{3 are the} same or different and selected from hydrogen; -C ₈ alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl and n-octyl; 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;

The substituted Ci-Cs-alkyl groups may be mentioned as examples: mono- or polyhalogenated C 1 -C ₈ -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,

Bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl are particularly preferred; - Ci-Cs-alkyl groups which are substituted with one or more functional groups such as amino groups, hydroxyl groups, thioether groups, thiol groups, carboxyl groups or guanidine groups; the following functionalized alkyl groups are particularly preferred: -CH ₂ -CH ₂ -CH ₂ -CH ₂ -NH ₂ , -CH (OH) -CH ₃ ,

-CH ₂ -OH, -CH ₂ -CH ₂ -CH (OH) -CH ₂ -NH ₂ , -CH ₂ -CH ₂ -SCH ₃ ,

-CH ₂ -CONH ₂ ;

-CH ₂ -CH ₂ -COOH, -CH ₂ -CH ₂ -C0NH ₂ ; -CH ₂ -COOH,

-CH ₂ -CH ₂ -NH-C (NH ₂ ) ₂ ; - C ₃ -C cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred; Examples of substituted cycloalkyl groups include:

2-methylcyclopentyl, 3-methylcyclopentyl, cis-2, 4-dirthylcyclotyl, trans-2, 4-dimethylcyclopentyl, cis-2, 5-dimethylcyclopentyl, trans-2, 5-dimethylcyclopentyl, 2, 2, 5 , 5-tetramethylcyclopentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, cis-2, 6-dirnethylcyclohexyl, trans-2,6-

Dimethylcyclohexyl, cis-2, 6-diisopropylcyclohexyl, trans-2, 6-diisopropylcyclohexyl, 2,2,6, 6-tetramethylcyclohexyl, 2-methoxycyclo tyl, 2-methoxycyclohexyl, 3-methoxycyclopentyl, 3-methoxycyclohexyl, 2-chlorocyclo pe tyl, 3-chlorocyclopentyl, 2, 4-dichlorocyclopentyl, 2 ^' , 2, 4, 4-tetrachlorocyclopentyl, 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2, 5-dichlorocyclohexyl, 2,2, 6, 6-tetrachlorocyclohexyl, 2-thiomethylcyclopentyl, 2-thiomethylcyclohexyl, 3-thio-methylcyclopentyl, 3-thiomethylcyclohexyl and other derivatives; - C -C ₃ aralkyl, preferably C ₇ - to C ₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl ( 1-methyl-1-phenyl-ethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl; - Cι-C6 ₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenyl anthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl; - C ₆ -Ci4-aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenan- ^{■ "} thryl, 3-phenanthryl, 4- Phenanthryl and 9-phenanthryl, identical or differently substituted by one or more - Ci-Cs-alkyl groups, 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, n-hep- tyl, iso-heptyl and n-octyl; preferably Ci-Cς-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;

Examples of the substituted Ci-Cs-alkyl groups are: mono- or poly-halogenated Ci-Cs-alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl,

Perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl; C ₃ -C -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,

Cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;

C ₇ -C ₃ aralkyl, - preferably C - to -C phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1-methyl -l-phenylthyl), 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferably benzyl; C ₆ -Ci ₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;

Halogen, for example fluorine, chlorine, bromine or iodine, particularly preferably fluorine or chlorine;

Cχ-C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso -Hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy; Cg-Ci ₄ aryloxy groups such as phenoxy, ortho-cresyloxy, meta-cresyloxy, para-cresyloxy, α-naphthoxy, β-naphthoxy or 9-anthry1oxy; Silyl groups SiRR ⁵ R ⁶ , where RR ^{6 are} independently selected from hydrogen, Ci-Cs-alkyl groups, benzyl radicals and C ₆ -Ci ₄ aryl groups; preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert.-butyldimethylsilyl, tert.-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl and x-tri-para-groups; the trimethylsilyl group and the tert-butyldi ethylsilyl group are particularly preferred; Silyloxy groups 0-SiR ⁴ R ⁵ R ⁶ , where R ⁴ -R ^{6 are} independently selected from hydrogen, Ci-Cs-alkyl groups, benzyl radicals and C ₆ -Cι ₄ aryl groups; preferred are the trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert.-butyldimethylsilyloxy, tert. the trimethylsilyloxy group and the tert are particularly preferred. -Butyldi - methylsilyloxy group; five- to six-membered nitrogen-containing heteroaryl radicals such as N-pyrrolyl, pyrrol-2-yl, pyrrol-3-yl, iV-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1,2, 4- Triazol-3-yl, 1,2, 4-triazol-4-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5- Pyrimidinyl, N-indolyl, 2-indolyl, 3-indolyl and N-carbazolyl; five- to six-membered nitrogen-containing heteroaryl residues such as, for example, IV-pyrrolyl, pyrrol-2-yl, pyrrol-3-yl, .W-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, l, 2.4 Triazol-3-yl, l, 2,4-triazol-4-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyrida- zinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, N-indolyl, 2-indolyl, 3-indolyl and N-carbazolyl, the same or different monosubstituted or polysubstituted by Ci-Cs-alkyl groups, 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 -Dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl and n-octyl; preferably Cχ-C ₆ 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, isobutyl, sec-butyl and tert-butyl; Examples of the substituted Ci-Cs-alkyl groups are: mono- or poly-halogenated Ci-Cs-alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, particularly fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl are preferred;

C ₃ -C-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; are preferred

Cyclopentyl, cyclohexyl and cycloheptyl;

C ₇ -C ₃ aralkyl, preferably C ₇ - to C-phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1-methyl -l-phenyl-ethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl; C ₆ -C ₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-A thryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;

