Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0041—Optical brightening agents, organic pigments
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
  • C08L91/06—Waxes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/006—Preparation of organic pigments
  • C09B67/0063—Preparation of organic pigments of organic pigments with only macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

• the invention relates to pigment concentrates containing at least one dye pigment, a polyethylene axle which is produced from ethylene and optionally one or more olefins with a metallocene catalyst, optionally a thermoplastic and optionally additives.
• pigments are marketed in the form of a pigment concentrate, as this makes processing easier when coloring plastics.
• These formulations generally contain, in addition to the pigment, a dispersant, for example a wax, and optionally a thermoplastic, mostly a polyolefin.
• the thermoplastic is also called a carrier polymer.
• the wax serves to finely distribute the pigment in the formulation and to stabilize it in this distribution.
• a commercially available formulation of such a pigment concentrate (“masterbatch") contains 25% by weight of pigment, 10% by weight of wax and 65% by weight of a polyethylene plastic.
• a polyethylene wax is often used as the wax, which can be obtained, for example, by radical polymerization or Ziegler-Natta catalysis.
• the polyethylene wax can be modified polar, for example by oxidation.
• the ratios of the individual components can be varied within certain limits.
• the pigment agglomerates must be wetted well by the wax so that the agglomerates do not clump together.
• a small number of larger pigment agglomerates contributes less to the color effect of the pigment in question than a larger number of smaller pigment agglomerates.
• the viscosity of the melt should be as low as possible so that during the formulation, which is usually carried out by mixing at a temperature above the melting temperature of the wax, the melted wax can penetrate well through the cavities within the agglomerates of the pigment. The shear forces thus exerted make it easier for the agglomerates to split into the primary particles.
• the wetting ability of the waxes should also be good.
• polar groups can be introduced into a wax by several process steps.
• One method is to partially break down the wax using atmospheric oxygen or peroxide compounds.
• hydrogen peroxide (H 2 0) or dialkyl peroxides can be used as peroxide compounds.
• Partial degradation methods introduce hydroxyl groups and carboxyl groups into the macromolecules as polar groups. These polar groups are unevenly distributed across the molecule, which means that the molecular chains of the waxes are not optimally wettable.
• Another method is to use polar comonomers such as acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or vinyl acetate, which can optionally be saponified.
• polar comonomers can act as catalyst poisons for Ziegler-Natta catalysts and therefore the catalysts lose activity.
• Another disadvantage is that the comonomers are not incorporated evenly into the waxes. Usually, comonomers prefer to incorporate into the short-chain molecules, which leads to undesirably non-uniform properties of the wax.
• thermoplastics and moldings with the concentrates according to the invention. It was found that metallocene-polyethylene waxes can be used much better as dispersants in pigment concentrates than conventional polyethylene waxes.
• the pigment concentrates contain the following components:
• At least one dye pigment the dye pigments being selected from inorganic or organic dye pigments.
• Iron oxide black Iron oxide black, iron-manganese black, spinel black, soot; orange spinels and corundum, cadmium orange, chrome orange, lead molybdate; - aluminum or Cu / Zn alloy;
• organic pigments examples are:
• Metal phthalocyanines such as phthalocyanine blue or phthalocyanine green, furthermore perylene red, diaryl yellow, isoindoline yellow,
• Quinophthalone pigments quinacridone pigments, benzimidazolone pigments, malachite green, thioindigo, monoazo pigments, disazo pigments, lacquered azo pigments, naphthol AS pigments, benzimidazolone pigments, diketopyrrolopyrroles, indanthronations, azokondes Anthraquinone pigments, pyrazolones, perinones, aminoketone pigments, indigo or triphenylmethane pigments.
• Polyethylene wax which is a wax-like molding compound made of polyethylene or copolymers of ethylene, each with 0 to 20 mol% of one or more comonomers such as propene, 1-butene, 1-pentene, 1-hexene, 1-octene , 1-decene or 1-ündecen. Polyethylene wax with 0 to 10 mol% of propene, 1-butene, 1-pentene or 1-hexene is preferred.
