WO2010020399A1 - Amélioration de la transparence de polypropylène contenant des cires de métallocène - Google Patents

Amélioration de la transparence de polypropylène contenant des cires de métallocène Download PDF

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Publication number
WO2010020399A1
WO2010020399A1 PCT/EP2009/005989 EP2009005989W WO2010020399A1 WO 2010020399 A1 WO2010020399 A1 WO 2010020399A1 EP 2009005989 W EP2009005989 W EP 2009005989W WO 2010020399 A1 WO2010020399 A1 WO 2010020399A1
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WO
WIPO (PCT)
Prior art keywords
waxes
range
metallocene
transparency
polypropylene
Prior art date
Application number
PCT/EP2009/005989
Other languages
German (de)
English (en)
Inventor
Joachim Kohler
Original Assignee
Clariant International Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Priority to EP09777955A priority Critical patent/EP2318458A1/fr
Publication of WO2010020399A1 publication Critical patent/WO2010020399A1/fr

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Classifications

    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • 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

  • This invention relates to improving the transparency of PP-H (polypropylene homopolymer) through the use of metallocene catalyzed polyolefin waxes, so-called metallocene waxes.
  • PP-H Due to its semi-crystalline character, PP-H is in and of itself an opaque polymer and therefore not suitable for full or semitransparent applications. It has been found that this disadvantage can be reduced by the addition of a minimum concentration of certain metallocene waxes.
  • PP Polypropylene
  • PP-H-dominated packaging market For some fields of application, such as packaging, containers or covers, there are often requirements for a minimum transparency. For example, to be able to read or recognize past markings or packaged goods, or not to minimize the light output of a light source (PlasticsEurope "Production and Consumption Data for Plastics in Germany including Utilization 2003", study by Consultic Marketing & Industrie redesign GmbH vom August 27, 2004, pages 26ff).
  • Regular PP-H is suitable for many applications in terms of mechanical requirements and barrier properties. For those with the o. G. Transparency requirements, however, is in most cases the opacity of PP-H an exclusion criterion.
  • Polypropylene homopolymer (PP-H) is known from the prior art, polymerized from only one, repeating monomer, the propylene: HH
  • the spatial arrangement of the methyl group present on every other carbon atom may vary.
  • isotactic PP favors the formation of crystalline domains, e.g. B. during cooling from the melt ("Hostalen PP" product data sheet HFKR 102 D-9020-022 Hoechst AG, February 1990 issue, page 2).
  • PP-H is therefore also referred to as semi-crystalline polymer with low transparency.
  • PP-copo PP copolymer
  • PP-R random copolymers
  • PP-B block copolymers
  • PP-B has a high toughness, especially at low temperatures.
  • PP-R types are predominantly used in highly transparent applications (Amemiya T, Kitade S, Kozai I, Minakami S, Takahashi K, Tayano T, Japan Polychem Corp., Application PRAI JP 2004-382168, 28.12.2004).
  • the arbitrary arrangement of the ethylene sequences in the PP-R polymer chain leads to a high amorphous content and thus to a very good transparency.
  • the copolymerization of propylene with ethylene to PP-R is a way to obtain a polypropylene with good transparency.
  • the schematic structure of a PP-R from the propyl (P) and ethyl (E) groups may be as follows:
  • nucleating agents such as metal stearates, benzoates, carbonates, phosphates, etc.
  • metal stearates, benzoates, carbonates, phosphates, etc. have in particular those from the Class of sorbitol esters has proven to be most effective, particularly with regard to mechanical and optical properties ("Plastics Additive Handbook", 5 m edition, Chapter 18 "Nucleating Agents for Semi-crystalline Polymers", pages 960 ff).
  • BOPP biaxially oriented PP
  • the crystallinity is increased by aligning the polymer chains and, on the other hand, the refractive index in the different planes is made uniform.
  • BOPP is also bound to this one processing method.
  • Food packaging does not accept deterioration of organoleptic properties and is an exclusionary criterion.
  • a "smelly" PP sachet as a bread package is unthinkable and unacceptable; -
  • the mechanical properties of the PP-H end article must not be impaired, as otherwise certain applications can no longer be operated, or only to a limited extent. Examples include packaging such as canisters, bottles and beakers, which among other things also exert a protective function against external, mechanical effects;