Halogen, for example fluorine, chlorine, bromine or iodine, particularly preferably fluorine or chlorine; -C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso -Hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy; ^c ₆ -Ci ₄ aryloxy groups such as phenoxy, orho-cresyloxy, meta-cresyloxy, para-cresyloxy, α-naphthoxy, β-naphthoxy or 9-anthryloxy; Silyl groups SiRR ⁵ R ⁶ , where R ⁴ -R ^{6 are} independently selected from hydrogen, Cj-Cs-alkyl groups, benzyl radicals and C ₆ -Ci ₄ aryl groups; preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert.-butyldimethylsilyl, tert.-butyldiphenylsilyl, tribenzylsilyl, triphenylsilylx and the tri-para-group; the trimethylsilyl group and the tert are particularly preferred. -Butyldi ethylsilylgruppe; - Silyloxy groups 0-SiRR ⁵ R ⁵ , where R ⁴ -R ^{6 are} independently selected from hydrogen, Ci-Cs-alkyl groups, benzyl radicals and Cg-Ci ₄ -aryl groups; 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;

Ci-Cs-alkyl substituted with a 5- to 6-membered heteroaromatic Y, preferably methyl substituted with a 5- to 6-membered heteroaromatic, such as 3-indolylmethyl or 5-imidazolylmethyl.

In a particular embodiment, two adjacent radicals R ¹ to R ³ are covalently linked to one another and form a 5 to 10-membered ring. For example, R ¹ and R ^{2 can be} together: - (CH ₂ ) ₃ - (trimethylene), - (CH ₂ ) ₄ - (tetramethylene), - (CH) s- (pentamethylene), - (CH ₂ ) ₆ - (Hexamethylene), -CH ₂ -CH = CH-, -CH ₂ -CH = CH-CH ₂ -, -CH = CH-CH = CH-, -0-CH ₂ -0-, -0-CHMe-O -, -0-CH- (C ₆ H ₅ ) -0-, -0-CH ₂ -CH ₂ -0-, -0-CMe ₂ -0-, -NMe-CH ₂ -CH ₂ -NMe-, -NMe-CH-NMe- or -0-SiMe ₂ -0- with Me = CH ₃ . In a preferred example, R ¹ and R ² together form a trimethylene unit, which in turn can be substituted one or more times with C ¹ -C 6 -alkyl or with hydroxyl groups, C ¹ -C 6 -alkyl being as defined above.

y is an integer from 0 to 4, more preferably y 0 L ¹ are identical or different and are selected from inorganic or organic neutral ligands, for example phosphines of the formula (R ⁷⁾ _X PH ₃ - _K or amines of the formula (R ⁷ ) χNH ₃ -χ, where x is an integer from 0 and 3. But also ethers (R ⁷ ) 0 such as, for example, dialkyl ethers, for example diethyl ether, or cyclic ethers, such as, for example, tetrahydrofuran, H ₂ O, alcohols (R ⁷ ) OH such as methanol or ethanol, pyridine, pyridine derivatives of the formula C ₅ Hs_ _x (R ⁷ ) _x , such as 2-picoline, 3-picoline, 4-picoline, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine or 3,5-lutidine, CO, -C-C ₁₂ 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 inorganic or organic anionic ligands, for example from halide ions such as fluoride, chloride, bromide or iodide, chloride and bromide are preferred,

Amide anions (R ⁷ ) _h NH_ _h , where h is an integer from 0 to 2,

-C-C ₆ alkyl anions such as (CH ₃ ) ^_ , (C ₂ H ₅ ) -, (C ₃ H ₇ ) ^~ , (n-CH ₉ ) ^_ , (tert.-C ₄ H ₉ ) ^_ or (C ₆ Hi ₄ ) -;

Allyl anions or methallyl anions, benzyl anions or Ce-Ci ₄ aryl anions such as (C _δ Hs) -.

The radicals R ^{7 are the} same or different and are selected independently of one another

Hydrogen,

Ci-Cs-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-heptyl, iso-heptyl and n-octyl; 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-dimethyl-propyl, 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; Benzyl radicals and - C ₆ -Cχ ₄ aryl groups, such as phenyl, 1 ~ naphthyl,

2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl; C ₅ -C 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, identical or differently substituted by one or more Ci-Cs-alkyl groups, 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, n-heptyl, iso-heptyl and n-octyl; 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-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferably C 1 -C ₄ -Al yl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec-butyl and tert-butyl; Examples of the substituted Ci-Cs-alkyl groups are: mono- or poly-halogenated Ci-Cs-alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl are particularly preferred Fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl; C ₃ -C -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;

C -C ₃ aralkyl, preferably C ₇ - to Cχ ₂ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1-methyl -l-phenylethyl), 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferably benzyl;

C ₆ -C ₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9th -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;

Halogen, for example fluorine, chlorine, bromine or iodine, particularly preferably fluorine or chlorine; - Cχ-C ₆ -alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, n- Hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy; C ₆ -C ₄ aryloxy groups such as phenoxy, ortho-cresyloxy, meta-cresyloxy, para-cresyloxy, α-naphthoxy, β-naphthoxy or 9-anthryloxy;

Silyl groups SiR ⁴ R ⁵ R ⁶ , where RR ^{6 are} independently selected from hydrogen, Ci-Cs-alkyl groups, benzyl radicals and C ₆ -Cχ ₄ aryl groups; preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl,

Di ethylthexylsilyl, tert-butyldimethylsilyl, tert. -Butyl - diphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-para-xylylsilyl group; the trimethylsilyl group and the tert-butyldimethylsilyl group are particularly preferred; - Silyloxy groups 0-SiRR ⁵ R ⁶ , where R ⁴ -R ^{6 are} independently selected from hydrogen, Ci-Cs-alkyl groups, benzyl radicals and C ₆ -Cι ₄ ^' aryl groups; the trimers are preferred thylsilyloxy-, triethylsilyloxy-, triisopropylsilyloxy-, diethylisopropylsilyloxy-, dimethylthexylsilyloxy-, tert.-butyldimethylsilyloxy-, tert.-butyldiphenylsilyloxy-, triben- zylsilyloxy-, triphenylsilylyl- di-oxyl-di-oxyl-di-oxyl-silyloxy- the trimethylsilyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred; z is an integer from 1 to 3; x is an integer from 0 to 3.