• the average molar masses M w of these polyolefin waxes are from 500 to 20,000 g, preferably from 2,000 to 10,000 g and particularly preferably 3,000 to 8,000 g.
• the Q values are in the range from 1.5 to 5, preferably from 1.8 to 3.5 and particularly preferably from 2 to 3.
• the melting points of these waxes are from 80 to 165 ° C., preferably from 100 to 140 ° C. and particularly preferably from 105 to 120 ° C.
• thermoplastic as a carrier polymer, this plastic being, for example, polyethylene, polypropylene, polystyrene, polyoxymethylene, polystyrene copolymers such as styrene-butadiene copolymers, acrylonitrile-butadiene-styrene terpolymers or polyvinyl chloride and copolymers of ethylene with 0, 1 to 20 mol% of 1-butene,
• antioxidants such as antioxidants; preferred are antioxidants such as sterically hindered phenols or sterically hindered amines "HALS"; hindered phenols of the Irganox ® brands from Ciba are most preferred.
• the proportions of the various components can be varied within wide limits. The proportions are adjusted to one another so that they add up to a total of 100% by weight.
• the pigment or pigments are in minimum quantities of
• the upper limit is 60% by weight, in particular 45% by weight, because the pigments are the most expensive component of the pigment concentrates.
• the wax is used in pigment concentrates containing carrier polymer in an amount of at least 1% by weight, at least 2% by weight is preferred, because below this proportion by weight, adequate wetting of pigment and carrier polymer is not ensured.
• the maximum used is preferably 30% by weight of wax and particularly preferably 20% by weight, because the wax properties in the end product can cause the mechanical properties of the molded plastic body or sheet material to be colored to deteriorate.
• 90% by weight is expedient in pigment concentrates which are to be produced without using the carrier polymer.
• the minimum for the wax content of a pigment concentrate free of carrier polymer is 40% by weight, because otherwise the concentrate will be too expensive.
• Carrier polymers are optionally added. In the case in which carrier polymer is used, it is used in a proportion of at least 30% by weight, because this facilitates the subsequent mixing in of the pigment concentrate in the production of the plastic moldings and plastic sheets. A reasonable upper limit is 80% by weight.
• Aggregates are only added optionally and then in small quantities.
• a reasonable lower limit for antioxidants such as Irganox® is 0.1% by weight, because below this amount no significant protection against oxidation is possible; 0.5% by weight is preferred and 1% by weight is particularly preferred.
• the upper limit is 5% by weight, because otherwise the processing properties of the pigment are visibly impaired by the low molecular weight component; 2% by weight are preferred and 1.5% by weight is particularly preferred.
• Another class of additives are lead salts such as, for example, basic lead sulfate or lead stearate or mixtures thereof, which are added in amounts of 0.5 to 2% by weight, preferably 1.0 to 1.5% by weight.
• Metallocene polyethylene waxes are known per se. They are described for example in EP-A 0 321 851 and in EP-B 0 602 509. A process for the production of these metallocene polyolefin waxes is disclosed in EP-B 0 602 509. For this purpose, a sandwich compound according to formula I a - e is used as the metallocene. In formula I a
• M is an element from the series Ti, Zr, Hf, V, Nb or Ta in the oxidation state +4; preferably Ti, Zr or Hf and particularly preferably Zr or Hf;
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• C ⁇ ⁇ C ⁇ 2 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, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably Ci-C ß- alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n
• cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,
• Ci-Cg 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 or
• NR 17 R 18 wherein R 17 and R 18 independently of one another from hydrogen, C] _- -CC alkyl groups, C -Cj .
• Alkenyl groups and C 6 -C 4 aryl groups are selected which can form a saturated or unsaturated 5- to 10-membered ring; the dimethylamino, the diethylamino, the diisopropylamino, the methylphenylamino group and the diphenylamino group are preferred.
