Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/06—Polystyrene
• • 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
  • C08L23/08—Copolymers of ethene

Definitions

• the invention relates to the use of polyolefin waxes and their polar-modified derivatives with particular suitability as lubricants and Tre ⁇ nffen for the processing of plastics.
• plastics are processed in the
• Lubricants perform a variety of tasks during processing. You are responsible for ensuring that a plastic in the processing machine opens up in a targeted and sufficient manner and is present as a homogeneous melt. Lubricants also prevent the plastic melt from sticking too strongly to hot machine parts.
• An overview of the lubricants used in plastics and their functionality can be found in R. Gumbleter, H. Müller (Ed.): “Kunststoffadditive", 3rd edition, Hanser Verlag, Kunststoff 1989, pp. 443 ff.
• the state of the art is the use of polyolefin waxes and their polar modified derivatives in a wide range of processing thermoplastics.
• the waxes are produced by the Ziegler process, in a high-pressure polymerization or by degradation reactions and, if necessary, polar modified (cf. Ullmann's Encyclopedia of Industrial Chemistry, Weinheim, Basel, Cambridge, New York, Tokyo, 5th Ed., Vol. A 28, S 146 ff).
• polyolefin waxes is generally understood to mean the homo- and copolymers of ethene, propene and other ⁇ -olefins.
• Polar modified polyolefin waxes are oxidized or grafted with polar reagents.
• polystyrene polymers polypropylene, polyethylene and their copolymers
• thermoplastics polyyesters, polyamides, polycarbonates, styrene polymers, polyoxymethylenes and thermoplastic elastomers
• polar vinyl polymers polyvinyl chloride and copolymers of vinyl chloride, chlorinated polyethylene
• polyolefin waxes and their polar modified derivatives in the area of rigid PVC are usually used in this field of application for regulating the melting behavior and the tendency to stick to the processing units. They are usually used in combination with other waxes, such as montan waxes, fatty acid derivatives or paraffins.
• the use of such products is in the literature (eg K. Worschech: Lubricant for PVC in: G. Becker, D. Braun (ed.): Kunststoff-Handbuch Polyvinylchlorid Bd. 2/1, 2nd edition, Hanser Verlag, Kunststoff Pp. 571 ff.) And in the patent literature, such as US Pat. No. 5,414,035 and WO-96 11 228.
• calender foils in particular for blister packs and credit cards and for injection molding, in particular for pipe fittings.
• the calender foils are characterized by high transparency, Stability and plate-out resistance.
• the injection molded parts show improved finished part properties.
• polyolefin waxes are used in various forms as lubricants. They can be added to a plastic as a pure product in various ways. Polyolefin waxes are also used as a mixture (powder blend or melt blend) in combination with other lubricants such as montan waxes and their salts, fatty acid derivatives and their salts, paraffins, other polyolefin waxes and their polar modified derivatives, amide waxes, silicones and fluoroplastics. Furthermore, polyolefin waxes are part of additive mixtures (one packs) which, in addition to lubricants, e.g. Thermal stabilizers, costabilizers, UV absorbers, antioxidants, light stabilizers, antistatic agents, fillers, pigments and processing aids can contain.
• additive mixtures one packs
• Polyolefin waxes are added to the ongoing polymerization process during the manufacture of a plastic. Furthermore, they are added to a polymer before a processing step. Various processes are possible: polyolefin waxes can be powdered onto a polymer, compounded in or introduced into a plastic in a cold or warm powder mixing process.
• polyolefin waxes used in technology have some disadvantages in their use as lubricants and release agents in plastics.
• Conventional waxes have to be added in relatively large amounts so that they are optimal
• the dosage can be reduced to avoid general disadvantages of lubricants, e.g. Reduce plate-out, deposits or reduced printability.
• the invention therefore relates to the use of polyolefin waxes produced by means of metallocene catalysts, the polyolefin waxes being homopolymers of ethylene or copolymers of
• Ethylene with one or more 1-olefins and as 1-olefins linear or branched, substituted or unsubstituted olefins with 3-18 C atoms, are used as lubricants and release agents for plastics.
• the 1-olefins preferably comprise 3 to 6 carbon atoms. examples for this are
• Copolymers of ethylene with propene or 1-butene are preferred.
• the copolymers consist of 70-99.9, preferably 80-99% by weight of ethylene.
• the substituent is preferably an aromatic radical which is in conjugation with the double bond of the 1-olefin.
• Metallocene catalysts for the preparation of the polyolefin waxes are chiral or nonchiral transition metal compounds of the formula M 1 L X.
• the transition metal compound M 1 L X contains at least one metal central atom M 1 to which at least one ⁇ ligand, for example a cyclopentadienyl ligand, is bonded.
