EP4720188A1 - Composition polymère - Google Patents

Composition polymère

Info

Publication number
EP4720188A1
EP4720188A1 EP24722243.3A EP24722243A EP4720188A1 EP 4720188 A1 EP4720188 A1 EP 4720188A1 EP 24722243 A EP24722243 A EP 24722243A EP 4720188 A1 EP4720188 A1 EP 4720188A1
Authority
EP
European Patent Office
Prior art keywords
polymer composition
accordance
propylene
iso
ethylene
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.)
Pending
Application number
EP24722243.3A
Other languages
German (de)
English (en)
Inventor
Qizheng Dou
Minna Aarnio-Winterhof
Francis Costa
Dietrich Gloger
Jeroen Oderkerk
Jessica HESSELGREN
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 GmbH
Original Assignee
Borealis GmbH
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 GmbH filed Critical Borealis GmbH
Publication of EP4720188A1 publication Critical patent/EP4720188A1/fr
Pending legal-status Critical Current

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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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition

Definitions

  • the present invention pertains to a polymer composition (C) comprising a heterophasic propylene-ethylene copolymer (HECO), a propylene homopolymer (PP-H) and preferably a high-density polyethylene (HDPE).
  • C polymer composition
  • HECO heterophasic propylene-ethylene copolymer
  • PP-H propylene homopolymer
  • HDPE high-density polyethylene
  • the present invention further pertains to an article, preferably a film, comprising such a polymer composition and use of such article in packaging applications.
  • Heterophasic propylene compositions which are widely used for packaging products comprising two phases: a matrix phase, which can be a homopolymer or copolymer of propylene and a dispersed phase (so-called elastomeric phase) that is an ethylene-propylene rubber.
  • a matrix phase which can be a homopolymer or copolymer of propylene
  • a dispersed phase that is an ethylene-propylene rubber.
  • heterophasic propylene compositions are known to be high-impact materials over a wide range of temperatures.
  • the improved impact behavior is mainly attributed to the presence of the dispersed phase, compensating the brittle behavior of homopolymer or copolymers of propylene due to their crystallinity.
  • a major disadvantage of the dispersed phase then becomes stiffness that is lowered due to interruption of crystallinity.
  • the same dispersed phase may be responsible for an improved impact behavior and lowered stiffness, if not designed properly.
  • Another major disadvantage of having a multiple-phase system is optical properties that are not ideal. The presence of a matrix phase and a dispersed phase may cause the light being scattered at the interface between matrix and dispersed phase, causing more hazy appearance of the article made of such heterophasic propylene composition.
  • WO 2018/077663 A1 discloses a heterophasic propylene composition with a melt flow rate MFR2 of at most 6.0 g/10 min, comprising propylene homopolymer in an amount of higher than or equal to 80 wt.-%, an elastomeric ethylene-propylene rubber fraction in an amount of less than 20 wt.-%, a polymeric nucleating agent and at least one further nucleating or clarifying agent.
  • WO 2018/077663 A1 focuses on solving this problem with the use of nucleating agents.
  • WO 2007/071447 A1 discloses a polyolefin composition containing at least 80 wt.-% of a heterophasic propylene copolymer, a polymeric nucleating agent and up to 20 wt.-% of low- density polyethylene. Even though WO 2007/071447 A1 aims to improve optical properties along with mechanical properties, it proposes the use of polymeric nucleating agent and the low-density polyethylene for that purpose.
  • the present invention relates to a polymer composition that meets the mentioned requirements.
  • the present invention relates to a polymer composition (C) comprising: a) a heterophasic propylene-ethylene copolymer (HECO) having a melt flow rate (MFR2) as determined at 230 °C under a load of 2.16 kg in accordance with ISO 1133 of from 0.1 to 15.0 g/10 min, in an amount of from 50 to 99 wt.-% based on the total weight of the polymer composition (C), comprising: a1) a crystalline matrix that is a propylene homopolymer or a copolymer of propylene and ethylene and/or C3-C12 alpha olefins; a2) an amorphous propylene-ethylene elastomer (EPR); wherein the heterophasic propylene-ethylene copolymer (HECO) is further characterized by its crystalline fraction (CF) and soluble fraction (SF) as determined by CRYSTEX QC analysis, wherein the soluble fraction (SF) has an ethylene content of from 10
  • the present invention further relates to an article, preferably a film, comprising the polymer composition (C) as described herein.
