EP1352016A1 - Utilisation de propylenes terpolymeres pour la fabrication de films - Google Patents

Utilisation de propylenes terpolymeres pour la fabrication de films

Info

Publication number
EP1352016A1
EP1352016A1 EP01998586A EP01998586A EP1352016A1 EP 1352016 A1 EP1352016 A1 EP 1352016A1 EP 01998586 A EP01998586 A EP 01998586A EP 01998586 A EP01998586 A EP 01998586A EP 1352016 A1 EP1352016 A1 EP 1352016A1
Authority
EP
European Patent Office
Prior art keywords
films
propylene
use according
film
days
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Withdrawn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
EP01998586A
Other languages
German (de)
English (en)
Inventor
Manfred Grünberger
Anton Wolfsberger
Jürgen Emig
Dirk Leistner
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.)
Borealis Polyolefine GmbH
Original Assignee
Borealis AG
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 Borealis AG filed Critical Borealis AG
Priority to EP01998586A priority Critical patent/EP1352016A1/fr
Publication of EP1352016A1 publication Critical patent/EP1352016A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08J2323/14—Copolymers of propene

Definitions

  • the present invention relates to the use of propylene terpolymers for the production of films.
  • the present invention relates to the use of propylene terpolymers comprising propylene, a higher C 4 -C 8 ⁇ -olefine and a small fraction of ethylene as third component.
  • Films produced from this polymer have excellent mechanical properties (balanced stiffness/tenacity ratio), optical properties and low blooming behaviour as well as an extraordinary fast slip agent migration and low COF (Coefficient of Friction) values.
  • Polyolefin polymers have gained wide acceptance and usage in numerous commercial applications because of their relatively low costs and desirable properties.
  • plastic films such as cast films, blown films, mono- and biaxially oriented films and coating. These plastic films can for example be used for various flexible and rigid packaging, e.g. for food, medicals, textiles, flowers, stationery etc.
  • films In addition it is important for films to exhibit good processability and good conversionabiiity in terms of tensile properties, stiffness and frictional behaviour. Satisfactory frictional behaviour is also important for comfortable usage of films, e.g. for films used in office organization applications, especially for very thin cast films with thicknesses below 50 ⁇ m.
  • Frictional behaviour is usually measured as dynamic COF according to DIN 53 375.
  • the achievable COF depends on a variety of parameters, e.g. type and concentration of slip agent and the migration velocity of the slip agent.
  • the migration of slip agent is relatively slow and the best achievable Coefficient of Friction is too high for some applications.
  • a polymer composition which comprises 0.5% to 20% of butene-1 and 80% to 99.5% of propylene and from 0% to 0.35% of the composition of a synthetic amorphous silica antiblock agent.
  • the polymer composition and films therefrom have favourable optical (haze) and mechanical properties (tensile modulus and elongation at break) and meet certain solubles requirements.
  • propylene butene random copolymers were introduced in the late 90's in Europe for film applications to overcome some problems with propylene ethylene random copolymers as above described and shown in table 3.
  • propylene butene random copolymers are improving the blooming behaviour (due to its much lower extractables) and stiffness in comparison to propylene ethylene random copolymers with higher ethylene content at the same melting range and sealability.
  • a propylene terpolymer which comprises 20 to 60 wt% of a copolymer of propylene and ethylene, containing 1 to 5 wt% of ethylene, and 40 to 80 wt% of a copolymer of propylene together with ethylene and a C -C 8 ⁇ -olefin, the ethylene content being 1 to 5 wt% and C -C 8 ⁇ -olefin content being 6 to 15 wt%.
  • a propylene terpolymer which comprises 0.3 to 3 wt% of ethylene and 1 to 15 wt% of at least one C -C 8 ⁇ -olefin. This terpolymer can be used for the production of films having good sealing properties.
  • a polymer composition comprised of (i) a propylene terpolymer and (ii) a slip agent where the propylene terpolymer is comprised of 0.3 - 0.8 wt% of ethylene 2.0 - 15.0 wt% of at least one C 4 -C 8 ⁇ -olefin and 84.2 - 97.7 wt% of propylene for the production of films which exhibit the following properties: a) a dynamic Coefficient of Friction (COF) after storage for 3 days at 23 °C of smaller than 0.30 (measured according to DIN 53 375) b) a blooming behaviour, measured in terms of haze according to ASTM D 1003-92 after storage for 14 days at 40 °C which shows a deterioration of no more than 100 % of the original value which is measured after storage for 4 days at 23 °C.
  • COF dynamic Coefficient of Friction
  • the lower limit for the ethylene content of the propylene terpolymers used is 0.32 wt%, preferably 0.34 wt%, more preferably 0.36 wt% and most preferably 0.38 wt%.
