WO2001098379A1 - Lösemittelhaltige pasten, enthaltend polyolefinwachs - Google Patents
Lösemittelhaltige pasten, enthaltend polyolefinwachs Download PDFInfo
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- WO2001098379A1 WO2001098379A1 PCT/EP2001/006825 EP0106825W WO0198379A1 WO 2001098379 A1 WO2001098379 A1 WO 2001098379A1 EP 0106825 W EP0106825 W EP 0106825W WO 0198379 A1 WO0198379 A1 WO 0198379A1
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- butyl
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- propyl
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- 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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/092—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- 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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/06—Other polishing compositions
- C09G1/08—Other polishing compositions based on wax
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- 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
- C08J2391/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2391/06—Waxes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
Definitions
- the present invention relates to solvent-containing pastes containing, as a component, a polyolefin wax which is produced from one or more olefins by catalysis with a single-site catalyst based on a tri-pnicogen-cyclohexane complex of a transition metal from groups 5 to 8 of the periodic table.
- the present invention further relates to a process for the preparation of the solvent-containing pastes according to the invention, process for the care of surfaces such as floors or wall coverings, which consist of wood, ceramic, linoleum or modern plastics such as PVC, for the care of painted metal surfaces such as external parts of motor vehicles or Boot or to care for leather z. B. shoes, boots, saddles or leather bags / cases using the solvent-based pastes according to the invention.
- Pastes containing solvents are used on a large scale to care for various surfaces, for example floors, cars or leather goods such as shoes. They contain at least one wax, one or more solvents and optional additives. During care, the paste is applied to the one to be treated
- the solvent evaporates and leaves the wax as a fine film, which is also referred to below as a protective coating.
- This film protects the surface treated in this way, for example mechanically, but also against the effects of air.
- Important properties for the user of the solvent-based pastes are the paste hardness, a measure of the paste consistency, the surface quality, the gloss, the heat stability and the drying time.
- the drying time generally depends heavily on the type and amount of solvent. What is usually desired is the lowest possible solvent content with good processability, e.g. low viscosity of the paste.
- Pastes containing solvents usually contain several components. The most important component are the polyolefin waxes. However, other natural and synthetic waxes are usually added to the pastes. Examples of natural waxes are the carna ⁇ ba waxes imported from Brazil, as well as montan wax raffinates, paraffin waxes and micro waxes. A well-known additive is metal stearates. There is an overview for example in üllmann's Enyclopedia of Technical Chemistry, 5th edition, Vol. A 28, p. 108 ff., Weinheim, 1996).
- Hydrocarbons or hydrocarbon mixtures such as petrol or turpentine oil, are used as solvents.
- polyolefin waxes usually in amounts of 10 to 15 G w. -%, based on the total amount of paste.
- the most suitable waxes are polyolefin waxes. These can be achieved, for example, by radical polymerization of ethylene in a high-pressure process (cf. üllmann's Enyclopedia of Industrial Chemistry, 4th edition, keywords: waxes, vol. 24, p. 36 ff., Thieme Verlag Stuttgart, 1977) or by Ziegler-Natta- Polymerization of ethylene or propylene obtained (DE-A 15 20 914, EP-A 0 584 586). These methods can be used to obtain polyolefin waxes that have a broad molecular weight distribution and uneven comonomer incorporation. The low molecular weight components present in these products usually lead to a reduced hardness of the finished protective coatings.
- waxes • is preferred polyethylene grow, known obtained by metallocene catalysis.
- polyolefin waxes produced by metallocene catalysis have a narrow molecular weight distribution and therefore contain only very small proportions of low molecular weight polyolefin chains, which usually impair the mechanical properties of the waxes. Accordingly, polyolefin waxes obtainable by metallocene catalysis cause an improved hardness of the protective coatings produced therewith from the solvent-containing pastes described. However, a further improvement is desirable for use. It is observed that the solvent-containing pastes have a greatly increased viscosity even at relatively low concentrations of the wax to be applied.
- Nu 1 to Nu 3 are selected independently of one another from the pnico genes, preferably N or P, Nu 1 and Nu 2 are preferably each N and particularly preferably Nu 1 to Nu 3 are N.