  • the present invention further relates to use of the article, more preferably the film as disclosed herein in packaging applications.
  • a “propylene homopolymer” as used herein indicates a polymer that mainly consists of monomer units of propylene and comprises up to 0.1 mol-% comonomer units.
  • a “propylene copolymer” as used herein indicates a polymer that comprises monomer units of propylene and comonomer units. When the comonomers of the polymer are distributed randomly along the polymer chain, the propylene copolymer is called as “random” and when the comonomers of the polymer are distributed as blocks along the chain, the propylene copolymer is called as “block”.
  • Heterophasic propylene-ethylene copolymer indicates polymer compositions comprising two phases: a crystalline phase that is a propylene homopolymer or copolymer of propylene and ethylene and/or another comonomer, and an amorphous phase that is an elastomeric rubber (usually ethylene-propylene rubber, EPR).
  • a “unimodal polymer” as used herein refers to a polymer having a single fraction, usually produced in a single-reactor system. When a polymer contains multiple fractions differing from each other by at least one property, such as molecular weight, it is called as “multimodal” (bimodal, if there are two fractions present).
  • the polymer composition (C) comprises a heterophasic propylene-ethylene copolymer (HECO) in an amount of from 50 to 99 wt.-%, a propylene homopolymer (PP-H) in an amount of from 1 to 30 wt.-%, and optionally a high density polyethylene (HDPE) in an amount of from 0 to 20 wt.-%, based on the total weight of the polymer composition (C).
  • HECO heterophasic propylene-ethylene copolymer
  • PP-H propylene homopolymer
  • HDPE high density polyethylene
  • the polymer composition (C) has at least one or more, preferably all of the following properties:
  • tensile modulus in machine direction measured on 400 pm cast film in accordance with ISO 527-3, of from 200 to 1000 MPa, more preferably from 400 to 950 MPa,
  • tensile modulus in transverse direction measured on 400 pm cast film in accordance with ISO 527-3, of from 200 to 1000 MPa, more preferably from 400 to 850 MPa,
  • haze measured on 400 pm cast film in accordance with ASTM D1003-00, of from 5 to 40%, more preferably from 10 to 30%.
  • polymer composition (C) may preferably have at least one or more of the properties as listed above, it is the most preferred when it has all the mentioned properties.
  • the polymer composition (C) has at least one or more, preferably all of the following properties: - a Charpy Notched Impact Strength (NIS), measured on 80x10x4 mm specimens at 23 °C in accordance with ISO 179 1eA, of from 15 to 70 kJ/m 2 , more preferably from 20 to 50 kJ/m 2 ,
  • NIS Charpy Notched Impact Strength
  • NIS Charpy Notched Impact Strength
  • polymer composition (C) may preferably have at least one or more of the properties as listed above, it is the most preferred when it has all the mentioned properties.
  • HECO Heterophasic propylene-ethylene copolymer
  • the heterophasic propylene-ethylene copolymer (HECO) according to the present invention comprises a crystalline matrix that is a propylene homopolymer or a copolymer of propylene and ethylene and/or C3-C12 alpha olefins; and an amorphous propylene-ethylene elastomer (EPR).
  • Crystalline matrix is preferably a homopolymer of propylene, preferably with a melt flow rate (MFR 2 ) as determined at 230 °C under a load of 2.16 kg in accordance with ISO 1133 of from 0.5 to 10.0 g/10 min, more preferably of from 1.0 to 3.5 g/10 min.
  • MFR 2 melt flow rate
  • heterophasic propylene-ethylene copolymer is in an amount of from 60 to 90 wt.-%, based on the total weight of the polymer composition (C).
  • the heterophasic propylene-ethylene copolymer has a melt flow rate (MFR2) as determined at 230 °C under a load of 2.16 kg in accordance with ISO 1133 of from 0.1 to 15.0 g/10 min. It is preferred that the melt flow rate (MFR 2 ) as determined at 230 °C under a load of 2.16 kg in accordance with ISO 1133 ranges from 0.5 to 10.0 g/10 min, more preferably from 1.0 to 7.0 g/10 min.
  • the heterophasic propylene-ethylene copolymer is further characterized by its crystalline fraction (CF) and soluble fraction (SF) as determined by CRYSTEX QC analysis, wherein the soluble fraction (SF) has an ethylene content of from 10 to 50 wt.-% based on the weight of the soluble fraction (SF).