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"), 1, 6-cyclodecenyl ligands or 1, 5, 9-all-frans cyclododecatrienyl ligands.

In a further special embodiment, L ^{1 is} tetramethylethylenediamine, only one nitrogen coordinating with the nickel.

The stereochemistry on the C atom that carries R ¹ is in the case that R ¹ ? H can be controlled by the choice of the amino acid. L-amino acids are generally more accessible, and therefore the L configuration on the C atom that carries R ¹ is preferred.

The amino acid complexes of the general formula I according to the invention are advantageously prepared by deprotonation of an amino acid of the general formula II,

in which the variables are as defined above, with a strong base, followed by reaction with a suitable metal compound of the general formula M (L ^X ) _{z +} ιL ² X ¹ , where

X ^{1 is selected} from halide such as fluoride, chloride, bromide or iodide, preferably fluoride or bromide, or C 1 -C ₄ alcoholate such as, for example, methanolate, ethanolate or tert-butanolate

and the remaining variables are as defined above.

Suitable bases are the bases customary in transition metal chemistry, such as, for example, lithium diisopropylamide “LDA”, alkyllithium compounds, such as, for example, methyllithium and n-butyllithium, and alcoholates, such as, for example, sodium methoxide, potassium methariolate, sodiumethanolate, potassiumethanolate, sodiumisopropyl panolat or potassium tert. butanolate, alcoholates being preferred. These alcoholates are usually used as a solution in the corresponding alcohol, but can also be used as a solid. For the deprotonation of the amino acids of the general formula II, the alcoholate solutions can be freshly prepared or commercially available solutions can be used. It is preferred to use freshly prepared alcoholate solutions, the concentration of which is usually determined by titration.

The reaction conditions for the deprotonation are generally not critical, reaction temperatures from -20 ° C. to + 80 ° C. and reaction times from 1 to 60 minutes are preferred. In order to overcome the very low solubility of the amino acids of the general formula II in some cases, it is necessary to disperse the amino acids well, for which vigorous stirring and working with ultrasound have proven useful.

The molar ratios of base to amino acid can be selected within certain limits, molar ratios of 1.1: 1 to 1: 1.1 having proven preferred and equimolar amounts having proven particularly preferred.

The deprotonated amino acids can be isolated and stored for several months, taking care to exclude moisture during storage. In a preferred embodiment of the method according to the invention, however, the deprotonated amino acid is not isolated and the deprotonated amino acid is further processed in situ.

The deprotonated amino acid is reacted with a metal compound of the general formula M (L ¹ ) _{z +} ιL ² X ¹ . The reaction conditions for the reaction are generally not critical. Reaction temperatures from -20 ° C. to + 80 ° C. and reaction times from 1 minute to 10 hours are preferred, 1 to 5 hours being particularly preferred. The order of addition of the reagents can be chosen arbitrarily. The molar ratios of metal bond to deprotonated amino acid can be selected within certain limits, with equimolar amounts having proven to be particularly preferred.

The production of the suitable metal compounds is known in principle; production instructions can be found, for example, in SY Desjardins et al., J. ^" Organomet. Chem. 1996, 515, 233. The reaction mixtures are worked up by the operations customary in complex chemistry, such as crystallization, filtration, precipitation, centrifugation or chromatography, preferably with temperature-controlled columns. When selecting the cleaning methods, care must be taken to ensure that the equivalent of the ligand L ^{1 which is} split off in the course of the preparation of the amino acid complexes of the general formula I according to the invention is separated off as quantitatively as possible. A separation of the salts from X ¹ obtained during the synthesis, for example depending on the base used LiX ¹ , NaX ¹ or KX ¹ , is advantageous.

The aminosaur complexes of the general formula I according to the invention are obtained in many cases as mixtures of isomers. Separation of the isomers is possible in some cases. However, separation of the isomers is not necessary for use in the polymerization.

So that the organometallic compounds of the general formula I are active in polymerization, they can be activated with an activator, which can also be referred to as a cocatalyst, the use of an activator being the preferred embodiment of the present invention.

Suitable cocatalysts are aluminum alkyls of the general formula Al (R ^k ), lithium alkyls of the general formula LiR ^k and alumoxanes, aluminum alkyls of the general formula AI (R ^k ) ₃ and alumoxanes being particularly preferred.

The radicals R ^{k are the} same or different and -CC ₂ -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl , iso-pentyl, 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-do-decyl; 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.

The structure of the aluminoxanes is not exactly known. They are products which are obtained by careful partial hydrolysis of aluminum alkyls (see DE-A 30 07 725). These products are not in pure form, but as mixtures of open-chain and cyclic structures of type III a and b. In formula III a and b

lil a III b, the radicals R ^{m are the} same or different and independent of one another

-CC 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 C ₁ -C1 ₅ -AI- 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, methyl is particularly preferred; C ₃ -C ₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;

C - to C ₂ o-aralkyl, preferably C ₇ - to -C ₂ -phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1-phenyl -butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl, or

C _δ -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, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl; and n is an integer from 0 to 40, preferably from 0 to 25 and particularly preferably from 0 to 22.

Cage-like structures for aluminoxanes are also discussed in the literature (Y. Koide, SG Bott, AR Barron Organometallics 1996, 15, 2213-26; AR Barron Macromol. Symp. 1995, 97, 15). Regardless of what the structure of the aluminoxanes actually looks like, they are suitable as cleaning alkyls and as cocatalysts for the organometallic compounds of the general formula I according to the invention. Aluminoxanes are dosed in significant molar excesses. How to choose a molar ratio M: AI of 1: 5 to 1: 5000, preferably 1:10 to 1: 1000 and particularly preferably 1:50 to 1: 500.

Mixtures of two or more aluminum alkyls or lithium alkyls can also be used as cocatalyst and cleaning alkyl. Mixtures of aluminum alkyls with lithium alkyls are also suitable.