- X 1 to X 3 are selected from
- Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being particularly preferred
- Ci-Cis-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-p
- cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,
- 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-C ⁇ -alkoxy preferably Ci-Cö-alkoxy such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, isopentoxy , n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy or NR 10 R 1: L, wherein R 10 and R 11 are independently selected from are hydrogen, C ⁇ -2 alkyl, C 2 -C ⁇ 2 alkenyl, and C 6 -C 4 aryl are selected form a saturated or unsaturated 5- can form up 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 N-piperidyl group and the N-pyrrolidinyl group;
- amino groups with unsaturated rings are the N-pyrryl group, the N-indolyl group and the N-carbazolyl group;
- X 1 to X 3 are preferably the same, very particularly preferably X 1 to X 3 are chlorine.
- R 1 to R 3 are independent of one another
- Ci-Cis-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- ⁇ onyl, n-decyl, and n dodecyl; preferably Ci-C ö alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl,
- C 1 -C 4 alkyl substituted one or more times with donor atoms, e.g. non-cyclic or cyclic ethers, alcohols, ketals, thioethers or amines; for example methoxymethyl, ethoxymethyl, ethoxyethyl, ⁇ -hydroxyethyl, ⁇ -ethoxypropyl, (2-ethylhexyloxy) propylidene, methoxyethoxypropylidene or ⁇ -dimethylaminopropyl;
- C 1 -C 12 -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 2 -C 12 alkenyl preferably C 2 - to ⁇ -C 8 alkenyl such as vinyl, allyl, but-3-en-1-yl, ⁇ -pentenyl, ⁇ -hexenyl, ⁇ -heptenyl, and ⁇ -octenyl;
- 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 - to C o ⁇ 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 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,
- Silyl SiR 12 R 13 R 14 where R 12 to R 14 are independently selected from hydrogen, C 1 -C 2 alkyl, C 7 -C 5 aralkyl and C 6 -C 4 aryl; trimethylsilyl-, triethylsilyl-, triisopropylsilyl-, diethylisopropylsilyl-, dimethyl-thexylsilyl-, tert.
- Siloxy OSiR 12 R 13 R 14 where R 12 to R 14 are independently selected from hydrogen, C 1 -C 2 alkyl, C 5 -C 5 aralkyl and C 6 -C 4 aryl; trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert.
- Ci-Ce alkoxy 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;
- Ci4-aryl which is in turn substituted with one or more C ⁇ -C ⁇ 2 alkyl, C ⁇ -C ⁇ 2 -alkenyl, C 3 -C ⁇ 2 -cycloalkyl, C 6 -C ⁇ 4 -aryl, silyl SiR 12 R 13 R 14 , siloxy 0 SiR 12 Ri 3 Ri 4 or -CC alkoxy, these groups being specified as above; R 4 to R 9 are independent of one another
- Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
- -C-C ⁇ a-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-
- - C 1 -C 2 alkyl substituted one or more times with donor atoms, for example non-cyclic or cyclic ethers, alcohols, ketals, thioethers or amines; for example methoxymethyl, ethoxymethyl, ethoxyethyl, ⁇ -hydroxyethyl, ⁇ -ethoxypropyl, (2-ethylhexyloxy) propylidene, methoxyethoxypropylidene or ⁇ -dimethylaminopropyl;
- 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 Trifluoromethyl and perfluorobutyl;
- C 1 -C 2 alkenyl preferably C to ⁇ -C 8 alkenyl such as vinyl, allyl, but-3-en-1-yl, ⁇ -pentenyl, ⁇ -hexenyl, ⁇ -heptenyl, and ⁇ -octenyl ;
- C 3 -C -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
- C to C 20 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-phenylbutyl, 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,
- Silyloxy SiR 12 R 13 R 14 where R 12 to R 14 are selected independently of one another from hydrogen, C 1 -C 1 -alkyl, C -C 8 -s aralkyl and C 6 ⁇ Ci 4 -aryl; trimethylsilyl-, triethylsilyl-, triisopropylsilyl-, diethylisopropylsilyl-, dimethylthexylsilyl-, tert.