  • the heterophasic propylene-ethylene copolymer preferably has at least one or more, preferably all of the following properties according to CRYSTEX QC analysis: - a crystalline fraction (CF) in an amount of from 70 to 95 wt.-% and a soluble fraction (SF) in an amount from 5 to 30 wt.-%, based on the total weight of the heterophasic propyleneethylene copolymer (HECO),
  • C2 total ethylene (C2) content of from 0.5 to 25 wt.-%, more preferably from 1 to 15 wt.-%,
  • C2 ethylene (C2) content of crystalline fraction (CF) of from 0.5 to 25 wt.-%, more preferably from 1 to 20 wt.-%,
  • C2 ethylene (C2) content of soluble fraction (SF) of from 20 to 40 wt.-%, more preferably from 25 to 35 wt.-%,
  • IV intrinsic viscosity of soluble fraction (SF), determined in accordance with DIN ISO 1628/1 (in Decalin 135 °C), of from 0.5 to 10.0 dL/g, more preferably of from 1.0 to 5.0 dL/g.
  • heterophasic propylene-ethylene copolymer may preferably have at least one or more properties according to CRYSTEX QC given above, it is the most preferred when it has all of the mentioned properties.
  • the heterophasic propylene-ethylene copolymer may be produced in a multistage polymerization process, comprising the steps of: a) preparing the crystalline matrix that is a propylene homopolymer or a copolymer of propylene and ethylene and/or C3-C12 alpha-olefins by a1) polymerizing in a first reactor propylene to obtain a first propylene polymer fraction, a2) transferring the first propylene polymer fraction to a second reactor, and polymerizing in the second reactor propylene to obtain a second propylene polymer fraction, b) preparing a disperse phase of the heterophasic propylene copolymer by b1) transferring the first propylene polymer fraction and the second propylene polymer fraction to a third reactor, and polymerizing in the third reactor propylene and ethylene, to obtain a third propylene polymer fraction, wherein polymerizing in steps a1), a2) and b1) is
  • the first reactor is preferably a slurry phase reactor, such as a loop reactor. It is preferred that the operating temperature in the first reactor, preferably the loop reactor, is in the range from 62 to 95 °C, more preferably in the range from 65 to 90 °C, still more preferably in the range from 70 to 85 °C.
  • the pressure in the first reactor preferably in the loop reactor, is in the range from 20 to 80 bar, preferably 30 to 70 bar, like 35 to 65 bar.
  • the first reactor preferably the loop reactor, a propylene homopolymer is produced.
  • the first propylene polymer fraction is a propylene homopolymer fraction.
  • a ratio of the feed of hydrogen to the feed of propylene is 0.10 to 0.6 mol/kmol, more preferably 0.15 to 0.50 mol/kmol, and most preferably 0.20 to 0.45 mol/kmol.
  • the average residence time in the first reactor is typically from 15 to 120 min, preferably from 20 to 80 min.
  • the average residence time T can be calculated from equation (1) below:
  • VR is the volume of the reaction space (in case of a loop reactor, the volume of the reactor, in case of the fluidized bed reactor, the volume of the fluidized bed)
  • Qo is the volumetric flow rate of the product stream (including the polymer product and the fluid reaction mixture).
  • the production rate is suitably controlled by the catalyst feed rate and temperature. It is also possible to influence the production rate by suitable selection of the monomer concentration. The desired monomer concentration can then be achieved by suitably adjusting the propylene feed rate.
  • the second reactor preferably is a first gas phase reactor, such as a first fluidized bed gas phase reactor. It is preferred that the operating temperature in the second reactor, preferably the first gas phase reactor, is in the range from 65 to 95 °C, more preferably in the range from 70 to 85 °C. Preferably, the pressure in the second reactor, preferably in the first gas phase reactor, is in the range from 5 to 50 bar, preferably 15 to 40 bar. The average residence time in the second reactor, preferably the first gas phase reactor, is typically 30 to 130 min. Reference is made to equation (1) above.
  • a propylene homopolymer is produced in the second reactor, preferably the first gas phase reactor.
  • the second propylene polymer fraction is a propylene homopolymer fraction.
  • hydrogen is added in the second reactor in order to control the molecular weight, i.e. the melt flow rate MFR2.
  • the hydrogen to propylene ratio (H2/C3 ratio) in the second reactor, preferably the first gas phase reactor is in the range from 2.0 to 9.0 mol/kmol, more preferably 4.0 to 8.0 mol/kmol.