  • the upper limit for the ethylene content of the propylene terpolymers used is 0.70 wt%, preferably 0.60 wt%, more preferably 0.50 wt% and most preferably 0.45 wt%.
  • the lower limit for the C 4 -C 8 ⁇ -olefin content of the propylene terpolymers used is 3.5 wt%, preferably 5.0 wt%, more preferably 6.5 wt% and most preferably 7.5 wt%.
  • the upper limit for the C -C 8 ⁇ -olefin content of the propylene terpolymers used is 13.5 wt%, preferably 12.0 wt%, more preferably 10.5 wt% and most preferably 9.5 wt%.
  • the at least one C 4 -C 8 ⁇ -olefin can be any one or mixtures of 1 -butene, 1-pentene, 4- methyl-1-pentene, 1-hexene, 1-heptene or 1-octene, where 1-butene is preferred.
  • the films according to the present invention have a dynamic COF of less than 0.30, preferably of less than 0.25, more preferably of less than 0.20 and most preferably of less than 0.18.
  • the above polymer compositions for the production of films with a blooming behaviour, measured in terms of haze according to ASTM D 1003-92 after storage for 14 days at 40 °C which shows a deterioration of no more than 80 %, preferably of no more than 60 % of the original value which is measured after storage for 4 days at 23 °C.
  • the haze of 80 ⁇ m thick cast film is e.g. deteriorating from an original value of 1.4 % to 2.1 % - which is a deterioration of 50%.
  • the films exhibit the following properties: c) a tensile modulus according to DIN 53457 of at least 350 MPa for a 50 ⁇ m film and d) a penetration energy according to DIN 53 373 of at least 28 J/mm for a 50 ⁇ m film.
  • the above polymer compositions for the production of films with a tensile modulus of at least 360 MPa, more preferably of at least 370 MPa and most preferably of at least 385 MPa. It is further preferred to use the above described polymer composition for the production of films showing a penetration energy of at least 30 J/mm, preferably of at least 33 J/mm, more preferably of at least 36 J/mm and most preferably of at least 39 J/mm.
  • the polymer composition comprises only from 0.01 to 0.30 wt% of an organic slip agent.
  • the lower limit for the slip agent content of the polymer composition used is 0.05 wt%, preferably 0.08 wt%, more preferably 0.10 wt% and most preferably 0.12 wt%.
  • the upper limit for the slip agent content of the polymer composition used is 0.25 wt%, preferably 0.22 wt%, more preferably 0.20 wt% and most preferably 0.18 wt%.
  • the organic slip agent comprises any one or mixtures of erucic acid amide (EAA) and/or oleic acid amide (OAA).
  • the organic slip agent comprises erucic acid amide.
  • Erucic acid amide is known to contribute rather little to a "bloom" layer, but shows a smaller migration velocity than for example oleic acid amide.
  • a slip agent can be used which consists solely or to at least 50% of erucic acid amide, the rest being e.g. oleic acid amide.
  • the COF after 3 days is much smaller than with known polymer compositions and films therefrom.
  • the films which are produced using the above described polymer composition have a COF after storage for 14 days of smaller than 0.18, preferably smaller than 0.15, more preferably smaller than 0.14 and most preferably smaller than 0.13.
  • haze In addition to the above described blooming characteristics (referred to as haze), it is preferred to use the above described polymer compositions for the production of films with a blooming behaviour measured as gloss after storage for 14 days at 40 °C of at least 115 %, preferably of at least 120 %, more preferably of at least 125 % and most preferably of at least 130 %.
  • a polymer composition comprised of a propylene terpolymer which has a proportion of polymer soluble in cold xylene at 23 °C of no more than 5 %, preferably of no more than 4.5 %, more preferably of no more than 4.0 %.
  • the films produced from polymer compositions containing these terpolymers meet the solubles requirements which are necessary for applications in food packaging.
  • the films according to the present invention have a preferred thickness of from 10 to 2000 ⁇ m.
  • the preferred production technology for the films is the cast film technology.
  • the films which are obtainable according to the present invention are advantageously used for the production of sterilizable lamination films, packaging films for FFS plants and for thin cast films, e.g as a substitute for BOPP films.
  • the polymerization process for the production of the propylene terpolymers according to the invention may be a continuous process or a batch process utilizing known methods and operating in liquid phase, optionally in the presence of an inert diluent, or in gas phase or by mixed liquid-gas techniques.
  • the process is preferably carried out in the presence of a stereospecific catalyst system.
  • any ordinary stereospecific Ziegler-Natta catalysts can be used.
  • An essential component in those catalysts are solid catalyst components comprising a titanium compound having at least one titanium-halogen bond, an internal electron donor compound and a magnesium halide in active form as a carrier for both the titanium component and the donor compound.