Mixtures of different aluminoxanes are particularly preferred activators in which polymerization is carried out in a solution of a paraffin, for example n-heptane or isododecane. A particularly preferred mixture is the CoMAO commercially available from Witco GmbH with a formula of [(CH ₃ ) o, g (iso- C ₄ H ₉ ) ₀ , ιAlO] _n .

Suitable activators for amino acid complexes of the general formula I abstract a ligand L ¹ or L ² according to the common idea. Instead of aluminoxanes of the general formula III a or b or the above-described aluminum or boron compounds with electron-withdrawing radicals, the activator can be, for example, olefin complexes of rhodium or nickel.

Preferred nickel (olefin) _a complexes commercially available from Aldrich with a = 1, 2, 3 or 4 are Ni (C ₂ H ₄ ) ₃ ,

Ni (1,5-cyclooctadiene) "Ni (COD)", Ni (1,6-cyclodecadiene) _, or Ni (1,5,9-aIl-fcrans-cyclododecatriene). Ni (COD) ₂ is particularly preferred.

Mixed ethylene / 1,3-dicarbonyl complexes of rhodium are particularly suitable, for example rhodium acetylacetonate-ethylene Rh (acac) (CH ₂ = CH) ₂ , rhodium-benzoylacetonate-ethylene Rh (C ₆ H ₅ -CO-CH-C0- 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 = CH) is the most suitable. This connection can be made according to R. Cramer from Inorg. Syntli. 1974, 15, 14 synthesize.

Some amino acid complexes of the general formula I can be activated by ethylene. The ease of the activation reaction depends crucially on the nature of the ligand L ¹ .

The selected amino acid complexes of the general formula I and the activator together form a catalyst system.

The activity of the catalyst system according to the invention can be increased by adding further aluminum alkyl of the general formula Al (R) ₃ or aluminoxanes, in particular when connecting fertilize the general formula II a or II b or the above-mentioned aluminum or boron compounds with electron-withdrawing radicals can be used as activators; Aluminum alkyls of the general formula Al (R) ₃ or aluminoxanes can also act as molecular weight regulators. Another effective molecular weight regulator is hydrogen. The molar mass can be regulated particularly well by the reaction temperature and the pressure. In the event that the use of a boron compound as described above is desired, the addition of an aluminum alkyl of the general formula AI (R ^m ) _{3 is} particularly preferred.

It has been found that the amino acid complexes of the general formula I according to the invention are suitable for polymerizing and copolymerizing olefins. They polymerize and copolymerize ethylene and propylene particularly well.

Pressure and temperature conditions during the polymerization can be chosen within wide limits. A range from 0.5 bar to 4000 bar has proven to be suitable as the pressure, 10 to 75 bar or high-pressure conditions from 500 to 2500 bar are preferred. A temperature of 0 to 120 ° C. has proven to be suitable, preferably 40 to 100 ° C. and particularly preferably 50 to 85 ° C.

The following olefins are suitable as monomers: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-undecene, ethylene being particularly preferred.

Suitable comonomers are α-olefins, such as 0.1 to 20 mol% of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene,

1-octene, 1-decene or 1-undecene. But isobutene, styrene and norbornene are also suitable comonomers.

Toluene, ortho-xylene, meta-xylene, para-xylene or ethylbenzene have proven to be suitable as solvents, as well as mixtures thereof, and furthermore - under high pressure conditions - supercritical ethylene.

If the use of aluminum alkyl or lithium alkyl as cleaning alkyl proves to be useful, it is advantageous to meter the aluminum alkyl or lithium alkyl as a solution in a hydrocarbon separately from the catalyst system. However, it is also possible to meter the cleaning alkyl together with the amino acid complexes of the formula I according to the invention. The catalyst systems according to the invention have also proven to be hydrogen-controllable, ie by adding hydrogen the molecular weight of the polymers obtainable by the catalyst systems according to the invention can be reduced. At sufficiently Wasserstoffzugäbe ^'waxes are obtained, wherein the hydrogen concentration required also depends on the type of polymerization used. Thus, using the complexes according to the invention, by adding hydrogen, polyethylene waxes with a molecular weight M _w of a maximum of 20,000 g, preferably a maximum of 10,000 g and particularly preferably a maximum of 7,500 g, can be produced.

The amino acid complexes of the general formula I according to the invention can also be used together with metallocenes for the catalysis of olefin polymerization. For this purpose, they can be activated together or separately from the metallocenes and also metered together or separately.

If the amino acid complexes of the general formula I according to the invention can be used in polymerization processes such as suspension processes, bulk polymerization processes or gas phase processes, it is necessary to immobilize them on a solid support. Otherwise, polymer morphology problems (lumps, wall coverings, blockages in pipes or heat exchangers) may arise, which force the system to switch off. Such an immobilized amino acid complex of the general formula I is referred to as a catalyst. Preferred catalysts contain one or more amino acid complexes with an activator immobilized on a support material.

It has been found that amino acid complexes of the general formula I can be deposited well on a solid support. Suitable carrier materials are, for example, porous metal oxides of metals from groups 2-14 or mixtures thereof, furthermore sheet silicates and zeolites. Preferred examples of metal oxides of groups 2-14 are Si0, B0 ₃ , Al ₂ 0 ₃ , MgO, CaO and ZnO. Preferred layered silicates are montmorrilonite or bentonite; MCM-41 is used as the preferred zeolite.

Particularly preferred carrier materials are spherical silica gels and aluminosilicate gels of the general formula Si0 ₂ -a Al ₂ 0 ₃ , where a generally stands for a number in the range from 0 to 2, preferably 0 to 0.5. Such silica gels are commercially available, for example silica gel SG 332, Sylopol® 948 or 952 or S 2101 from WR Grace or ES 70X from Crosfield. Average particle diameters from 1 to 300 μm, preferably from 20 to 80 μm, have proven suitable as the particle size of the carrier material, the particle diameter being determined by known methods such as sieving methods. The pore volume of these carriers is from 1.0 to 3.0 ml / g, preferably from 1.6 to 2.2 ml / g and particularly preferably from 1.7 to 1.9 ml / g. The BET surface area is 200 to 750 m / g, preferably 250 to 400 m ² / g.