• amino groups with saturated rings are the -piperidyl group and the -pyrrolidinyl group;
• amino groups with unsaturated rings are the W-pyrryl group, the N-indolyl group and the i ⁇ 7-carbazolyl group;
• E is selected from C, Si, Ge or Sn; C and Si are preferred;
• n is selected from the numbers 1, 2 or 3; n is preferably 1 or 2 and particularly preferably 1;
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• -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 Ci-Cg-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl,
• C 2 -C 1 -alkenyl preferably C 2 - to ⁇ -Cg-alkenyl such as vinyl, allyl, but-3-en-1-yl, ⁇ -pentenyl, ⁇ -hexenyl, ⁇ -heptenyl and ⁇ -octenyl;
• C -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• C 7 - to C 2 o- aryl preferably C 7 - to C 2 -phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1st Phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferably benzyl,
• C 6 -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, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl,
• Ci-C ö alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert.
• R 1 to R 8 are independent of one another
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• -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 ⁇ - alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n
• mono- or poly-halogenated C 1 -C 2 alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, fluoromethyl, difluoromethyl, tri fluoromethyl and perfluorobutyl;
• C 2 -C 2 alkenyl preferably C 2 - to ⁇ -C 8 alkenyl such as vinyl, allyl, but-3-en-l-yl, ⁇ -pentenyl, ⁇ -hexenyl, ⁇ -heptenyl, and ⁇ -octenyl ;
• 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 7 to C 20 aralkyl preferably C 7 to C ⁇ 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,
• C 6 -C X4 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,
• Siloxy groups OSiR 19 R 20 R 21 where R 19 to R 21 are independently hydrogen, C ⁇ -C ⁇ 2 alkyl groups, C 3 -C 2 cycloalkyl groups, Cg-C- aryl groups, substituted C 6 -Ci 4 - Aryl groups, C ⁇ -C ⁇ alkoxy groups, benzyl groups and C 6 -Ci 4 aryl groups are selected; trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dirnethylthexylsilyloxy, ter are preferred. -Butyldime- thylsilyloxy-, tert.
• Ci-Cg 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;
• a special embodiment are metallocenes according to formula Ib.
• M is an element from the series Ti, Zr, Hf, V, Nb or Ta in the oxidation state +4; preferably Ti, Zr or Hf and particularly preferably Zr or Hf; X and Y are independent of each other
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• C ⁇ -C ⁇ 2 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, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n- dodecyl; preferably -C 6 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-penty
• C 3 -Ci 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 - 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,
• C 6 -C 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 penyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• Ci-Ci 2 alkoxy groups preferably Ci-C ⁇ 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 or
• R 17 and R 18 are independently selected from hydrogen, -CC 12 alkyl groups, C 2 -C 2 alkenyl groups, benzyl groups and C ö -C- aryl groups, which are saturated or unsaturated Can form 5- to 10-membered ring; the dimethylamino, the diethylamino, the diisopropylamino, the methylphenylamino group and the
• amino groups with saturated rings are the W-piperidyl group and the i ⁇ J-pyrrolidinyl group ;
• amino groups with unsaturated rings are the W-pyrryl group, the W-indolyl group and the N-carbazolyl group;
• E is selected from C, Si, Ge or Sn; C and Si are preferred;
• n is selected from the numbers 1, 2 or 3; n is preferably 1 or 2 and particularly preferably 1;
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• -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 6 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso
• C 3 -Ci 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred,
• C 7 - 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, C 6 -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, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl,
• C 6 -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
• R 1 , R 2 , R 5 , R 6 and R 9 to R 16 are independent of one another
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• -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 6 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, is
• mono- or poly-halogenated -CC alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, tri fluoromethyl and perfluorobutyl;
• C 2 -C ⁇ alkenyl preferably C 2 - to ⁇ -C 8 alkenyl such as vinyl, allyl, but-3-en-l-yl, ⁇ -pentenyl, ⁇ -hexenyl, ⁇ -heptenyl, and ⁇ -octenyl;
• 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 7 - 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,
• C 6 -C 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,
• Siloxy groups OSiR 19 R 20 R 21 where R 19 to R 21 independently of one another are hydrogen, C ⁇ -C 12 alkyl groups, C 3 -C ⁇ cycloalkyl groups, C 6 -C ⁇ 4 aryl groups, substituted C 6 -Ci 4 - Aryl groups, -CC 2 alkoxy groups, benzyl groups and C 6 -C 4 aryl groups are selected; trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert.
