EP0876420A1 - Film a orientation biaxiale constitue de polypropylene obtenu au moyen d'un catalyseur de metallocene - Google Patents

Film a orientation biaxiale constitue de polypropylene obtenu au moyen d'un catalyseur de metallocene

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Publication number
EP0876420A1
EP0876420A1 EP96941044A EP96941044A EP0876420A1 EP 0876420 A1 EP0876420 A1 EP 0876420A1 EP 96941044 A EP96941044 A EP 96941044A EP 96941044 A EP96941044 A EP 96941044A EP 0876420 A1 EP0876420 A1 EP 0876420A1
Authority
EP
European Patent Office
Prior art keywords
propylene
cio
alkyl
aryl
cycloalkyl
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP96941044A
Other languages
German (de)
English (en)
Inventor
Peter John Vaughan Jones
Roland Hingmann
Franz Langhauser
Bernd Lothar Marczinke
Murray Horton
David Fischer
Günther SCHWEIER
Meinolf Kersting
Wolfgang Bidell
Heike Gregorius
Ulrich Moll
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0876420A1 publication Critical patent/EP0876420A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene

Definitions

  • Biaxially oriented polypropylene film made of metallocene polypropylene
  • the present invention relates to the use of homopolycarbonates merisaten of propylene or copolymers of propylene with C 2 - to C ⁇ o -A lk-l -enen 'the monomers with metallocene catalysts are obtainable by the polymerization of the corresponding ⁇ a biaxially oriented for producing single or multilayer polypropylene film.
  • Plastics in particular olefin polymers or polyvinyl chloride (PVC), are widely processed into foils with a thickness of 0.1 to 200 ⁇ m. These films can consist of a single layer or can be constructed from several layers, which are usually formed from different polymers (laminate film, coextrusion film).
  • plastic films are currently the packaging industry and here mainly the packaging of foodstuffs and luxury foods. Films are also used for the production of adhesive tapes, labels and electrical insulation films.
  • the favorable properties should, not least for ecological reasons, unite a film with the smallest possible, constant film thickness and good machinability (easy to process at high stretching speeds).
  • the orientation (stretching) of the films in the longitudinal and transverse directions, based on the extrusion direction, after the extrusion of the polymer has been used (biaxially oriented films, bo process).
  • the polymers previously used for this have disadvantages; be it that, in order to be suitable for the bo process, they have to be mixed with foreign polymers as additives (DE-A 43 37 251) or that they may only have a very low melt flow index (MFI), for example less than 1 g / 10 min (EP-A 333 824).
  • MFI melt flow index
  • a disadvantage of the additive admixture mentioned is that the additives can settle on important parts of the processing machines, such as rollers and screws, which can lead to malfunctions in the processing machines.
  • the present invention was therefore based on the object to remedy the described disadvantages and in particular to provide a thin film which contains little or no foreign polymers as processing additives and can also be prepared from polymers with a higher melt flow index than, for example, 1 g / 10 mm, in particular with the bo process, and has good mechanical and optical properties, for example gloss.
  • the film can be made up of one or more layers.
  • It generally contains an essential component of a propylene homopolymer or a copolymer of propylene and an alk-1-ene or more alk-1-enes, selected from the group consisting of ethylene, 1-butene, 1-pentene, 1-hexene, 1 -Hepten, 1-octene, 1-nonen, 1-decene or 4-methyl-1-pentene, or it contains mixtures of these polymers, the mixing ratios not being critical.
  • Statistical copolymers are generally used as copolymers.
  • the homopolymers of propylene or the copolymers of propylene with C 2 -C 1 -C 1 -alk-1-enes can be obtained by polymerizing the corresponding monomers with metallocene catalysts.
  • Metallocene catalysts are to be understood here as substances which generally consist of a combination of a transition metal compound or a plurality of transition metal compounds, preferably of titanium, zirconium or hafnium, which contains at least one ligand which, in the broadest sense, is a derivative of cyclopentadienyl ligand, with one Activator, also called cocatalyst or metallocenium ion-forming compound, is formed and, in general, has a polymerization-active smd in relation to the monomers described.