  • metallocene waxes such as. As Licocene PP 1302, PP 6102, PP 2602, PE 4201 or PPSI 3262, the transparency of PP-H increased to over 81% and thus a significant improvement to the PP-H produced by known methods can be achieved. This positive effect is achieved without changing the color or mechanical properties of the articles equipped with them. It is irrelevant whether the metallocene waxes are incorporated in a compound or added as a masterbatch or pure substance in polymer processing. The metered addition can be carried out gravimetrically, or else by means of a physical premix, or as a preparation or in pure form by side metering on the extruder. A change in the PP-H processing conditions, such as temperature profile, residence times, shear rate in the extruder, etc. is not necessary.
  • Metallocene compounds of the formula (I) are used for the preparation of the metallocene polyolefin waxes used according to the invention.
  • This formula also includes compounds of the formula (Ia)
  • M 1 is a Group IVb, Vb or VIb metal of the Periodic Table, for example, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, preferably titanium , Zirconium, hafnium.
  • R 1 and R 2 are identical or different and represent a hydrogen atom, a C1-C1 0, preferably Ci-C 3 alkyl, in particular methyl, a C1-C1 0 -, preferably Ci-C 3 alkoxy group, a C 6 - Ci 0 , preferably C 6 -C 8 -aryl, a C 6 -C 0 -, preferably C 6 -C 8 -aryloxy, a C 2 -C 1 0 , preferably C 2 -C 4 -alkenyl, a C 7 -C 40 -, preferably C 7 -Cio-arylalkyl group, a C 7 -C 4 O-, preferably C 7 -C 2 alkylaryl group, a C 8 -C 4 O-. preferably C 8 -C 12 arylalkenyl group or a halogen, preferably chlorine atom.
  • R 3 and R 4 are identical or different and denote a mononuclear or polynuclear hydrocarbon radical which can form a sandwich structure with the central atom M 1 .
  • R 3 and R 4 are preferably cyclopentadienyl, indenyl, tetrahydroindenyl, benzoindenyl or fluorenyl, it being possible for the basic units to carry additional substituents or to bridge them with one another.
  • one of the radicals R 3 and R 4 may be a substituted nitrogen atom, wherein R 24 has the meaning of R 17 and is preferably methyl, tert-butyl or cyclohexyl.
  • R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are identical or different and denote a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C 1 -C 10, preferably C 1 -C 4, alkyl group, a C 6 -C O -, preferably C 6 -C 8 -aryl group, a C1-C1 0 -, preferably Ci-C 3 alkoxy group, a -NR 1 V, -SR 16 -, -OSiR 1 V, -SiR 1 V or -PR 16 2 radical, where R 16 is a C1-C10-, preferably -C 3 alkyl group or C 6 -C 0 -, preferably C 6 -C 8 - aryl group, or in the case of Si- or P-containing radicals is also a halogen atom, preferably chlorine atom, or each two adjacent radicals R 5 , R 6
  • R is 13 R 17 ? 17 R 17 R 17 R 17
  • R 17 , R 18 and R 19 are identical or different and are a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C 1 -C 30 , preferably C 1 -C 4 -alkyl, in particular methyl, group, a CiC-io-fluoroalkyl, preferably CF 3 group, a C 6 -C
  • M 2 is silicon, germanium or tin, preferably silicon and germanium.
  • R 11 and R 12 are the same or different and have the meaning given for R 17
  • m and n are the same or different and are zero, 1 or 2, preferably zero or 1, where m plus n is zero, 1 or 2, preferably zero or 1.
  • R 14 and R 15 have the meaning of R 17 and R 18 .
  • Indenyl-cyclopentadienyl-zirconium dichloride isopropylidene (1-indenyl) (cyclopentadienyl) zirconium dichloride, isopropylidene (9-fluorenyl) (cyclopentadienyl) zirconium dichloride,
  • Phenylmethylsilyl-bis-1- (2-methyl-indenyl) zirconium dichloride and in each case the alkyl or aryl derivatives of these metallocene dichlorides.
  • Suitable cocatalysts for metallocenes of the formula (I) are organoaluminum compounds, in particular alumoxanes or else aluminum-free systems such as R 20 x NH 4 . x BR 21 4 , R 20 x PH 4- ⁇ BR 21 4 , R 20 3CBR 21 4 or BR 21 3 .
  • x is a number from 1 to 4, the radicals R 20 are identical or different, preferably identical, and are C 1 -C 10 -alkyl or C 6 -C 8 -aryl or two radicals R 20 form together with the they combine a ring and the radicals R 21 are the same or different, preferably the same, and are C 6 -C 8 -aryl which may be substituted by alkyl, haloalkyl or fluorine.
  • R 20 is ethyl, propyl, butyl or phenyl and R 21 is phenyl, pentafluorophenyl, 3,5-bis-trifluoromethylphenyl, mesityl, xylyl or ToIyI.
  • organoaluminum compound such. As triethylaluminum, tributylaluminum and others and mixtures suitable.