  • the catalysts can contain - as internal electron donor - compounds selected from ethers, ketones, lactones, compounds containing N, P and/or S atoms and esters of mono and dicarboxylic acids.
  • a further essential component of the catalyst is an organoaluminium compound, such as an alkylaluminium compound. Additionally, an external electron donor is generally used.
  • propylene terpolymer it is preferred to use a polymerization process based on at least one reactor and an optional second polymerization step comprising at least one gas phase reactor.
  • the catalyst system Before the catalyst system is used in the actual poylmerization process it is optionally pre- polymerized with small amounts of ⁇ -olefins in order to enhance catalyst performance and to improve the morphology of the end product.
  • the optionally prepolymerized catalyst system and a monomer mixture comprised of propylene, ethylene and at least one C 4 -C 8 ⁇ -olefin is fed into a reactor.
  • the at least one C 4 -C 8 ⁇ -olefin can be any one or mixtures of 1 -butene, 1- pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene or 1-octene. Particularly preferred is 1- butene.
  • the amount of propylene can be 59 to 89 wt%
  • the amount of ethylene can be 0.2 to 1.0 wt%
  • the amount of C 4 -C 8 ⁇ -olefin can be 10 to 40 wt%.
  • Polymerization can be carried out in the presence of the previously mentioned organoaluminium compound and an external donor compound at temperatures lower than 90 °C and pressures in the range of 10 to 90 bar, preferably 30 to 70 bar.
  • the polymerization is carried out in such conditions that 50 to 100 wt%, preferably 75 to 99 wt% of the end product is polymerized in the first reactor.
  • a suitable metallocene catalyst capable of catalyzing the formation of a propylene terpolymer can be used.
  • a suitable metallocene catalyst comprises a metallocene/activator reaction product impregnated in a porous support at maximum internal pore volume.
  • the catalyst complex comprises a ligand which is typically bridged, and a transition metal of group IVa ... Via , and an organoaluminium compound.
  • the catalytic metal compound is typically a metal halide.
  • a terpolymer in which the content of ethylene monomer is in the range of 0.2 to 1.0 wt%, preferably 0.3 to 0.7 wt% and the content of C 4 -C 8 ⁇ -olefin is in the range of 3 to 15 wt%, preferably of 5 to 12 wt%.
  • Hydrogen is added, when desired, into the first reactor for adjusting the molecular weight of polymer, as conventional.
  • reaction medium is optionally transferred into a second reactor, which can be a gas phase reactor.
  • the polymerization can be carried out at a temperature of 60 to 90 °C and at a pressure higher than 5 bar, preferably higher than 10 bar.
  • propylene and other monomers can be added into the second reactor.
  • Hydrogen can also be added into the gas phase reactor, if desired.
  • the precise control of the polymerization conditions and reaction parameters is within the skill of the art. After the polymerization in the first and the optional second reactor is finished, the polymer product is recovered by conventional procedures.
  • the resulting polymer particles may be pelletized in a conventional compounding extruder with various additives, which are generally used in thermoplastic polymer compositions, such as stabilizers, antioxidants, acid neutralizing agents, ultraviolet absorbers, clarifying agents, antiblocking agents, antistatic agents, antifogging agents, etc.
  • additives such as stabilizers, antioxidants, acid neutralizing agents, ultraviolet absorbers, clarifying agents, antiblocking agents, antistatic agents, antifogging agents, etc.
  • the polymer material contains at least one slip agent which may be derived from fatty acid amides, like erucic acid amide (EAA), oleic acid amide (OAA) or behenic acid amide (BAA), which may be added directly in the compounding step or during the processing of films in the way of an external masterbatch.
  • EAA erucic acid amide
  • OAA oleic acid amide
  • BAA behenic acid amide
  • the propylene terpolymer can be used for all extrusion and injection technologies.
  • they are used for technologies for extruded bi- and monoaxially - and non oriented films like cast, blown and rollstack films and coating in a film thickness range between 10 to 2000 ⁇ m.
  • the polymer compositions were processed to 30 ⁇ m, 50 ⁇ m and 80 ⁇ m thick cast films by conventional chill roll technology.
  • a Barmag extruder with a cylinder diameter of 60 mm and a screw with a length of 30 x diameter (incl. mix- and shear part) was used.
  • the feeding zone was notched and water cooled.
  • Molten material was cooled with a water cooled chill roll with a diameter of 450 mm and a mat surface followed by a second cooling roll with a diameter of 300 mm and a mat surface.
  • Set temperatures of chill roll and second cooling roll were 15 °C and 25 °C.
  • the films produced from polymer compositions containing these terpolymers are applicable for a variety of uses.