- Silyloxy OSiR 12 R 13 R 14 where R 12 to R 14 are independently selected from hydrogen, C 1 -C 2 alkyl, C 1 -C aralkyl and Cs-Ci 4 -aryl; trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert. -Butyldimethylsilyloxy, tert-butyldiphenylsilyloxy, tribenzylsilyloxy, triphenylsilyloxy and the tri-para-xylylsilyloxy group; the trimethylsilyloxy group and the tert. -Butyldimethylsilyloxy distr;
- C 1 -C 6 -alkoxy preferably C 1 -C 6 -alkoxy 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 -aryl which is in turn substituted with one or more C ⁇ -C ⁇ 2 -alkyl, C ⁇ 2 -alkenyl, C 3 -C ⁇ 2 -cycloalkyl, C 6 -C ⁇ 4 -aryl, silyl SiR 12 R 13 R 14 , siloxy OSiR 1 Ri 3 Ri 4 or -CC 2 alkoxy, these groups being specified as above;
- R 1 to R 3 are preferably the same in each case.
- R 4 , R 6 and R 8 are each the same, and preferably R 4 , R 6 and R 8 are each hydrogen.
- R 4 to R 9 are very particularly preferably hydrogen.
- the triazacyclohexane ligands necessary for the synthesis of these very particularly preferred compounds can be synthesized particularly well.
- the preparation of the particularly preferred triazacycloalkane ligands for complexes of the general formula I is known per se.
- the compounds of the general formula I for the synthesis of the very particularly preferred compounds, in which R 4 to R 9 are each hydrogen and the radicals R 1 to R 3 are in each case identical, can be very particularly easily obtained by mixing formaldehyde, for example in the form of formalin Synthesize solution and the associated amine R 4 -NH 2 .
- Various synthetic routes for these complex ligands are described, for example, in F. Weitl, et al. J. Am. Chem. Soc. 1979, 101, 2728; M. Takahashi, S. Takamoto, Bull. Chem. Soc. Japan 1977, 50, 3413; T.
- the metal complexes in particular the chromium complexes, can be obtained in a simple manner if the corresponding metal salts such as e.g. Reacts metal chlorides or metal carbonyls with the ligand, e.g. B. P. Chaudhuri, K. Wieghardt, Prog. Inorg. Chem. 1987, 35, 329 or G.P. Stahley et al., Acta Crystall. 1995, C51, 18th
- Suitable cation-forming compounds are selected aluminum or boron compounds with electron-withdrawing radicals (for example trispentafluorophenylborane, trispentafluorophenylaluminium, N, N-dimethylanilinium-tetrakis-pentafluorophenylborate, tri-n-butylarrraonium-tetrakis-pentyluoro-nentafluorophenylborate, lanilinium tetrakis (3,5-bisperfluoromethyl) phenylborate, trin-butylammonium tetrakis ⁇ 3,5-bisperfluoromethyl) phenylborate and tritylium tetrakispentafluorophenylborate).
- electron-withdrawing radicals for example trispentafluorophenylborane, trispentafluorophenylaluminium,
- activators for complexes of the general formula I are described in DE-A 199 35 407, in PCT / EP 0002716 or in Angew. Chem., Int. Ed., 1994, volume 33, page 1877.
- Preferred are dimethylanilinium-tetrakis-pentafluorophenylborate, tritylium-tetrakispentafluorophenylborate and trispentafluorophenylborane.
- boron or aluminum compounds are used as activators for the complexes of the general formula I, they are generally used in a molar ratio of 1:10 to 10: 1, based on M; preferably 1: 2 to 5: 1 and particularly preferably 1: 1.5 to 1.5: 1.
- Another suitable class of cation-forming compounds are the aluminoxanes of the general formula II a to b.
- aluminoxanes 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.
- radicals R 15 are independent of 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 Ci-C ⁇ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-
- 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, or
- 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; and
- n is an integer from 0 to 40, preferably from 1 to 25 and particularly preferably from 2 to 22.
- 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 ) 0 9 (iso- CH 9 ) 0 , ⁇ AlO] n .
- Useful molar ratios M: Al are in the range from 1:10 to 1:10 000, preferably 1:50 to 1: 1000 and particularly preferably 1: 100 to 1: 500.
- the selected complex of general formulas I and the cation-forming compound together form a catalyst system.