  • Such catalysts are for example m EP-A 0 545 303, EP-A 0 576 970 and
  • the metallocene catalysts according to the invention generally contain as active constituents
  • X ⁇ X 2 fluorine, chlorine, bromine, iodine, hydrogen, -C ⁇ to Cio-alkyl, C 6 - to -C 5 aryl, -OR 6 or -NR 6 R 7
  • Aryl residue means
  • R 1 to R 5 hydrogen, C ⁇ ⁇ to Cio-alkyl, 5- to 7-gl ⁇ edr ⁇ ge ⁇
  • Cycloalkyl which in turn can carry a C ⁇ to C ⁇ A alkyl as a substituent, C 6 - to Ci 5 ⁇ aryl or
  • Arylalkyl where appropriate also two adjacent ones Residues can together stand for 4 to 15 C-containing cyclic groups, or S ⁇ (R 8 ) 3 with
  • R 8 Ci to Cio-alkyl, C 6 - bis C ⁇ 5 aryl or C 3 - to CiQ-cycloalkyl,
  • R 9 to R 13 are hydrogen, -C ⁇ to -C ⁇ 0 alkyl, 5- to 7-gl ⁇ edr ⁇ ges
  • Cycloalkyl may carry in turn em C ⁇ ⁇ to C ⁇ o ⁇ alkyl as a substituent, C - to C-aryl or arylalkyl and wherein optionally two adjacent radicals can stand on facing cyclic groups together are 4 to 15 carbon atoms, or
  • R 14 C x - to Cio-alkyl, C 6 - to -C 5 aryl or C 3 - to
  • R 4 and Z together form a grouping ⁇ [Y (R 15 ) (R 16 )] n -E- in which
  • R 15 , R 16 for hydrogen, C ⁇ ⁇ to C 10 alkyl, C 3 - to C ⁇ 0 cyclo alkyl or C $ - to C ⁇ 5 aryl
  • NR 17 or PRi7 means
  • R 18 Ci to Cio-alkyl, C e - to -C 5 aryl, C 3 - to Cio-cycloalkyl or alkylaryl
  • metallocenes does not only mean the bis ( ⁇ -cyclopentadienyl) metal complexes.
  • the radicals X 1 , X 2 can be the same or different, preferably smd the same.
  • R 1 and R 9 are the same and stand for hydrogen or C ⁇ ⁇ to C ⁇ o ⁇ alkyl groups
  • R 9 and R 13 are smd and for hydrogen, a methyl, ethyl, iso-propyl or tert. -Butyl group stand
  • R 2 , R 3 , R 10 and R 11 have the meaning
  • R 2 and R 10 have hydrogen or two adjacent radicals R 2 and R 3 and R 10 and R 11 together represent cyclic groups containing 4 to 12 carbon atoms,
  • M stands for titanium, zirconium or hafnium, Y for silicon, germanium, tin or carbon and ⁇ i , x 2 for chlorine or Ci to C 4 alkyl.
  • Examples of particularly suitable complex compounds include Dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (indenyl) zirconium dichloride, dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride, ethylene bis (cyclopentadienyl) zirconiumdichkonyldichloride (ethylene bis) dirconium dichloride,
  • Tetramethylethylene-9-fluorenylcyclopentadienylzirconium dichloride dimethylsilanediylbis (-3-tert.butyl-5-methylcyclopentad ⁇ enyl) - zirconium dichloride,
  • X 2 represents chlorine or C ⁇ ⁇ to C 10 alkyl
  • R 1 to R 3 and R 5 for hydrogen, C ⁇ ⁇ to Cio-alkyl, C 3 - to
  • Cio-cycloalkyl C 6 to C 5 aryl or S 5 (R 8 ) 3 , or where two adjacent radicals stand for cyclic groups having 4 to 12 C atoms.
  • Metallocene complexes of the general formula (I) in which at least one of the radicals R 1 to R 5 is different from hydrogen are particularly preferred.
  • Compounds of the formula (Ia) are preferably used, such as dimethylsilanediylbis (-2-methyl-indenyl) zirconium dichloride and dimethylsilanediylbis (indenyl) zirconium conium dichloride, very particularly preferred is the dimethylsilane diyl-bis- [3,3'- (2-methylbenzmdenyl)] zirconium dichloride as the transition metal compound (I).
  • transition metal compounds (I) can be carried out by methods known per se, the reaction of the appropriately substituted cycloalkenylamones with halides of the transition metals, for example titanium, zirconium, hafnium, vanadium, niobium or tantalum, being preferred. Examples of corresponding production processes are described, inter alia, in the Journal of Organometallic Chemistry, vol. 369 (1989), pages 359 to 370.
  • R 19 is a -C ⁇ to C 4 alkyl group, preferred
  • Methyl or ethyl group and m is an integer from 5 to 30, preferably 10 to 25.
  • oligomeric alumoxane compounds are usually prepared by reacting a solution of trialkylaluminum with water and are, inter alia, m EP-A 284 708 and US A 4,794,096.
  • the oligomeric alumoxane compounds obtained in this way are present as mixtures of both linear and cyclic chain molecules of different lengths, so that m is to be regarded as the mean.
  • the alumoxane compounds can also be present in a mixture with other metal alkyls, preferably with aluminum alkyls. It has proven to be advantageous to use the metallocene complexes and the oligomeric alumoxane compound in amounts such that the atomic ratio between aluminum from the oligomeric alumoxane compound and the transition metal from the metallocene complexes is in the range from 10: 1 to 10 6 : 1, in particular in the range Range from 10: 1 to 10 4 : 1.