  • supported single-center catalysts can also be used. Preference is given to catalyst systems in which the residual contents of support material and cocatalyst do not exceed a concentration of 100 ppm in the product.
  • metallocene catalyzed, unmodified but also grafted polyolefin waxes can be used.
  • unmodified polyolefin metallocene waxes are to be preferred, and within this product range, the PP metallocene waxes have been found to be particularly suitable.
  • Metallocene waxes which can be used according to the invention have a molecular weight Mn in the range from 500 to 15,000 g / mol, preferably in the range from 1,000 to 13,000 and / or a viscosity in the range from 30 to 10,000 mPa.s, preferably from 50 to 8,000 (measured at 170 ° C C for PP waxes and 140 ° C for PE (polyethylene) waxes).
  • the metallocene waxes are used in concentrations in the range from 0.1 to 10% by weight, preferably from 1 to 5% by weight, based on the total weight of the mixture.
  • the metallocene waxes shown in the diagram 1 such as.
  • Licocene ® PP 1302, PP 6102, PP 2602, PE 4201 or PPSI 3262 it is irrelevant whether it is an isotactic, syndiotactic or atactic PP-H.
  • the effect is not limited to a certain viscosity range of the PP-H, so that a transparency improvement in an MFI (MeIt Flow Index) range of 0.2-50 g / 10min, but especially in the range of 0.3-40 g / 10min (at 230 0 C / 2.16 kg) is achieved.
  • MFI MeIt Flow Index
  • the present invention also relates to a process for the preparation of the polypropylene homopolymer waxes according to the invention having a transparency ⁇ 81% by blending polypropylene homopolymer waxes with 0.1 to 10 wt.% Of one or more metallocene waxes having a molecular weight Mn in the range of 500 to 15000 g / mol and a viscosity in the range of 30 to 10,000 mPa.s (at 170 0 C or 140 0 C), melting and then extruding and granulating the mixture.
  • the premixing of the individual components can be advantageous and can be carried out at room temperature in a suitable mixing apparatus.
  • the heat energy can be introduced via friction, via separate heating of the mixing trough or in both ways.
  • a pre-tempering to about 25 0 C is considered advantageous. Higher starting temperatures in the hot mix lead to clumping of the carrier and formation of bottom deposits. Cooling of the mixing trough after the last mixing phase to the pre-treatment temperature is also advantageous.
  • a mixture of the individual components is produced.
  • the mixture is done with appropriate mixing technique.
  • the preparation of mixtures can be omitted, however, by feeding the individual components of a recipe directly to the extrusion plant.
  • the said mixture is then fed by means of a suitable metering device to an extrusion plant.
  • these are single or twin-screw extruders, but it is also possible to use continuous and discontinuous kneaders or compactors.
  • the subsequent granulation takes place via strand and Kopfgranul réelle, but also spraying is possible.
  • the high-transparency polypropylene homopolymers according to the invention are particularly suitable for the production of polypropylene articles by injection molding, Extrusion, thermoforming, extrusion blow molding, sintering, rotomolding, pressing or calendering.
  • An improved transparency of PP homopolymer plays a role mainly in PP films in layer thicknesses of 25-1000 ⁇ m and PP thick-wall articles in the thickness ranges above 1 mm.
  • Applications are films such. As cover films, protective films, packaging films, etc. which are produced by a blow molding or calendering, or containers such as canisters, bottles, cups, etc. which z. B. in the deep drawing, injection molding or blow molding.
  • Licocene waxes does not affect other finishing processes or their effects on PP-H.
  • coloring with pigments stabilizing with additives, such as antioxidants or light stabilizers, equipping with antistatic agents, etc.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des homopolymères de polypropylène ayant une transparence supérieure à 81 %, ainsi que leur procédé de production. Ces homopolymères de polypropylène contiennent une ou plusieurs cires de métallocène-polyoléfine à une concentration allant de 0,1 à 10 % en poids et ont une masse moléculaire Mn dans la fourchette de 500 à 15 000 g/mole et une viscosité dans la fourchette de 30 à 10 000 mPa·s (à 170 °C pour le PP ou 140 °C pour le PE).
PCT/EP2009/005989 2008-08-22 2009-08-19 Amélioration de la transparence de polypropylène contenant des cires de métallocène WO2010020399A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09777955A EP2318458A1 (fr) 2008-08-22 2009-08-19 Amélioration de la transparence de polypropylène contenant des cires de métallocène