• Ci-C ⁇ 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;
• M is an element from the series Ti, Zr, Hf, V, Nb or Ta in the oxidation state +4; preferably Ti, Zr or Hf and particularly preferably Zr or Hf;
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• C ⁇ -C ⁇ 2 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, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n- dodecyl; preferably -C 6 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-penty
• C 7 - 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,
• C 6 -C 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;
• Ci-Ci 2 alkoxy groups preferably Ci-C ⁇ 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 or
• R 17 and R 18 are independently selected from hydrogen, -CC 2 alkyl groups, C 2 -Ci 2 alkenyl groups and C 6 -Ci 4 aryl groups, which are a saturated or unsaturated 5- to 10th - can form a ring; the dimethylamino, the diethylamino, the diisopropylamino, the methylphenylamino group and the diphenylamino group are preferred.
• Examples of amino groups with saturated rings are the N-piperidyl group and the 2 ⁇ 7-pyrrolidinyl group;
• amino groups with unsaturated rings are the -pyrryl group, the -indolyl group and the N-carbazolyl group;
• R 1 to R 8 and R 22 and R 23 are independent of one another
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• -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] _- C 6 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-p
• halogenated C 1 -C 2 alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, tri - fluoromethyl and perfluorobutyl;
• C 2 -C ⁇ alkenyl preferably C - to ⁇ -C a alkenyl such as vinyl, allyl, but-3-en-l-yl, ⁇ -pentenyl, ⁇ -hexenyl, ⁇ -heptenyl, and ⁇ -octenyl;
• C 3 -C 12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• C 7 - to C 2 o ⁇ aralkyl preferably C - 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,
• C 6 -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, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl,
• Siloxy OSiR 19 R 20 R 21 wherein R 19 to R 21 independently of one another from are hydrogen, Ci -lkyl phenomenon 2 -A, C 2 -C 2 -alkenyl, C 3 -C ⁇ 2 -cycloalkyl, C 6 -C ⁇ 4 aryl, substituted C 6 -C 4 aryl, C 1 -C 2 alkoxy groups, benzyl groups and C 6 -C 4 aryl groups selected; trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dirnethylthexylsilyloxy, tert.
• C 6 -C 4 aryl groups which are themselves substituted by one or more C ⁇ -C ⁇ 2 alkyl groups, C -C ⁇ 2 alkenyl groups, C 2 -C cycloalkyl, C 6 -C 4 aryl groups, siloxy OSiR 11 R 12 R 13 or C] _- Ci 2 alkoxy groups, these groups being as specified above;
• a special embodiment are metallocenes according to formula I d.
• Formula I d is metallocenes according to formula I d.
• M is an element from the series Ti, Zr, Hf, V, Nb or Ta in the oxidation state +4; preferably Ti, Zr or Hf and particularly preferably Zr or Hf,
• X and Y are independent of each other Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred;
• -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 Ci-C ⁇ - alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl,
• 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 7 - 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,
• C 6 -Ci 4 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9- Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• C 1 -C 2 alkoxy groups preferably C 1 -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 or
• R 17 and R 18 are independently selected from hydrogen, -CC 2 alkyl groups, benzyl groups and C ⁇ -C- aryl groups, which can form a saturated or unsaturated 5-10 membered ring; the dimethylamino, the diethylamino, the diisopropylamino, the methylphenylamino group and the diphenylamino group are preferred.