• substituents such as halogen, alkyl, alkoxy or aryl groups can be bound to the metal central atom M 1 .
• M 1 is preferably a
• Cyclopentadienyl ligand is understood to mean unsubstituted cyclopentadienyl radicals and substituted cyclopentadienyl radicals such as methylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl or octa-tetra-hydrofluoryl or octa-tetra-hydrofluoryl or octa.
• the ⁇ ligands can be bridged or unbridged, whereby single and multiple bridging - also via ring systems - are possible.
• the term metallocene also includes compounds with more than one metallocene fragment, so-called multinuclear metallocenes. These can have any substitution pattern and bridging variant.
• the individual metallocene fragments of such multinuclear metallocenes can be of the same type or different from one another. Examples of such multinuclear metallocenes are e.g. described in EP-A-0 632 063.
• non-polar metallocene waxes their derivatives obtained by polar modification can also be used.
• the modification is carried out, for example, by oxidation with oxygen or gases containing oxygen or by grafting with polar monomers, for example maleic acid or its derivatives.
• polar monomers for example maleic acid or its derivatives.
• the metallocene-based polyolefin waxes described can be added to a plastic in various forms:
• the polyolefin waxes can be individually drummed onto cold or warm carriers (e.g. the plastic), compounded, or mixed into a plastic in a cold or warm powder mixing process. They can be used as a powder or melt blend together with other lubricants such as montan waxes and their salts, fatty acid derivatives and their salts, paraffins, other polyolefin waxes and their polar modified derivatives, amide waxes, silicones and fluoroplastics.
• cold or warm carriers e.g. the plastic
• other lubricants such as montan waxes and their salts, fatty acid derivatives and their salts, paraffins, other polyolefin waxes and their polar modified derivatives, amide waxes, silicones and fluoroplastics.
• the polyolefin waxes can be used as a component of additive mixtures (one packs). These one-packs consist of various lubricants, thermal stabilizers, costabilizers, UV absorbers, antioxidants, light stabilizers, antistatic agents, fillers, pigments, processing aids and other active ingredients.
• the polyolefin waxes are preferably used in micronized form in mixtures of predominantly powdered starting materials. They can be added in the polymerization during the manufacture of a plastic.
• the polyolefin waxes are preferably used pre-dispersed in the form of wax concentrates (masterbatches) in a carrier plastic (e.g. polyolefin).
• a carrier plastic e.g. polyolefin
• stick-free times are usually determined with two-roll mills.
• a ready-to-use PVC mixture is placed on a rolling mill (190 ° C, 15/20 RPM, gap width approx. 0.5 mm) and the time until the PVC melt sticks is measured.
• a long, tack-free period means that the tested lubricant has a good release effect.
• the separating effect of lubricants in engineering plastics is usually quantified by means of demolding force measurements during injection molding.
• demolding force measurements For this purpose, a cylindrical sleeve is produced using the injection molding process and the maximum force required to remove the sleeve from the tool is registered as the removal force.
• a low demolding force shows a good separation effect of the lubricant used.
• Example 1 550 N, dosage 0.3%
• Example 2 650 N, dosage 0.3%
• Example 3 500 N, dosage 0.3%
• Comparison 1 900 N, dosage 0.3%
• Comparison 2 980 N, dosage 0.3%
• Comparison 3 850 N, dosage 0.3%
• the separating effect of lubricants in polyolefins is usually quantified by means of demolding force measurements during injection molding.
• demolding force measurements For this purpose, a cylindrical sleeve is produced using the injection molding process and the maximum force required to demold the sleeve from the tool is given as Demolding force registered.
• a low demolding force shows a good separation effect of the lubricant used.
• Example 1 750 N, dosage 0.1%
• Example 2 700 N, dosage 0.1%
• Example 3 600 N, dosing 0.1% Comparison 1: 900 N, dosing 0.1%

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Lubricants (AREA)
• Moulds For Moulding Plastics Or The Like (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2000
  • 2000-03-29 DE DE10015593A patent/DE10015593A1/de not_active Ceased
• 2001
  • 2001-03-14 WO PCT/EP2001/002864 patent/WO2001072855A1/de not_active Ceased
  • 2001-03-14 US US10/239,605 patent/US7192909B2/en not_active Expired - Fee Related
  • 2001-03-14 JP JP2001571784A patent/JP2003528948A/ja not_active Withdrawn
  • 2001-03-14 HK HK03106388.4A patent/HK1054043A1/zh unknown
  • 2001-03-14 DE DE50109697T patent/DE50109697D1/de not_active Expired - Fee Related
  • 2001-03-14 ES ES01931521T patent/ES2262646T3/es not_active Expired - Lifetime
  • 2001-03-14 CN CN01807411A patent/CN1420897A/zh active Pending
  • 2001-03-14 EP EP01931521A patent/EP1274748B1/de not_active Expired - Lifetime

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