  • Coordination complex compounds selected from the group of strong, neutral Lewis acids, ionic compounds with Lewis acidic cations and ionic compounds with Bronsted acid can also be used as cations as the metallocenium ion-forming compound B).
  • Main group of the periodic table means, in particular B, Al or Ga, preferably B,
  • X 3 , X 4 and X 5 for hydrogen, C x - to Cio-alkyl, C 6 - to -C 5 aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 C atoms in the alkyl radical and 6 to 20 C.
  • T is an element of I. to VI. Main group or the I. to VIII.
  • Subgroup of the periodic table means Q l to Q z for simply negatively charged residues such as Ci bis
  • Ci to Cio-cycloalkyl which optionally can be substituted with Ci to Cio alkyl groups, halogen, Ci to C 28 alkoxy, C 6 - to C i5 aryloxy, silyl or mercaptyl groups
  • a represents integers from 1 to 6
  • d corresponds to the difference a z, but d is greater than or equal to 1.
  • Carbonium cations, oxomum cations and sulfonium cations as well as katiom transition metal complexes are particularly suitable.
  • the triphenylmethyl cation, the silver cation and the 1, 1 '-dimethylferrocenyl cation should be mentioned.
  • non-coordinating counterions especially boron compounds, as they are also called in WO 91/09882, preferably tetrakis (pentafluorophenyl) borate.
  • the molar ratio of boron from the compound forming the metallocenium ion to transition metal from the metallocene complex is in the range from 0.1: 1 to 10: 1, in particular in the range from 1: 1 to 5: 1.
  • the metallocenium-forming compounds B) are usually used alone, in a mixture with one another or in a mixture with organometallic compounds of the first to third main groups of the Periodic Table of the Elements, for example n-butyllithium, di-n-butylmagnesium, butyloctylmagnesium, trimethylaluminium, triethylaluminum, triisobutylaluminum, diisobutylumium d ⁇ d used, the mixing ratio of the components to one another being generally not critical.
  • Methylaluminoxane or Tr ⁇ s- (penta fluorophenyl) boron is preferably used as the compound B) forming metallocenium ions, and in particular methylaluminoxane.
  • the metallocene catalysts according to the invention can also be used on a support material.
  • the carrier materials used are preferably finely divided carriers which preferably have a particle diameter in the range from 1 to 300 ⁇ m, in particular from 30 to 70 ⁇ m.
  • Suitable carrier materials are, for example, silica gels, preferably those of the formula ⁇ 0 2 • a A1 2 0 3 , in which a is a number in the range from 0 to 2, preferably 0 to 0.5; this is alumo silicates or silicon dioxide.
  • Such products are commercially available, for example Silica Gel 332 from Grace.
  • Other carriers include, inter alia, polyolefins, such as polypropylene.
  • the propylene polymers can be prepared in the usual reactors used for the polymerization of olefins either discontinuously or preferably continuously.
  • Suitable reactors include continuously operated ones
  • Ruhr kettles where it is also possible to use a series of several Ruhr kettles connected in series.
  • the polymerization reactions can be carried out in the gas phase in suspension, in liquid and in supercritical monomers or in inert solvents.
  • the polymerization conditions are not critical per se. Pressures of 100 to 350,000 kPa, preferably 100 to 250,000 and ms, particularly 100 to 100,000 kPa, temperatures of 0 to 400 ° C, preferably 20 to 250 ° C and in particular 50 to 100 ° C have proven to be suitable.
  • the homopolymerizations of propylene or the copolyme ⁇ sations of propylene with C 2 - to C ⁇ o-Alk-1-enes in emer stirred gas phase such as the NOVOLEN ® -Propylenpolymer ⁇ sat ⁇ onsclar from BASF durcn.
  • Well suited process conditions for this are polymerization pressures in the range of 1000 to 4000 kPa and polymerization temperatures in the range of 50 to 100 ° C.
  • the average molecular weight of the polymers can be controlled using the methods customary in polymerization technology, for example by adding molecular weight regulators, such as Hydrogen, which leads to a reduction in the molecular weight of the polymer or by varying the polymerization temperature, high polymerization temperatures usually also leading to reduced molecular weights. 5
  • molecular weight regulators such as Hydrogen