Contamination adhering to the carrier material, in particular

To remove moisture, the carrier materials can be heated before doping, with temperatures of 45 to 1000 ° C being suitable. Temperatures of 100 to 750 ° C are particularly suitable for silica gels and other metal oxides. This baking should take place over a period of 0.5 to 24 hours, whereby

15 baking times of 1 to 12 hours are preferred. The printing conditions depend on the chosen process; the heating can be carried out in a fixed bed process, a stirred tank or else in a fluid bed process. In general, the heating can take place at atmospheric pressure. Are advantageous

20 however reduced pressures from 0.1 to 500 mbar, a range from 1 to 100 mbar is particularly advantageous and a range from 2 to 20 mbar is very particularly advantageous. For fluid bed processes, on the other hand, it is advisable to work at a slightly elevated pressure, the pressure in a range from greater than 1 bar to

25 5 bar, preferably 1.1 to 1.5 bar is selected.

Chemical pretreatment of the support material with an alkyl compound such as aluminum alkyl Al (R ^m ) ₃ , lithium alkyl LiR ^k or an alumoxane of the general formula II a or II b is also possible.

30

For a polymerization in the suspension process, those suspending agents are used in which the desired polymer is insoluble or only slightly soluble, because otherwise in the parts of the plant in which the product contains the suspending agent

35 is separated, deposits of the product appear and forcing repeated shutdowns and cleaning operations. Suitable suspending agents are saturated hydrocarbons such as, for example, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane and cyclohexane, isobutane being preferred.

40

Pressure and temperature conditions during the polymerization can be chosen within wide limits. A range from 0.5 bar to 150 bar has proven to be suitable as the pressure, 10 to 75 bar being preferred. The temperature range is from 0 to

45 120 ° C has been found to be suitable, preferably 40 to 100 ° C and particularly preferably 50 to 85 ° C. The following olefins are suitable as monomers: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-undecene.

The catalysts of the invention have also proven to be hydrogen-controllable, i.e. by adding hydrogen, the molecular weight of the polymers obtainable by the catalysts according to the invention can be reduced. If enough hydrogen is added, waxes are obtained, and the required hydrogen concentration also depends on the type of polymerisation system used. It is also observed that the

Activity of the catalysts of the invention increases with hydrogen additions.

The catalysts of the invention can also be used together with one or more other polymerization catalysts known per se. So you can along with

Ziegler-Natta catalysts, supported metallocene catalysts of the transition metals of groups 4 to 6 of the periodic table of the elements,

Late transition metal catalysts (WO 96/23010),

Fe or Co complexes with pyridyldiimine ligands as described in

WO 98/27124 are disclosed, or else chrome oxide catalysts according to Phillips can be used.

It is possible, on the one hand, to mix different catalysts with one another and to dose them together, or to use co-supported complexes on a common support, or to meter different catalysts separately into the polymerization vessel at the same or at different points.

The polymerization process according to the invention gives polymers, preferably polyethylene, which is distinguished by high molar masses and a small number of branches. The polyethylene obtainable by the process according to the invention is particularly suitable for films.

It was also found that the amino complexes of the general formula I according to the invention, in particular those with M = Ni, can be used in a particular way for polymerization or copolymerization. tion of 1-olefins, preferably ethylene, are suitable in emulsion polymerization processes.

In addition to other 1-olefins as comonomers, such as propene, 1-butene, 1-hexene, 1-octene, 1-decene, styrene, norbornene or isobutene, polar comonomers can also be incorporated with the aid of the catalyst system according to the invention, where 0.1 to 50 mol% of comonomer can be used. Are preferred

- Acrylates such as acrylic acid, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid (2-ethyl) hexyl ester, acrylic acid n-butyl ester or acrylic acid tert. butyl; Methacrylic acid, methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid n-butyl ester or methacrylic acid tert-butyl ester;

Vinyl carboxylates, vinyl acetate being particularly preferred, unsaturated dicarboxylic acids, maleic acid, unsaturated dicarboxylic acid derivatives being particularly preferred, maleic anhydride and maleic alkylimides such as maleic acid methyl imide being particularly preferred.

Terpolymers with at least 2 of the monomers listed above and ethylene can also be prepared.

The emulsion polymerization of the 1-olefins using the amino complexes of the general formula I according to the invention can be carried out in a manner known per se.

The order in which the reagents are added during the polymerization is not critical. For example, gaseous monomer can first be pressed onto the solvent or liquid monomer can be metered in, and then the catalyst system is added. But you can also first dilute the catalyst system solution with additional solvent and then add monomer.

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 demands on 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 is 10 ° C, since the rate of polymerization decreases at low temperatures. A minimum temperature of 40 ° C. is preferred, and 65 ° C. is particularly preferred. The maximum sensible temperature is 350 ° C. and preferably 150 ° C., particularly preferably 100 ° C.

Before the polymerization, the amino acid complex of the general formula I is dissolved in an organic solvent or in water. Stirring or shaking for several minutes ensures that the solution is clear. Depending on the solubility of the substance in question, the stirring time can be between 1 and 100 minutes.

At the same time, if necessary, the activator is dissolved in a second portion of the same solvent or in acetone.

Aromatic solvents such as benzene, toluene, ethylbenzene, ortho-xylene, meta-xylene and para-xylene and mixtures thereof are suitable as organic solvents. Cyclic ethers such as tetrahydrofuran and dioxane or non-cyclic ethers such as diethyl ether, di-n-butyl ether, diisopropyl ether or 1,2-dimethoxyethane are also suitable. Ketones such as acetone, methyl ethyl ketone or diisobutyl ketone are also suitable, as are amides such as dimethylformamide or dirnethylacetamide. Mixtures of these solvents with one another are also suitable, as are mixtures of these solvents with water or alcohols such as methanol or ethanol.