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008039279A DE102008039279A1 (de) 2008-08-22 2008-08-22 Transparenzverbesserung von Polypropylen mit Metallocenwachsen
DE102008039279.0 2008-08-22

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Publication Number Publication Date
WO2010020399A1 true WO2010020399A1 (fr) 2010-02-25

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PCT/EP2009/005989 WO2010020399A1 (fr) 2008-08-22 2009-08-19 Amélioration de la transparence de polypropylène contenant des cires de métallocène

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EP (1) EP2318458A1 (fr)
DE (1) DE102008039279A1 (fr)
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030050381A1 (en) * 2000-03-01 2003-03-13 Gerd Hohner Dispersion of pigments in polypropylene
US20060032765A1 (en) * 2003-05-07 2006-02-16 Basell Polyolefine Transparent polypropylene containers for packaging shoes
US20070080483A1 (en) * 2005-10-07 2007-04-12 Mitsui Chemicals, Inc. Process for producing injection molded product
WO2007104689A1 (fr) * 2006-03-16 2007-09-20 Clariant International Ltd Cires modifiées, procédé pour la préparation de celles-ci et utilisation de celles-ci

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030050381A1 (en) * 2000-03-01 2003-03-13 Gerd Hohner Dispersion of pigments in polypropylene
US20060032765A1 (en) * 2003-05-07 2006-02-16 Basell Polyolefine Transparent polypropylene containers for packaging shoes
US20070080483A1 (en) * 2005-10-07 2007-04-12 Mitsui Chemicals, Inc. Process for producing injection molded product
WO2007104689A1 (fr) * 2006-03-16 2007-09-20 Clariant International Ltd Cires modifiées, procédé pour la préparation de celles-ci et utilisation de celles-ci

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Clariant presents additional waxes and colours at RETEC 2005", ADDITIVES FOR POLYMERS, ELSEVIER ADVANCED TECHNOLOGY, vol. 2005, no. 11, 1 November 2005 (2005-11-01), pages 3 - 4, XP025366530, ISSN: 0306-3747, [retrieved on 20051101] *

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Publication number Publication date
DE102008039279A1 (de) 2010-02-25
EP2318458A1 (fr) 2011-05-11

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