- the activity of this catalyst system can be increased further by adding one or more further aluminum alkyl compounds of the general formula A1 (R 15 ) 3 .
- Aluminum alkyls of the general formula A1 (R 15 ) 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 residence time.
- Modern large-scale manufacturing processes for polyolefin waxes are solution processes, suspension processes, bulk polymerisation processes in liquid or supercritical monomer as well as gas phase processes, the latter being agitated gas phases or gas phase fluidized bed processes.
- Catalyst systems consisting of complexes of the general formulas I and activator can be deposited well on a solid support.
- Suitable carrier materials are, for example, porous metal oxides of metals from groups 2 to 14 or mixtures thereof, furthermore sheet silicates, but also solid halides of metals from groups 1, 2 and 13 and polymers such as polyethylene or polypropylene.
- Preferred examples of metal oxides of groups 2 to 14 are Si0 / B 2 0 3 , Al0 3 , MgO, CaO and ZnO.
- Preferred layered 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 Si0 2 -a A1 2 0 3 , where a generally stands for a number in the range from 0 to 2, preferably 0 to 0.5.
- silica gels are commercially available, for example silica gel 332, Sylopol® 948 or Sylopol 952 or S 2101 from WR Grace or ES 70X from Crosfield.
- 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 2 / g, preferably 250 to 400 m 2 / g.
- the carrier materials can be heated before 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; 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 complex of the general formula I and the activator.
- the volume of the suspending agent is 1 to 20 times the pore volume of the catalyst support.
- the catalyst can then be separated from the suspending agent by a suitable method, such as filtering, centrifuging or evaporating.
- the catalyst can be prepolymerized with small amounts of monomer before the actual polymerization.
- the prepolymerization can be terminated by metering in a reversible catalyst poison or by stopping the monomer metering and then metering the prepolymerized catalyst into the polymerization system.
- olefins are suitable as monomers: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-ündecene, ethylene being particularly preferred.
- Suitable comonomers are ⁇ -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 is also a suitable comonomer.
- An antistatic can be added to the reaction mixture in order to avoid electrostatic charging of the polymerization system or the product, which can sometimes be observed in polymerizations.
- Suitable antistatic agents are dilute solutions of aliphatic alcohols, for example isopropanol, in paraffins as in for example n-heptane.
- Other suitable antistatic agents are commercially available from Stadont® brands from DuPont.
- the procedure is advantageously such that the polyolefin wax is melted and then preheated solvent is added.
- thorough mixing of the hot paste is advantageous, which can be achieved by stirring, shaking or similar operations known to the person skilled in the art.
- Benzene or turpentine oil are advantageously used as solvents.
- the quantitative ratio chosen is over 20% by weight, preferably over 25% by weight and particularly preferably> 30% polyolefin wax. Less wax can also be used, but then the solvent-containing pastes contain high amounts of solvent, which is undesirable.
- additional components are optionally added; for example montan waxes, carna ⁇ ba waxes, metal stearates, antioxidants such as the Irganox® brands from Ciba, or paraffin waxes.
- the mixture is then allowed to stir for a period of at least 1 minute and at most one hour at a temperature just above the solidification point, and the final step is cooling.
- the target temperature is room temperature or colder, but not below -78 ° C.
- the paste hardness is determined after 24 hours.
- Clariant wax PE 520 commercially available from Clariant AG.