Acetone and water and mixtures of acetone and water are preferred, the mixing ratio being arbitrary. The amount of solvent is also not critical, but it should be ensured that the amino acid complex and the activator can dissolve completely, otherwise a loss of activity can be expected. If necessary, the dissolving process can be accelerated by ultrasound treatment.

An optional emulsifier can be dissolved in a third portion of the solvent or together with the complex.

The amount of emulsifier is selected so that the mass ratio between monomer and emulsifier is greater than 1, preferably greater than 10 and particularly preferably greater than 20. The less emulsifier that has to be used, the more favorable it is. The activity in the polymerization is clearly increases when an emulsifier is added. This emulsifier can be non-ionic or ionic in nature.

Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO grade: 3 to 50, alkyl radical: C ₄ -C ₁₂ ) and ethoxylated fatty alcohols (EO grade: 3 to 80; alkyl radical: C ₈ -C) ₃₆ ). Examples of this are the Lutensol ^® brands from BASF AG or the Triton ^® brands from Union Carbide.

Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: Cs to C ₁₂ ), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: Cι-Cιs) and ethoxylated alkylphenols (EO degree: 3 to 50 , Alkyl radical: C ₄ -C ₁₂ ), of alkyl sulfonic acids (alkyl radical: Ci2 ~ Ci8) ^{and <} - ^of alkylarylsulfonic acids (alkyl radical: C ₉ -Cιs).

Suitable cationic emulsifiers are generally a primary, secondary, tertiary or quaternary ammonium salt, alkanolammonium salt, pyridinium salt, imidazolinium salt, oxazolinium salt, morpholinium salt and thiazolinium salt, and a cs-cis-alkyl, aralkyl or heterocyclic radical inoxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (2V, N, -trimethylammonium) ethyl paraffinic acid esters, iV-cetylpyridinium chloride, JV-laurylpyridinium sulfate and N-cetyl-iV, N, N-trimidomethylammonium , IV-dodecyl-IV, N, _V-trimethylammonium bromide, N, IV-distearyl-IV, IV-dimethylammonium chloride and the gemini surfactant N, N '- (lauryldimethyl) ethylenediamine dibromide. Numerous other examples can be found in H. Stächen, Tensid-Taschenb ch, Carl-Hanser-Verlag, Munich, Vienna, 1981 and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.

The components - amino acid complex in solution, optionally the solution of the emulsifier and optionally the solution of the activator - are then added to the polymerization reactor. Stirred vessels and autoclaves and tubular reactors have proven to be useful as the polymerization reactor, and the tubular reactors can be designed as loop reactors.

The monomer or monomers to be polymerized are mixed in the polymerization medium. Water or mixtures of water with the solvents listed above can be used as the polymerization medium. It should be noted that the proportion of water is at least 50% by volume, based on the total mixture, preferably at least 90% by volume and particularly preferably at least 95% by volume.

The solutions of the amino acid complex, optionally the activator and optionally the emulsifier are combined with the mixture of monomer and aqueous polymerization medium. The order in which the various components are added is in itself not critical. However, it is necessary for the components to be combined so quickly that there is no crystallization of poorly soluble complex compounds which may occur as intermediates.

The process according to the invention provides polyolefins and olefin copolymers in high yields, i.e. the activity of the amino acid complexes according to the invention under the conditions of the emulsion polymerization is very high.

In principle, continuous and discontinuous processes are suitable as the polymerization process. Preference is given to semi-continuous processes (semi-batch processes) in which, after all components have been mixed, monomer or monomer mixtures are subsequently metered in during the polymerization.

Aqueous polymer dispersions are initially obtained by the process according to the invention.

The average particle diameters of the polymer particles in the dispersions according to the invention are between 10 and 1000 nm, preferably between 50 and 500 nm and particularly preferably between 30 70 and 350 nm. The distribution of the particle diameters can, but need not, be very uniform. For some applications, especially those with high solids (> 55%), broad or bimodal distributions are even preferred.

35 The polymers obtained by the process according to the invention have technically interesting properties. In the case of polyethylene, they have a high degree of crystallinity, which can be demonstrated, for example, by the number of branches. Less than 100 branches are found, preferred

40 fewer than 50 branches per 1000 C atoms of the polymer, determined by ^ H NMR and ¹³ C NMR spectroscopy.

The melting enthalpies of the polyethylenes obtainable by the process of this invention are greater than 100 J / g, preferably greater than 45 140 and particularly preferably greater than ^■ 180 J / g as measured by DSC. The molecular weight distributions of the polyethylenes obtainable by the process according to the invention are narrow, ie the Q values are between 1.1 and 3.5 and preferably between 1.5 and 3.1.

Another advantage of the dispersions according to the invention, in addition to the low price owing to the cheap monomers and processes, is that they are more weather-resistant than dispersions of polybutadiene or butadiene copolymers. Compared to dispersions of polymers with acrylates or methacrylates as the main monomer, the lower tendency to saponify can be mentioned as advantageous. Another advantage is that most monomers are volatile and unpolymerized residual monomers can be easily removed. Finally, it is advantageous that no molecular weight regulators such as, for example, tert. -Dodecylmer- captan must be added, which are difficult to separate on the one hand and smell unpleasant on the other.

The polymer particles as such can be obtained from the aqueous dispersions initially obtained by removing the water and, if appropriate, the organic solvent or solvents. Numerous common methods are suitable for removing the water and, if appropriate, the organic solvent or solvents, for example filtering, spray drying or evaporation. The polymers thus obtained have a good morphology and a high bulk density.

The particle diameters can be determined using light scattering methods. An overview can be found in D. Distler "Aqueous polymer dispersions", Wiley-VCH Verlag, 1st edition, 1999, chapter 4.