  • a 48 ⁇ m thick castfilm for bread packaging was produced at a Reifenhauser 90 castfilm mono extrusion line at a melt temperature of 235 °C, an output of 350 kg/h and a line speed of 82 m/min.
  • the film reel was cut later to a width of 437 mm.
  • the cut film was fed into a Lehmacher - sealing and cutting machinery for the production of bread bags with a heated wire at a temperature of 350°C.
  • Nr.5 C ⁇ d Raco 149 cycles/min
  • Nr.9 Ca/C ⁇ Raco 152 cycles/min
  • BOPP-films biaxially oriented polypropylene films
  • BOPP-films are very stiff and highly transparent films with good sealing properties. Films according to the invention are applicable as a substitute for some BOPP-films. While propylene ethylene random copolymers and propylene ethylene butene terpolymers with higher ethylene content show insufficient stiffness, the films according to the invention show an acceptable compromise between stiffness/sealing properties.
  • a film applicable as BOPP-substitute is e.g. constituted as a coextruded three layer film with an overall thickness of 15 to 30 ⁇ m, where both exterior layers are comprised of materials according to the invention and where the interior layer is comprised of a high crystalline propylene homopolymer.
  • Films according to the invention exhibit all of these properties and thus permit a reduction of cycle times on FFS-plants of up to 30 %.
  • Films according to the invention exhibit all of these properties and in addition they are sterilizable at 121 °C for 30 min.
  • the films according to the invention have higher starting toughness, less embrittlement and a smaller loss of optical properties compared to films from propylene butene or propylene ethylene random copolymers.
  • melt flow rate is that quantity of polymer in grams which the test apparatus standardized to DIN 53 735 extrudes within 10 minutes at a temperature of 230 °C under a weight of 2.16 kg.
  • Comonomer contents (ethylene and butene) were measured with Fourier transform infrared spectroscopy (FTIR) calibrated with 13 C-NMR.
  • FTIR Fourier transform infrared spectroscopy
  • Xylene solubles were determined at 25 °C according to ISO 6427.
  • the slip agent (EAA and/or OAA) is removed from the polymer by extracting 5-10 g of ground polymer sample in a Soxhlet apparatus with 110 ml chloroform for approximately 2.5 hours. After filtration of the extract, the amount of EAA and/or OAA is determined by GC using the internal standard method.
  • the dynamic Coefficient of Friction (COF) as a measure of the frictional behaviour of the film was determined according to DIN 53 375 on film samples with a thickness of 30 ⁇ m, where immediately after film production the film has been stored at room temperature (23°C). After storage for 1 , 3, 7 and 14 days the dynamic COF was measured at 23°C.
  • Gloss and haze as measures for the optical appearance of the film were determined according to DIN 67 530 (gloss) and ASTM D 1003-92 (haze), both on film samples with a thickness of 80 ⁇ m.
  • the penetration energy as a measure for toughness of the films was determined with Dynatest accordinging to DIN 53 373 on film samples with a thickness of 50 ⁇ m.
  • the tensile modulus as a measure for the stiffness of the films was determined according to DIN 53457 on film samples with a thickness of 50 ⁇ m.
  • the blooming behaviour as further measure of optical properties of the film was determined according to the following procedure:
  • the propylene ethylene 1 -butene terpolymer was polymerized in a continuous working polymerization system by using propylene, ethylene, 1 -butene, the catalyst compound C and cocatalysts (Triethylaluminium (TEAI), Electron donor (CMDMS)).
  • TEAI Triethylaluminium
  • CDMS Electron donor
  • catalyst compound C a commercial available Ziegler/Natta-catalyst (Titaniumchloride catalyst supported on MgCI 2 ), suitable for the production of propylene copolymers in a monomer suspension is used.
  • the polymerization is performed continuously in a prepolymerization reactor and a main polymerization reactor. Temperatures, pressures, catalyst-, monomer- and hydrogen feed in the separate polymerization steps as well as the polymer concentration in the main reactor are kept constant.
  • the molar mass of the terpolymer is controlled by adding hydrogen gas.
  • the concentration of hydrogen in the mixture of liquid monomers is continuously measured by gas chromatography. The relevant processing parameters and the analytical results of the resulting polymer are listed in tables 1 and 2.
  • the first polymerization step is performed in a small reactor (equipped with stirrer and cooling system), where an excess of a liquid mixture of the monomers propylene and 1- butene is prepolymerized for 9 minutes at 20°C. Therefore catalyst compound C, mixed with the cocatalyst compounds triethylaluminium (TEAI) and cyclohexyl-methyl- dimethoxysilane (CMDMS) as external electron donor, are continuously poured into the prepolymerization unit.
  • TEAI triethylaluminium
  • CDMS cyclohexyl-methyl- dimethoxysilane