  • the homopolymers of propylene according to the invention or copolymers of propylene with C 2 -C 1 -C -alk-1-enes generally have a melt flow rate (MFR) measured at 230 ° C. and a coating weight of 2.16 kg according to DIN 53735 in the range from 0.1 10 to 10000 g / 10 mm, preferably in the range from 2 to 10000 and in particular in the range from 2 to 500.
  • MFR melt flow rate
  • the average molecular weight Mw of the homopolymers of propylene according to the invention or copolymers of propylene with C 2 - 15 to C ⁇ o-Alk-1-enes, measured by the method of gel permeation chromatography (GPC) at 140 ° C in 1, 2, 4-trichlorobenzene against polypropylene standard, is usually in the range from 4,000 to 850,000, preferably in the range from 50,000 to 450,000 and in particular in the range from 100,000 to 450,000.
  • the molecular weight distribution of the propylene polymers Mw / Mn according to the invention is generally in the range from 1.2 to 6.0 and preferably in the range from 1.5 to 3.0.
  • Both the molecular weight Mw, the molecular weight distribution Mw / Mn and, in particular, the MFR value can also be set using the method of peroxidically initiated degradation of a starting polymer, advantageously in an extruder. 30 This method is known to the person skilled in the art.
  • the homopolymers of propylene according to the invention generally have a melting point, determined by the method of differential scanning calorimetry (DSC) in the range from 80 ° C to 35 165 ° C, preferably in the range from 135 ° C to 165 ° C and in particular in particular Range from 140 ° C to 165 ° C.
  • DSC differential scanning calorimetry
  • copolymers of propylene with C 2 - to C 1 -C 1 -en-enes according to the invention generally have a melting point, determined 40 using the differential scanning method (DSC).
  • Heating rate 20 ° C / mm. In the range from 60 ° C to 160 ° C, preferably in the range from 80 to 150 ° C and in particular in the range from 100 ° C to 150 ° C.
  • the pentad content mmmm of the homopolymer seed according to the invention is usually in the range from 60% to 99%, preferably in the range from 80% to 98%.
  • the chemically bound comonomer fraction of the copolymers of propylene according to the invention with C 2 -C 1 -C 1 -alk-1-enes, measured using the 13C-NMR spectroscopy method, is generally in the range from 0.001 to 35 mol%, preferably in the range from 0.01 to 15 mol%, based on the copolymer.
  • Propylene homopoly mesates or copolymers of propylene with C 2 - to C 1 -C 1 -alkenes which are very suitable in the context of the invention are obtained if the corresponding monomers are polymerized in the presence of a catalyst system according to the invention, which dimethylsilanediyl-bis- [3, 3 '- (2-methylbenz-indenyl)] zirconium dichloride as a metallocene complex (I) contains.
  • the propylene homopolymers or copolymers obtainable in this way then generally have the polymer properties already mentioned, such as MFR, Mw, Mw / Mn, melting point, pentad content and comonomer.
  • Preferred copolymers of propylene obtainable with the dimethylsilanediylbis [3, 3 '- (2-methylbenzenedenyl)] zirconium dichloride catalyst with C 2 - to C 1 -C 1 -alkenes, and random copolymers of propylene and ethylene with 0.1% to 10 mol%, preferably 0.2 to 7 mol%, based on the polymer, of units derived from ethylene, random copolymers of propylene and 1-butene with 0.5 to 20 mol%, preferably 1 to 15 mol%, based on the polymer, of derivatives derived from 1-butene, statistical terpolymers of propylene, ethylene and 1-butene with 0.1 to 10 mol%, preferably 0.2 to 7 mol% %, based on the terpolymer, of units derived from ethylene and 0.5 to 20 mol%, preferably 1 to 15 mol%, based on the terpolymer, of units derived from 1-
  • propylene homo- or copolymer or mixtures of these polymers according to the invention are usually melted in one or more extruders and the melt is extruded or coextruded through a slot die.
  • the film cooled below the melting point of the polymer is then biaxially stretched longitudinally and transversely to the extrusion direction, the stretching ratio in the longitudinal direction generally being in the range from 1 to 20, preferably in the range from 3.5 to 10, and the product the stretch Ratios in the longitudinal and transverse directions are generally in the range from 1 to 20, preferably in the range from 3.5 to 10.
  • the film can only be stretched in the same direction and then in the other direction (tenter process) or stretched in both directions can be carried out simultaneously (film blowing process, "bubble process").