The dispersions according to the invention can be used advantageously in numerous applications, such as paper applications such as paper coating or surface sizing, and also paints and lacquers, construction chemicals, adhesive raw materials, molded foams, textile and leather applications, carpet backing coatings, mattresses or pharmaceutical applications.

Working example:

General preliminary remarks

Abbreviations used: IR spectra: m: middle, s sharp; NMR spectra: s = singlet, m: multiplet,

o-Tol: ortho-toluyl, Ar: aryl, PE: polyethylene, tßu tert.-butyl, THF: tetrahydrofuran, ATE: aluminum triethyl All solvents were dried using standard methods, such as those listed in Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1984.

Unless otherwise stated, all reactions and cleaning operations were carried out with exclusion of air and moisture. Ether is always understood to mean diethyl ether and pentane n-pentane.

The polymer viscosity was determined according to ISO 1628-3. The molecular weights were determined by means of GPC. The following conditions were selected for the GPC tests based on DIN 55672: Solvent: 1, 2, 4-trichlorobenzene, flow: 1 ml / min, temperature: 140 ° C, calibration: PE standards, device: Waters 150C. The number of methyl groups was determined by means of IR spectroscopy.

1. Synthesis of trans- [Ni (o-Tol) Br (PPh ₃ ) ₂ ]

The compound trans- [Ni (o-Tol) Br (PPh)] was determined according to a slightly modified protocol from S.Y. Desjardins et al. , J. Organomet. Cnhem. 1996, 515, 233.

1.88 g (2.87 mmol) of Ni (PPh ₃ ) ₂ Cl (commercially available from ABCR GmbH & Co. KG, Karlsruhe) and 1.12 g (17.22 mmol) were placed in a 100 ml Schlenk flask. Zn powder, which had been dried beforehand by washing with a saturated aqueous MjCl solution and then drying at 110 ° C. 25 ml of THF and 0.69 ml (5.74 mmol) of 2-bromotoluene were then added. The suspension was stirred for about 35 minutes at 35 ° C in an ultrasonic bath with a KPG stirrer. The initially green-black suspension turned red-brown. The residue was then separated off by filtration through Celite® and about 40 ml of methanol were added to the filtrate. After several hours at -32 ° C the product had crystallized out. It was washed with cold methanol.

IR spectrum, ⁱ H-NMR spectrum and elemental analysis were consistent with the literature data. No further cleaning was necessary.

2. Synthesis of the complexes according to the invention 2.1. Synthesis of [Ni (NH ₂ CH ₂ C0 ₂ ) (o-Tol) (PPh ₃ )]

226.2 mg (0.3 mmol) of trans- [Ni (o-tol) Br (PPh ₃ ) ₂ ] were dissolved in 20 ml of THF at room temperature and placed in a Schlenk tube. 22.5 mg (0 3 mmol) of glycine in 10 ml of methanol were placed in a separate vessel and added by adding an equimolar amount of Na. triummethanolate solution deprotonated. The suspension thus obtained was added to the Schlenk tube with stirring. After adding about half of the suspension, the contents of the Schlenk tube turned light yellow. The mixture was left to stir at room temperature for a further 2 to 3 hours and the reaction mixture was observed to become cloudy as a result of precipitating NaBr. The precipitate was separated by centrifugation and the solution was concentrated under reduced pressure. The remaining orange-colored viscous residue was mixed with about 15 ml of diethyl ether and the resulting suspension was stirred for 40 minutes in order to separate off the triphenylphosphine which had been split off in the reaction. The product, which was very poorly soluble in ether, was centrifuged off and then washed with pentane.

15 IR (KBr): v (cm " ¹ ) 3332 m, 3282 m (NH), 1634 s (COO), 1609 s (NH).

iH-NMR (270 MHz, CD ₃ OD): δ 2.59 (s, 3H, CH ₃ -Ar), 3.19 (m, 2H, NH ₂ ), 3.36 (, 2H, CH ₂ NH) , 6.25-6.28 (, 4H, aromatic o-Tol. -H), 7.17-7.71 (m, 15H, PPh ₃ ). 20

³¹ P NMR (109.4 MHz, CD ₃ 0D): δ 28.36 (s, PPh ₃ ).

2.2. Synthesis of [Ni (NH ₂ CHC (CH ₃ ) ₃ CO ₂ ) (o-Tol) (PPh ₃ )]

25 350.0 mg (0.46 mmol) of trans- [Ni (o-tol) Br (PPh ₃ ) ₂ ] were dissolved in 20 ml of THF at room temperature and placed in a Schlenk tube. 60.3 mg (0.46 mmol) of L-tert-leucine in 20 ml of methanol were placed in a separate vessel and deprotonated by adding an equimolar amount of sodium methoxide solution. The so obtained

30 suspension was added to the Schlenk tube with stirring. After adding about 80% by volume of the suspension, the contents of the Schlenk tube turned light yellow. The turbidity that occurred due to the precipitation of NaBr disappeared when the remaining sodium methoxide was added. They were left at room temperature for a further 3 to 4 hours.

Stir 35 mertemperature. The solution was concentrated under reduced pressure. The remaining yellow-orange viscous residue was mixed with about 15 ml of diethyl ether and the resulting suspension was stirred for 40 minutes. The NaBr formed in the course of the reaction was separated by centrifugation and the in

40 ether readily soluble product was then isolated as follows: the ether was distilled off under reduced pressure and the light yellow residue was washed with hexane. The product was thus obtained in analytical form. The N, P isomers were not separated.

45 Although the washing solution contained certain amounts of product, the washing solution was not worked up.

IR (KBr): v (cm- ¹ ) 3435 m (NH), 1637 s (COO), - 1601 s (NH). 5 ⁱ H-M (270 MHz, CD ₃ OD): δ 1.27 (s, 9H, ^fc Bu), 2.47 (s, CH ₃ -Ar), 2.59 (s, CH ₃ -Ar) , 2.98 (s, IH, CH), 6.35-6.62 (m, 4H, aromatic o-Tol. -H), 7.22-7.73 (m, 15H, PPh ₃ ).