  • the prepolymer (product A) is continuously removed from the prepolymerization unit and passed over into the main reactor system (equipped with stirrer and cooling system), where under excess of a liquid mixture of the monomers propylene and 1 -butene, under addition of ethylene, the final terpolymer (B) is formed. Further a mixture of monomers (propyIene/1-butene/ethylene) and hydrogen (for molar mass control) are fed into the main reactor continuously. The polymer concentration is kept constant at 169 g/l. A part of the reactor content (polymer-/monomer excess) is continuously removed from the reactor into a degassing unit to separate the formed terpolymer (B) from unreacted monomer mixture by evaporation.
  • the separated terpolymer (B) was subjected to a steam treatment, to remove the unreacted monomers and volatile substances, and then dried.
  • the polymer powder was mixed with 300 pm calciumstearate, 500 pm tetrakis[methyIene(3,5-di-tert-butyl-4- hydroxy-hydrocinnamate)]methane, 1000 ppm tris(2,4-di-tert-butylphenyl)phosphite and 1500 ppm SiO 2 and pelletized in a conventional compounding line.
  • the propylene ethylene 1 -butene terpolymer was polymerized following the procedure described for example 1 under the conditions as mentioned in tables 1 and 2 for example 2.
  • the polymer powder was mixed with 300 ppm calciumstearate, 500 ppm tetrakis[methyIene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)]methane, 1000 ppm tris(2,4-di-tert-butylphenyl)phosphite and 1500 ppm SiO 2 and pelletized in a conventional compounding line.
  • the propylene ethylene 1 -butene terpolymer powder of example 2 was mixed with 300 ppm calciumstearate, 500 ppm tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy- hydrocinnamate)]methane, 1000 ppm tris(2,4-di-tert-butylphenyl)phosphite, 1500 ppm Si0 2 and 1500 ppm erucic acid amide and pelletized in a conventional compounding line.
  • Comparative example 4 Comparative example 4:
  • the propylene ethylene 1-butene terpolymer was polymerized following the procedure described for example 1 under the conditions as mentioned in tables 1 and 2 for example 4.
  • the polymer powder was mixed with 300 ppm calciumstearate, 500 ppm tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)]methane, 1000 ppm tris(2,4-di-tert-butylphenyl)phosphite, 1500 ppm SiO 2 and 1500 ppm erucic acid amide and pelletized in a conventional compounding line.
  • the propylene 1-butene copolymer was polymerized following the procedure described for example 1 under the conditions as mentioned in tables 1 and 2 for example 5 without the addition of ethylene.
  • the polymer powder was mixed with 300 ppm calciumstearate, 500 ppm tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)]methane,
  • the propylene ethylene 1-butene terpolymer powder of example 5 was mixed with 300 ppm calciumstearate, 500 ppm tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy- hydrocinnamate)]methane, 1000 ppm tris(2,4-di-tert-butylphenyl)phosphite, 1500 ppm Si0 2 and 2000 ppm erucic acid amide and pelletized in a conventional compounding line.
  • the propylene 1-butene copolymer was polymerized following the procedure described for example 1 under the conditions as mentioned in tables 1 and 2 for example 7 without the addition of ethylene.
  • the polymer powder was mixed with 300 ppm calciumstearate, 500 ppm tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)]methane,
  • comparative example 9 a commercially available polymer grade (Borealis RD226CF) was used.
  • the COF after storage for 3 days for all of the comparative examples is above 0.30 and only 0.17 for example 3.
  • a rapid onset of a low COF value is important for the film processing industry, because it allows shorter storage times of the films. This is usually tried to achieve with higher concentrations of slip agent, as can be seen from examples 5 and 6. Higher concentrations of slip agent, however, result in a deterioration of the blooming behaviour.
  • Example 3 shows lower gloss values due to higher slip agent content.
  • Example 9 shows about 6 to 14 % higher tenacity but 20 % lower stiffness compared to examples 4 and 5.
  • Example 8 is comparable to example 9 with respect to stiffness but shows a much lower penetration energy.
  • Example 7 is more or less comparable to example 9.
  • Example 1 and 7 show the same stiffness but example 1 has a remarkably higher tenacity.
  • Example 2 and 3 show the best ratio of stiffness and tenacity. Compared to example 9 they show an increase of stiffness of about 11 % and an increase of penetration energy of about 30%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne l'utilisation d'une composition polymère comprenant un propylène terpolymère, constitué de 0.3 - 0.8 % en poids d'éthylène, de 2.0 - 15.0 % en poids d'au moins une oléfine α C4-C8 et de 84.2 - 97.7 % en poids de propylène, pour réaliser des films dont les propriétés optiques et mécaniques sont mieux équilibrées.
EP01998586A 2000-11-28 2001-11-22 Utilisation de propylenes terpolymeres pour la fabrication de films Withdrawn EP1352016A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01998586A EP1352016A1 (fr) 2000-11-28 2001-11-22 Utilisation de propylenes terpolymeres pour la fabrication de films