  • the third reactor preferably is a second gas phase reactor, such as a second fluidized bed gas phase reactor. It is preferred that the operating temperature in the third reactor, preferably the second gas phase reactor, is in the range from 65 to 85 °C, more preferably in the range from 68 to 82 °C. Typically, the operating temperature in third reactor is lower than the operating temperature in the second reactor. Typically, the pressure in the third reactor, preferably in the second gas phase reactor, is in the range from 5 to 50 bar, preferably 15 to 40 bar.
  • the average residence time in the third reactor, preferably the second gas phase reactor, is typically 30 to 130 min. Reference is made to equation (1) above.
  • the disperse phase of the heterophasic propylene copolymer is produced, i.e. a copolymer of propylene and ethylene.
  • the ethylene to propylene ratio (C2/C3 ratio) in the third reactor, preferably the second gas phase reactor, is in the range from 300 to 1000 mol/kmol, more preferably 400 to 800 mol/kmol.
  • a preferred multistage process is the above-identified slurry-gas phase process, such as developed by Borealis and known as the Borstar® technology.
  • EP 0 887 379 A1 and EP 0 517 868 A1 are examples of EP applications.
  • heterophasic propylene-ethylene copolymer there may be a pre-polymerization conducted prior to the first polymerization step a).
  • a polypropylene is produced.
  • the pre-polymerization is conducted in the presence of the Ziegler-Natta catalyst system. However, this shall not exclude the option that at a later stage for instance further cocatalyst is added in the polymerization process, for instance in the first reactor.
  • the pre-polymerization reaction is typically conducted at a temperature of 0 to 60 °C, preferably from 15 to 50 °C, and more preferably from 20 to 45 °C.
  • the pressure in the pre-polymerization reactor is not critical but must be sufficiently high to maintain the reaction mixture in liquid phase. Thus, the pressure may be from 20 to 100 bar, for example 30 to 70 bar.
  • the average residence time in the prepolymerization reactor is typically 15 to 45 min. Reference is made to equation (1) above.
  • the pre-polymerization is conducted as bulk slurry polymerization in liquid propylene, i.e. the liquid phase mainly comprises propylene, with optionally inert components dissolved therein.
  • the mixture of the Ziegler-Natta catalyst system and the polypropylene produced in the pre- polymerization reactor is transferred to the first reactor.
  • the total amount of the polypropylene produced in the pre-polymerization reactor in the first, second and third propylene polymer fractions is rather low and typically not more than 5.0 wt.-%, more preferably not more than 4.0 wt.-%, still more preferably in the range from 0.1 to 4.0 wt.-%, like in the range 0.5 of to 3.0 wt.-%.
  • the catalyst used for the production of heterophasic propylene-ethylene copolymer may be a solid Ziegler-Natta catalyst (ZN-C), which comprises compounds (TC) of a transition metal of Group 4 to 6 of IIIPAC, like titanium, a Group 2 metal compound (MC), like a magnesium, and an internal donor (ID) being a non-phthalic compound, preferably a non- phthalic acid ester, still more preferably being a diester of non-phthalic dicarboxylic acids as described in more detail below.
  • ZN-C Ziegler-Natta catalyst
  • TC transition metal of Group 4 to 6 of IIIPAC
  • MC Group 2 metal compound
  • ID internal donor
  • the catalyst is in a preferred embodiment fully free of undesired phthalic compounds.
  • the solid catalyst is free of any external support material, like silica or MgCh, but the catalyst is self-supported.
  • the Ziegler-Natta catalyst can be further defined by the way as obtained. Accordingly, the Ziegler-Natta catalyst is preferably obtained by a process comprising the steps of a) ai) providing a solution of at least a Group 2 metal alkoxy compound (Ax) being the reaction product of a Group 2 metal compound (MC) and a monohydric alcohol (A) comprising in addition to the hydroxyl moiety at least one ether moiety optionally in an organic liquid reaction medium; or a2) a solution of at least a Group 2 metal alkoxy compound (Ax’) being the reaction product of a Group 2 metal compound (MC) and an alcohol mixture of the monohydric alcohol (A) and a monohydric alcohol (B) of formula ROH, optionally in an organic liquid reaction medium; or as) providing a solution of a mixture of the Group 2 alkoxy compound (Ax) and a Group 2 metal alkoxy compound (Bx) being the reaction product of a Group 2 metal compound (MC) and the monohydric alcohol (B
  • the magnesium alkoxy compounds as defined above can be prepared in situ in the first step of the catalyst preparation process, step a), by reacting the magnesium compound with the alcohol(s) as described above, or said magnesium alkoxy compounds can be separately prepared magnesium alkoxy compounds or they can be even commercially available as ready magnesium alkoxy compounds and used as such in the catalyst preparation process of the invention.