10 ³¹ P NMR (109.4 MHz, CD ₃ OD): δ 28.09 (s, PPh ₃ ), 28.86 (s, PPh ₃ ).

3. Examples of polymerization

60 mg (0.53 mmol) of triethyl-15 aluminum (as a 2 molar solution in n-heptane, from Witco) and 400 ml of isobutane were placed in a 1-1 autoclave. After pressing ethylene to a pressure of 40 bar and tempering to the temperature given in Table 1, the corresponding amount of amino acid complex was added via a lock. After 60 minutes, the 20 polymerizations were terminated by decompression.

Data on the polymerization conditions and the product properties can be found in Table 1.

25

30

35

40

45 Table 1: Polymerization results

[Ni (NH ₂ CH ₂ CO ₂ ) (o-tol) (PPh ₃ )]

η: Staudinger index CD

Claims

claims

1. amino acid complex of the general formula I,

where the variables are defined as follows:

M selected from Fe, Co, Ni, Pd, Pt or Ir, X selected from 0 or S;

R ¹ to R ^{3 are the} same or different and selected from

Hydrogen,

Ci-Cs-alkyl, substituted or unsubstituted,

C -Ci ₂ ~ cycloalkyl, substituted or unsubstituted, C ₇ -Cι ₃ aralkyl,

C ₆ -Ci ₄ aryl, unsubstituted or mono- or polysubstituted by the same or different substitution

Ci-Cs-alkyl, substituted or unsubstituted,

C ₃ -C ₂ cycloalkyl, C ₇ -C ₃ aralkyl,

C ₆ -C ₄ aryl,

Halogen,

-C ₆ alkoxy,

C ₆ -C ₄ aryloxy, SiR R ⁵ R ⁶ or 0-SiR R ⁵ R ⁶ , where R ⁴ -R ^{6 are} selected from

Ci-Cs-alkyl, C ₃ -C ₂ cycloalkyl, C -C ₃ aralkyl or

Ce -CC aryl; five- to six-membered nitrogen-containing heteroaryl radicals Y, unsubstituted or mono- or polysubstituted by the same or different substitution

Ci-Cs-alkyl, substituted or unsubstituted,

C ₃ -Ci2 cycloalkyl,

C ₇ -C ₃ aralkyl,

C ₆ -C ₄ - ryl, halogen,

Ci-C _δ alkoxy,

C ₆ -Ci ₄ aryloxy,

SiR ⁴ R ⁵ R ⁶ or 0-SiR R ⁵ R ⁶ , where R ⁴ -R ^{6 are} selected from C ₁ -C ₈ alkyl, C ₃ -Ci ₂ cycloalkyl, C -C ₃ aralkyl or C ₆ -C ₁₄ aryl,

CH ₂ -Y, wherein R ¹ and R ^{2 may be} linked together to form a 5- to 10-membered ring; y is an integer from 0 to 4;

L ^{1 is} an inorganic or organic neutral ligand; L ^{2 is} an inorganic or organic anionic ligand, where L ¹ and L ² can be linked to one another by one or more covalent bonds, for example an integer from 0 to 3.

2. Amino acid complex of formula I according to claim 1, in which the variables are selected as follows:

M is selected from Ni or Pd, X is 0, L ^{1 is} selected from

Phosphines (R ⁷ ) _X PH ₃ - _x , a inen (R ⁷ ) _X NH_ _X , ethers (R ⁷ ) ₂ 0, H ₂ 0, alcohols (R ⁷ ) OH,

pyridine,

Pyridine derivatives of the formula C ₅ H ₅ _ _X (R ⁷ ) _X N, CO,

C 1 -C ₂ alkyl nitriles, Cg-C ₄ aryl nitriles or ethylenically unsaturated double bond systems, where x is an integer from 0 to 3; L ^{2 is} selected from halide ions, amide anions (R ⁷ ) _h NH ₂ - _h where h is an integer from

0 to 2 is Ci-Cg-alkyl anions, allylan ion or methallylan ion, benzyl anion or C ₆ -Cχ ₄ aryl anions; R ^{7 are} identical or different and are selected from hydrogen, Ci-Cβ-alkyl, C ₃ -Cι ₂ cycloalkyl, C-Cχ ₃ aralkyl or Cg-Cι-aryl, substituted or unsubstituted; y 0; z 1.

3. Amino acid complexes of the formula I according to claim 1, in which the variables are defined as follows: M Ni,

L ¹ phosphines (R ⁷ ) _X PH ₃ _ _X with x = 0, 1, 2 or 3, L ² a benzyl or aryl anion; R ^{1 is} hydrogen, R ^{7 are the} same or different and are selected from hydrogen, Ci-Cg-alkyl, C ₃ -Ci ₂ -cycloalkyl, C ₇ -Cι ₃ aralkyl or Cg-Ci ₄ -aryl, substituted or unsubstituted.

4. A process for the preparation of amino acid complexes according to claims 1 to 3, characterized in that an amino acid of the general formula II

deprotonated and then reacted with a metal compound of the general formula M (L ¹ ) _{z +} ιL ² X ^{: L} , where X ^{1 is} selected from halide or alcoholate and the other variables are as defined above.

5. A process for the preparation of a supported catalyst for the polymerization or copolymerization of olefins, characterized in that one or more amino acid complexes according to claims 1 to 3 and optionally an activator are deposited on a solid support.

6. supported catalyst for the polymerization or copolymerization of olefins, containing one or more amino acid complexes of the general formula I, a solid support material and optionally an activator.

7. A process for the polymerization or copolymerization of olefins, characterized in that the polymerization or copolymerization is carried out in the presence of amino acid complexes as claimed in claims 1 to 3.

8. The method according to claim 7, characterized in that one carries out the polymerization or copolymerization in the presence of a supported catalyst according to claim 6.

9. The method according to claim 7, characterized in that one carries out the polymerization or copolymerization as an emulsion polymerization process or emulsion copolymerization process.