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP00125982A EP1209187A1 (fr) 2000-11-28 2000-11-28 Utilisation de terpolymères de propylène pour la préparation de films
EP00125982 2000-11-28
EP01998586A EP1352016A1 (fr) 2000-11-28 2001-11-22 Utilisation de propylenes terpolymeres pour la fabrication de films
PCT/EP2001/013602 WO2002044252A1 (fr) 2000-11-28 2001-11-22 Utilisation de propylenes terpolymeres pour la fabrication de films

Publications (1)

Publication Number Publication Date
EP1352016A1 true EP1352016A1 (fr) 2003-10-15

Family

ID=8170508

Family Applications (2)

Application Number Title Priority Date Filing Date
EP00125982A Withdrawn EP1209187A1 (fr) 2000-11-28 2000-11-28 Utilisation de terpolymères de propylène pour la préparation de films
EP01998586A Withdrawn EP1352016A1 (fr) 2000-11-28 2001-11-22 Utilisation de propylenes terpolymeres pour la fabrication de films

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP00125982A Withdrawn EP1209187A1 (fr) 2000-11-28 2000-11-28 Utilisation de terpolymères de propylène pour la préparation de films

Country Status (3)

Country Link
EP (2) EP1209187A1 (fr)
AU (1) AU2002216050A1 (fr)
WO (1) WO2002044252A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1302486A1 (fr) * 2001-10-09 2003-04-16 Borealis Technology Oy Procédé pour la préparation de copolymères de polypropylène
US20100075079A1 (en) * 2006-12-29 2010-03-25 Dow Global Technologies Inc. Ozone resistant compositions and articles
EP2020291A1 (fr) * 2007-07-31 2009-02-04 Borealis Technology Oy Utilisation de copolymères aléatoires en butène de propylène nucléé ou terpolymères pour la production de films soufflés stérilisables
EP2307496A1 (fr) 2008-07-02 2011-04-13 Dow Global Technologies Inc. Films et articles au bon goût et/ou aux performances odorantes
WO2011075492A1 (fr) 2009-12-18 2011-06-23 Dow Global Technologies Llc Films et articles préparés avec lesdits films
EP2666793A1 (fr) 2012-05-21 2013-11-27 Basell Poliolefine Italia S.r.l. Terpolymère à base de propylène
EP2743307A1 (fr) 2012-12-12 2014-06-18 Basell Poliolefine Italia S.r.l. Composition de polyoléfine
EP2813438A1 (fr) * 2013-06-11 2014-12-17 Basell Poliolefine Italia S.r.l. Terpolymères à base de propylène
CN106687522A (zh) * 2014-08-14 2017-05-17 伊奎斯塔化学有限公司 具有改进的澄清度和光泽度的三元共聚物组合物