  • the extrusion temperature of the polymer is usually in the range from 180 to 280 ° C., preferably in the range from 210 to
  • the person skilled in the art can determine the suitable temperature of the film which has cooled before stretching in a few experiments. It is usually in the range from 1 to 50 ° C., preferably in the range from 2 to 25 ° C. and in particular in the range from 2 to 10 ° C. below the value of the highest melting point, of the polymer or polymer mixture used for the extrusion the biaxial orientation per se is known to the person skilled in the art and, moreover, in the handbook of plastic extrusion technology, volume 2, ed. F. Hensen, Carl Hanser Verlag, Kunststoff, Vienna (1986), chapter 8, in particular 8.3.1, pages 243 to 270 , described in detail.
  • the thickness of the monolayer films according to the invention that can be obtained in this way is generally in the range from 0.1 to 150 ⁇ m, preferably in the range from 0.2 to 100 ⁇ m and in particular in the range from 0.4 to 70 ⁇ m.
  • the thickness distribution or "waviness" of the film transverse to the direction of extrusion is very low; it is generally in the range from 0.05 to 5%, preferably in the range from 0.05 to 1.5%.
  • the number of layers and their sequence are generally not critical, but two-layer or three-layer films are preferred.
  • the films according to the invention are distinguished by good optical, thermal and mechanical properties; they are very easy to work with and can be oriented especially at high stretching speeds.
  • the scatter value of the films according to the invention is generally in the range from 0.05 to 3.5%, preferably in the range from 0.05 to 2% and in particular in the range from 0.1 to 0 , 5%.
  • the gloss of the films according to the invention, measured according to ASTM D2457 at 20 °, is generally in the range from 50 to 200 skt, preferably in the range from 100 to 200 skt.
  • the modulus of elasticity of the films according to the invention is generally in the range from 800 to 6000 N / mm 2 , preferably in the range from 1000 to 5000 N / mm 2 and in particular in the range from 2000 to 4500 N / mm 2 .
  • the permeability of the films according to the invention to water vapor is generally in the range from 0.05 to 0.5 g / m 2 / d, preferably in the range from 0.1 to 0.3 g / m 2 / d .
  • the single-layer or multilayer films according to the invention can also contain the usual thermoplastic additives in the usual amounts.
  • Suitable additives are antistatic agents, lubricants, such as fatty acid amides, for example erucasaureamide, stabilizers, neutralizing agents, such as calcium stearate, pigments and also inorganic fillers, such as talc, aluminum oxide, aluminum sulfate, barium sulfate, calcium magnesium carbonate,
  • Silicon dioxide titanium dioxide and organic fillers such as polyester, polystyrene, polyamide and halogenated organic polymers.
  • the films according to the invention are distinguished, inter alia, by the fact that they can be produced from propylene polymers with a relatively high MFR value in the biaxial orientation process, and in that they have very good mechanical and optical properties (for example gloss), inter alia are thin and tearproof. Furthermore, the films according to the invention generally have good heat-sealing properties (low heat-sealing temperature), which predestines them, inter alia, for use in packaging. In multilayer films, a thin cover layer made of the inventive polypropylene film is usually sufficient, for example for favorable heat sealing properties. Furthermore, the foils according to the invention are very well suited, inter alia for reasons of the small thickness of the dielectric (foil), as an electrical insulating foil and in particular as a capacitor foil. Examples
  • Homopolypropylene which by means of N0V0LEN ® gas phase polymerization of propylene at a temperature of 60 ° C and a pressure of 2400 kPa, without hydrogen regulation of the molecular
  • the polymers were extruded and stretched bidirectionally at a temperature of 140 ° C. on a so-called tenter unit (bo process). This gave the o-PP films listed in Ta 20 belle 1 smd.
  • propylene was copolymerized with various comonomers (see Table 2) at 60 ° C and 2400 kPa in the presence of a dimethylsilanediyl bis [3,3 '(2-methylbenzmdenyl)] zirconium dichloride / methylaluminoxane catalyst fixed on silica gel.
  • the polymers were then further processed to bo foils ("bubble process").