• amino groups with saturated rings are the i ⁇ 7-piperidyl group and the W-pyrrolidinyl group;
• amino groups with unsaturated rings are N-pyrryl group, the N-indolyl group and the carbazolyl group;
• R 1 to R 3 , R 5 to R 7 and R 9 to R 16 are independent of one another
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• -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 6 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso
• halogenated C 1 -C 2 alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloroethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
• C -C alkenyl preferably C 2 - to ⁇ -C 8 alkenyl such as vinyl
• 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 7 - to C 20 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, C 6 ⁇ Ci 4 - ryl 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,
• Siloxy groups OSiR 19 R 20 R 21 where R 19 to R 21 independently of one another are hydrogen, -CC 2 alkyl groups, C 2 -C 2 -alkenyl, C 3 -C 2 -cycloalkyl, C 6 -C 4 -aryl, substituted C 6 -C 4 aryl, C ⁇ -C ⁇ 2 alkoxy groups, benzyl groups and C 6 -C ⁇ 4 aryl groups; trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert.
• C 1 -C 2 alkoxy groups preferably C 6 -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;
• M is an element from the series Ti, Zr, Hf, V, Nb or Ta in the oxidation state +4; preferably Ti, Zr or Hf and particularly preferably Zr or Hf;
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• C ⁇ -C 12 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, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n- Dodecyl, preferably C ⁇ -C 6 -Al yl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl,
• C 3 -C 12 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred,
• C - to C 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, C 6 -C 14 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthr / l, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenane : hryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
• C ⁇ -C ⁇ 2 alkoxy groups preferably C ⁇ -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 or
• R 17 and R 18 are independently selected from hydrogen, C ⁇ -C 6 alkyl groups and Cs-C ⁇ 4 aryl groups, which can form a saturated or unsaturated 5-10 membered ring; those are preferred
• Dimethylamino, the diethylamino, the diisopropylamino, the methylphenylamino group and the diphenylamino group Dimethylamino, the diethylamino, the diisopropylamino, the methylphenylamino group and the diphenylamino group.
• amino groups with saturated rings are the i ⁇ 7-peridyl group and the W-pyrrolidinyl group
• amino groups with unsaturated rings are the N-pyrryl group, the W-indolyl group and the N-carbazolyl group,
• E is selected from C, Si, Ge or Sn; C and Si are preferred;
• n is selected from the numbers 1, 2 or 3; n is preferably 1 or 2 and particularly preferably 1;
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• C ⁇ -C 12 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, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n- dodecyl; preferably C ⁇ -C 6 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-penty
• C -C ⁇ 2 alkenyl preferably C 2 - to ⁇ -Ca alkenyl such as vinyl, allyl, but-3-en-1-yl, ⁇ -pentenyl, ⁇ -hexenyl, ⁇ -heptenyl, and ⁇ -octenyl;
• cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred,
• 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,
• C 6 -C 14 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,
• C ⁇ -C ⁇ 2 alkoxy groups preferably C ⁇ -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, lumnHd wherein R and R 'together can form a saturated or unsaturated 4- to 9-membered ring;
• Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
• C ⁇ -C 12 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, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably C ⁇ -C 6 ⁇ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-
• mono- or poly-halogenated C ⁇ -C 1 alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, fluoromethyl, difluoromethyl, tri are particularly preferred - fluoromethyl and perfluorobutyl;
• C-C ⁇ 2 alkenyl preferably C to ⁇ -C 8 alkenyl such as vinyl, allyl, but-3-en-l-yl, ⁇ -pentenyl, ⁇ -hexenyl, ⁇ -heptenyl, and ⁇ -octenyl;
• 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,
• C 6 -C 14 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,
• Siloxy groups OSiR 19 R 20 R 21 where R 19 to R 21 independently of one another are substituted by hydrogen, C ⁇ -C 12 alkyl groups, C -C 1 alkenyl, C 3 -C 1 cycloalkyl, C 6 -C 14 aryl C 6 -C 14 aryl, C ⁇ -C 1 alkoxy groups, benzyl groups and C 6 -C 14 aryl groups selected; trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dirnethylthexylsilyloxy, tert.
• C ⁇ -C ⁇ 2 alkoxy groups preferably C ⁇ -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;
• two adjacent radicals can together form a saturated or unsaturated 4- to 9-membered ring, preferably 5- to 8-membered.