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4839234A (en) * 1986-05-13 1989-06-13 Sumitomo Chemical Company, Limited Polypropylene film
IT1243430B (it) * 1990-09-28 1994-06-10 Himont Inc Composizioni di polimeri cristallini del propilene aventi bassa temperatura
CA2098664A1 (fr) * 1992-06-30 1993-12-31 Hajime Sadatoshi Copolymere statistique a base de polypropylene et pellicule faite de cette matiere
JPH07241906A (ja) * 1994-03-03 1995-09-19 Tokuyama Corp 二軸延伸ポリオレフィンフィルム
DE29623683U1 (de) * 1996-04-09 1999-04-15 BP Chemicals PlasTec GmbH, 89165 Dietenheim Verpackung
FI104824B (fi) * 1997-06-24 2000-04-14 Borealis As Menetelmä propeenin terpolymeerien aikaansaamiseksi

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0244252A1 *

Also Published As

Publication number Publication date
EP1209187A1 (fr) 2002-05-29
WO2002044252A1 (fr) 2002-06-06
AU2002216050A1 (en) 2002-06-11

Similar Documents

Publication Publication Date Title
US5455303A (en) Linear low density polyethylene based compositions with improved optics
US8889794B2 (en) Resin compositions for extrusion coating
EP2176340B1 (fr) Composition de polypropylène stérilisable et résistant aux chocs
EP2173806B1 (fr) Utilisation de terpolymères propylène butène nucléés pour la production de films soufflés stérilisables
US20050197456A1 (en) Sealing layer resin compositions
EP2718365B1 (fr) Compositions de resine ameliorees pour revetement par extrusion
JP4844091B2 (ja) プロピレン系樹脂組成物およびそのフィルム
EP1023388A1 (fr) Composition de polypropylene convenant a la confection d'un film oriente a l'etat solide
CA2459938A1 (fr) Compositions de copolymere du propylene cristallines dotees d'une capacite d'adherence et de proprietes optiques ameliorees et d'une solubilite reduite
JP7411454B2 (ja) ポリプロピレン系複合フィルムおよびそれを用いた積層体
JP3703846B2 (ja) Ｌｌｄｐｅ−ベースの伸縮性多層フィルム
JP4468303B2 (ja) 延伸フィルム
WO2002044251A1 (fr) Utilisation de terpolymeres de propylene pour produire des feuils
US6159587A (en) Stretchable multilayer films
EP1352016A1 (fr) Utilisation de propylenes terpolymeres pour la fabrication de films
US6010772A (en) Stretchable multilayer films
JPS6319255A (ja) ポリプロピレン積層フイルム
EP1608506B1 (fr) Films multicouches
EP0879850A2 (fr) Composition à base de polymer d'oléfine, procédé de préparation, film et film métallisé comprenant cette composition
JPH11217469A (ja) ポリエチレン系樹脂の性能改良方法およびそれを用いたポリエチレン系樹脂の加工方法
EP1366117A1 (fr) Compositions a base de copolymeres de propylene aleatoire, procede de fabrication et feuilles multicouches thermoscellables les comprenant
EP1430096A1 (fr) Composes a base de polymere propylene et feuilles multicouches thermoscellables les contenant
JP3324084B2 (ja) 積層体
JPS5846139B2 (ja) 押出被覆用樹脂組成物
JPS64988B2 (fr)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030514

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LEISTNER, DIRK

Inventor name: EMIG, JUERGEN

Inventor name: WOLFSBERGER, ANTON

Inventor name: GRUENBERGER, MANFRED

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LEISTNER, DIRK

Inventor name: EMIG, JUERGEN

Inventor name: WOLFSBERGER, ANTON

Inventor name: GRUENBERGER, MANFRED

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LEISTNER, DIRK

Inventor name: EMIG, JUERGEN

Inventor name: WOLFSBERGER, ANTON

Inventor name: GRUENBERGER, MANFRED

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BOREALIS POLYOLEFINE GMBH

17Q First examination report despatched

Effective date: 20070905

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20091202