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

L'invention concerne l'utilisation d'homopolymères de propylène ou de copolymères de propylène avec des alc-1-ènes C2 à C10, que l'on peut obtenir par la polymérisation des monomères correspondants avec des catalyseurs de métallocène. Ces composés sont utilisés dans la production d'un film de polypropylène monocouche ou multicouche à orientation biaxiale.
EP96941044A 1995-11-30 1996-11-28 Film a orientation biaxiale constitue de polypropylene obtenu au moyen d'un catalyseur de metallocene Withdrawn EP0876420A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19544709 1995-11-30
DE19544709A DE19544709A1 (de) 1995-11-30 1995-11-30 Biaxial orientierte Polypropylenfolie aus Metallocen-Polypropylen
PCT/EP1996/005251 WO1997019980A1 (fr) 1995-11-30 1996-11-28 Film a orientation biaxiale constitue de polypropylene obtenu au moyen d'un catalyseur de metallocene

Publications (1)

Publication Number Publication Date
EP0876420A1 true EP0876420A1 (fr) 1998-11-11

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EP96941044A Withdrawn EP0876420A1 (fr) 1995-11-30 1996-11-28 Film a orientation biaxiale constitue de polypropylene obtenu au moyen d'un catalyseur de metallocene

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EP (1) EP0876420A1 (fr)
AU (1) AU1032497A (fr)
DE (1) DE19544709A1 (fr)
WO (1) WO1997019980A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19738051A1 (de) 1997-09-01 1999-03-04 Targor Gmbh Spritzgieß-Artikel aus Metallocen-Polypropylen
DE29822095U1 (de) 1998-12-11 1999-04-01 Elbtal Folien GmbH, 01640 Coswig Kunststoff-Folie
US7351478B2 (en) * 2001-03-16 2008-04-01 Fina Technology, Inc. Heat-seal films and method of manufacture

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Publication number Priority date Publication date Assignee Title
TW318184B (fr) * 1991-11-30 1997-10-21 Hoechst Ag
DE4242486A1 (de) * 1992-12-16 1994-06-23 Basf Ag Propylen-Homopolymere
EP0668157B1 (fr) * 1994-02-21 2003-05-21 Basell Polyolefine GmbH Films stratifiés thermosoudables en polyoléfines, procédé pour leur fabrication et leur utilisation
US5468440B1 (en) * 1994-05-06 1997-04-08 Exxon Chemical Patents Inc Process of making oriented film or structure
ES2221667T3 (es) * 1994-05-24 2005-01-01 Exxonmobil Chemical Patents Inc. Peliculas preparadas a partir de copolimeros de propileno y alfa olefina superior.
WO1995032235A1 (fr) * 1994-05-24 1995-11-30 Exxon Chemical Patents Inc. Resine thermo-scellable de copolymere de propylene amelioree et articles obtenus a partir de cette resine

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Title
See references of WO9719980A1 *

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DE19544709A1 (de) 1997-06-05
AU1032497A (en) 1997-06-19
WO1997019980A1 (fr) 1997-06-05

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