• two residues can be together:
• A is to be understood as oxygen, sulfur, NR 24 or PR 24 , where R 24 is selected from halogen, C ⁇ -C ⁇ 2 alkyl, C 3 -C ⁇ cycloalkyl, substituted or unsubstituted
• metal ocenes of the formulas I a-e are:
• metallocenes In order for metallocenes to be catalytically active, they must be activated with a compound that forms metallocenium ions.
• Suitable metallocenium ion-forming compounds are selected boron compounds with electron-withdrawing radicals (for example trispentafluorophenylborane, W, N-dimethylanilinium-tetrakis-pentafluorophenylborate, tri-n-butylammonium-tetrakis-pentafluorophenylborate, N, i7-tetrakluorophenyl (N, i7-dimethylisiline 3,5-bis-perfluoromethyl) -phenylborate, tri-n-butylammonium-tetra- (3,5-bis-perfluoromethyl) -phenylborate and tritylium-tetra-pentafluorophenylborate).
• aluminoxanes of the formulas II (eg DE-A 30 07 725).
• 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 purely available, but as mixtures of open-chain and cyclic structures of type II a and b. These mixtures are probably in dynamic equilibrium with one another.
• C ⁇ -C ⁇ 2 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, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n- Dodecyl; preferably C ⁇ -C6-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-p
• 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 7 - to C 2 o _A ralkyl preferably C 7 - to C ⁇ 2 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-propyl phenyl, 3-phenyl-propyl, 1- Phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl, or C 6 -C 14 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
• Metallocene and metallocenium ion-forming compound together form a catalyst system.
• the activity of this catalyst system can be increased further by adding a further aluminum alkyl compound of the general formula A1 (R 25 ) 3 .
• the addition of further aluminum alkyl not only increases the activity of the catalyst system; the aluminum alkyl also acts as a molecular weight regulator.
• Another effective molecular weight regulator is hydrogen.
• the molecular weight can be controlled in a targeted manner by means of the reaction temperature and the residence time.
• Modern large-scale manufacturing processes for polyolefin waxes are solution processes, suspension processes, bulk polymerization processes in liquid or supercritical monomer and gas phase processes, the latter being stirred gas phases or gas phase fluidized bed processes.
• metallocenes can be used in suspension processes, bulk polymerization processes or gas phase processes, it is advantageous 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.
• the catalyst system consisting of metallocene and activator 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, but also solid halides of metals from groups 1, 2 and 13.
• Preferred examples of metal oxides from groups 2-14 are Si0, B 2 0 3 , A1 2 0 3 , MgO, CaO and ZnO.
• Preferred Schich silicates are montmorrilonite or bentonite; preferred halides are MgCl 2 or amorphous A1F 3 .
• Particularly preferred carrier materials are spherical silica gels and aluminosilicate gels of the general formula SiO 2 -a Al 2 O 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 332 or S 2101 from WR Grace.
• Average particle diameters of 1-300 ⁇ m have proven successful as the particle size of the carrier material, preferably of
• the pore volume of these carriers is 1.0 to 3.0 ml / g, preferably 1.6 to 2.2 ml / g and particularly preferably 1.7 to 1.9 ml / g.
• the BET surface area is 200 to 750 m / g, preferably 250 to 400 m 2 / g.
• the carrier materials can be heated before the doping, temperatures of 45 to 1000 ° C. being suitable. Temperatures of 100 to 750 ° C are particularly suitable for silica gels and other metal oxides; for MgCl 2 supports, temperature ranges from 50 to 100 ° C. are preferred. This baking should take place over a period of 0.5 to 24 hours, with baking times of 1 to 12 hours being preferred.
• the printing conditions are not critical per se; the heating can take place at atmospheric pressure. However, reduced pressures from 0.1 to 500 mbar are advantageous, a range from 1 to 100 mbar is particularly advantageous and a range from 2 to 20 mbar is very particularly advantageous. Chemical pretreatment of the carrier material is also possible.
• the doping of the catalyst is generally carried out by slurrying the support material in a suspension medium and combining this suspension with the solution of the Komple system.
• the volume of the suspension medium is 1 to 20 times the pore volume of the catalyst carrier.