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Abstract
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/311,373 US6858071B2 (en) | 2000-06-20 | 2001-06-15 | Solvent-containing pastes containing in addition polyolefin wax |
EP01956479A EP1297028A1 (de) | 2000-06-20 | 2001-06-15 | Lösemittelhaltige pasten, enthaltend polyolefinwachs |
JP2002504334A JP2004501248A (ja) | 2000-06-20 | 2001-06-15 | ポリエチレンワックス成分を含む溶剤含有ペースト |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10029329 | 2000-06-20 | ||
DE10029329.8 | 2000-06-20 |
Publications (2)
Publication Number | Publication Date |
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WO2001098379A1 true WO2001098379A1 (de) | 2001-12-27 |
WO2001098379A8 WO2001098379A8 (de) | 2004-02-26 |
Family
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Family Applications (1)
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---|---|---|---|
PCT/EP2001/006825 WO2001098379A1 (de) | 2000-06-20 | 2001-06-15 | Lösemittelhaltige pasten, enthaltend polyolefinwachs |
Country Status (2)
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EP (1) | EP1297028A1 (de) |
WO (1) | WO2001098379A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6846356B2 (en) * | 2000-06-20 | 2005-01-25 | Basf Aktiengesellschft | Pigment concentrates and method for producing them |
US6860929B2 (en) * | 2000-06-20 | 2005-03-01 | Basf Aktiengesellschaft | Printing inks and lacquers containing polyolefin waxes |
Citations (6)
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EP0916700A2 (de) * | 1997-11-15 | 1999-05-19 | Clariant GmbH | Verwendung von Polyolefinwachsen in lösemittelhaltigen Pasten |
WO2000034211A1 (en) * | 1998-12-04 | 2000-06-15 | Bp Chemicals Limited | Oligomerisation process |
WO2000058369A1 (de) * | 1999-03-29 | 2000-10-05 | Basf Aktiengesellschaft | Verfahren zur polymerisation von olefinen |
WO2000058319A1 (de) * | 1999-03-29 | 2000-10-05 | Basf Aktiengesellschaft | Oligomerisierungskatalysator |
JP2001002723A (ja) * | 1999-06-24 | 2001-01-09 | Tosoh Corp | エチレンオリゴマー化触媒及びそれを用いたエチレンのオリゴマー化方法 |
WO2001062806A1 (de) * | 2000-02-26 | 2001-08-30 | Basf Aktiengesellschaft | Verfahren zur herstellung von polyethylenwachsen |
-
2001
- 2001-06-15 WO PCT/EP2001/006825 patent/WO2001098379A1/de not_active Application Discontinuation
- 2001-06-15 EP EP01956479A patent/EP1297028A1/de not_active Withdrawn
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EP0916700A2 (de) * | 1997-11-15 | 1999-05-19 | Clariant GmbH | Verwendung von Polyolefinwachsen in lösemittelhaltigen Pasten |
WO2000034211A1 (en) * | 1998-12-04 | 2000-06-15 | Bp Chemicals Limited | Oligomerisation process |
WO2000058369A1 (de) * | 1999-03-29 | 2000-10-05 | Basf Aktiengesellschaft | Verfahren zur polymerisation von olefinen |
WO2000058319A1 (de) * | 1999-03-29 | 2000-10-05 | Basf Aktiengesellschaft | Oligomerisierungskatalysator |
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DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; MIMURA, HIDEYUKI ET AL: "Ethylene oligomerization and its catalysts comprising chromium coordination compounds and alkylmetal compounds", XP002182464, retrieved from STN Database accession no. 134:72051 * |
KOEHN R D ET AL: "SELECTIVE TRIMERIZATION OF ALPHA-OLEFINS WITH TRIAZACYCLOHAXANE COMPLEXES OF CHROMIUM AS CATALYSTS", ANGEWANDTE CHEMIE. INTERNATIONAL EDITION, VERLAG CHEMIE. WEINHEIM, DE, vol. 39, no. 23, 4 December 2000 (2000-12-04), pages 4337 - 4339, XP000975912, ISSN: 0570-0833 * |
KOHN, RANDOLF D. ET AL: "Triazacyclohexane complexes of chromium as highly active homogeneous model systems for the Phillips catalyst", CHEM. COMMUN. (CAMBRIDGE) (2000), (19), 1927-1928, XP001039919 * |
TANI ET AL: "Preparation of.alpha.-olefin polymers by the use of vanadium or chromium complex catalysts", STN CAPLUS, XX, XX, vol. 129, no. 18, 2 November 1998 (1998-11-02), XP002139725 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6846356B2 (en) * | 2000-06-20 | 2005-01-25 | Basf Aktiengesellschft | Pigment concentrates and method for producing them |
US6860929B2 (en) * | 2000-06-20 | 2005-03-01 | Basf Aktiengesellschaft | Printing inks and lacquers containing polyolefin waxes |
Also Published As
Publication number | Publication date |
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WO2001098379A8 (de) | 2004-02-26 |
EP1297028A1 (de) | 2003-04-02 |
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