• the catalyst can then be separated from the suspending agent by a suitable method, such as filtering, centrifuging or evaporating.
• the polyolefin waxes obtained with the aid of one of the above-mentioned metallocene catalysts using one of the polymerization processes mentioned can be further processed into masterbatches by various methods, which have in common that wax and carrier polymer are melted in the decisive step, but the pigment is not, and that or the pigments and optional additives are incorporated.
• the components can optionally be premixed, for which drum or tumble mixers are particularly suitable. Micronizations can also be carried out optionally.
• Simple kneaders can be used for batch processes; Continuous processes can be carried out, for example, in high-speed mixers, single-screw extruders, twin-screw extruders, Buss kneaders, planetary roller extruders, open double-bowl kneaders or high-speed stirrers.
• the pigment concentrates are then granulated in the usual way.
• Strand granulators can be used for this purpose, in which the mixture is cooled as a strand under water and then cut into pellets or granules either in or after leaving the water bath.
• Perforated plates are also suitable as cutting means ("hot cutting process").
• pigment concentrate 0.01 to 10% by weight of pigment concentrate, preferably 0.5 to 5% by weight of pigment concentrate and particularly preferably 0.5 to 2.5% by weight of pigment concentrate, with
• polymer preferably 95 to 99.5 and particularly preferably 97.5 to 98.5% by weight polymer and optionally
• antioxidants or biocides being preferred additives.
• Suitable polymers are: polyethylene, polypropylene, polystyrene, polyoxymethylene, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyether sulfones, polysulfones, polyether ketones, polystyrene copolymers, acrylonitrile tril-butadiene-styrene terpolymers, polyamides such as nylon 6 or nylon 6,6, polyvinyl chloride and copolymers of ethylene with 0.1-20 mol% 1-butene, 1-pentene, 1-hexene, 4-methyl l-pentene, 1-octene, 1-decene or 1-undecene.
• the polymer to be colored and the carrier polymer of the masterbatch can be the same, but need not be.
• Simple kneaders can in turn be used for discontinuous processes; Continuous processes can be carried out, for example, in high-speed mixers, single-screw extruders, twin-screw extruders, Buss kneaders, planetary roller extruders, open double-bowl kneaders or high-speed mixers. Continuous processes are preferred.
• the moldings and fabrics can be produced by injection molding, film extrusion or casting at temperatures above the melting point of the polymer.
• the processing properties of the moldings and fabrics according to the invention are not adversely affected by the use of the pigment concentrates according to the invention.
• the shaped bodies and flat structures obtained by the process according to the invention differ from the commercially available shaped bodies and flat structures by a significantly higher brilliance in color.
• the mechanical properties of the materials are not adversely affected by the use of the pigment concentrates according to the invention.
• the metallocene polyethylene wax was produced in an apparatus as described in EP-B 0 602 509, example 1 or drawing on page 19.
• the polymerization was carried out at 60 ° C. without hydrogen, using isobutane instead of propane as the suspending agent.
• the wax thus obtained had the following properties: fixed point 128 ° C., M w : 4900 g, M n : 2200 g.
• polyethylene 60 wt .-% polyethylene (Lupolen ® 1800 S) as granules (commercially available from Mariac GmbH)
• polyethylene 60 wt .-% polyethylene (Lupolen ® 1800 S) as granules (commercially available from Mariac GmbH)
• the components were premixed in a high speed stirrer and heated to the melting point of the wax.
• the wax wetted the pigment, made it dust-free and contributed to the dispersion of the pigment in the wax phase.
• This mixture was then fed into a twin-screw extruder. The temperature was increased by a further 10 ° C. During this step, the PE granulate was covered with a thin layer of wax. After the extrusion, the pigment concentrate was cooled so carefully that the solidified pigment / wax layer was not separated from one another.
• the comparison products were produced analogously. Commercially available samples were used as waxes.
• 1 g of pigment concentrate from each of the examples given was provided with 91.5 g of Lupolen 50D and 7.5 g of TiO 2 as an optical brightener. mixes, mixed on a blow molding machine at 130 to 150 ° C and blow molded into canisters.

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