  • Illustrative monohydric alcohols (B) are of formula ROH, with R being straight-chain or branched C2-C16 alkyl residue, preferably C 4 to C10, more preferably C6to Cs alkyl residue.
  • the most preferred monohydric alcohol is 2-ethyl-1 -hexanol or octanol.
  • a mixture of Mg alkoxy compounds (Ax) and (Bx) or mixture of alcohols (A) and (B), respectively, are used and employed in a mole ratio of Bx:Ax or B:A from 10:1 to 1 :10, more preferably 6:1 to 1 :6, most preferably 4.1 to 1 :4.
  • Magnesium alkoxy compound may be a reaction product of alcohol(s), as defined above, and a magnesium compound selected from dialkyl magnesium, alkyl magnesium alkoxides, magnesium dialkoxides, alkoxy magnesium halides and alkyl magnesium halides. Further, magnesium dialkoxides, magnesium diaryloxides, magnesium aryloxyhalides, magnesium aryloxides and magnesium alkyl aryloxides can be used. Alkyl groups can be a similar or different C1-C20 alkyl, preferably C2-C10 alkyl.
  • Typical alkyl-alkoxy magnesium compounds when used, are ethyl magnesium butoxide, butyl magnesium pentoxide, octyl magnesium butoxide and octyl magnesium octoxide.
  • the dialkyl magnesium are used.
  • Most preferred dialkyl magnesium are butyl octyl magnesium or butyl ethyl magnesium.
  • magnesium compound can react in addition to the alcohol (A) and alcohol (B) also with a polyhydric alcohol (C) of formula R” (OH) m to obtain said magnesium alkoxide compounds.
  • Preferred polyhydric alcohols if used, are alcohols, wherein R” is a straight-chain, cyclic or branched C2 to C10 hydrocarbon residue, and m is an integer of 2 to 6.
  • the magnesium alkoxy compounds of step a) are thus selected from the group consisting of magnesium dialkoxides, diaryloxy magnesium, alkyloxy magnesium halides, aryloxy magnesium halides, alkyl magnesium alkoxides, aryl magnesium alkoxides and alkyl magnesium aryloxides. In addition a mixture of magnesium dihalide and a magnesium dialkoxide can be used.
  • the solvents to be employed for the preparation of the present catalyst may be selected among aromatic and aliphatic straight chain, branched and cyclic hydrocarbons with 5 to 20 carbon atoms, more preferably 5 to 12 carbon atoms, or mixtures thereof.
  • Suitable solvents include benzene, toluene, cumene, xylene, pentane, hexane, heptane, octane and nonane. Hexanes and pentanes are particular preferred.
  • the reaction for the preparation of the magnesium alkoxy compound may be carried out at a temperature of 40 °C to 70 °C. Most suitable temperature is selected depending on the Mg compound and alcohol(s) used.
  • the internal donor (ID) used in the preparation of the catalyst used in the present invention is preferably selected from (di)esters of non-phthalic carboxylic (di)acids, 1 ,3-diethers, derivatives and mixtures thereof.
  • Especially preferred donors are diesters of mono-unsaturated dicarboxylic acids, in particular esters belonging to a group comprising malonates, maleates, succinates, citraconates, glutarates, cyclohexene-1 ,2-dicarboxylates and benzoates, and any derivatives and/or mixtures thereof.
  • Preferred examples are e.g. substituted maleates and citraconates, most preferably citraconates.
  • Turbulence minimizing agent if used, is preferably selected from a-olefin polymers of a-olefin monomers with 6 to 20 carbon atoms, like polyoctene, polynonene, polydecene, polyundecene or polydodecene or mixtures thereof. Most preferable it is polydecene.
  • R a , R b and R c can be chosen independently from one another and can be the same or different.
  • silanes are (tert-butyl)2Si(OCH3)2, (cyclohexyl)(methyl)Si(OCH 3 ) 2 , (phenyl) 2 Si(OCH 3 )2 and (cyclopentyl) 2 Si(OCH 3 ) 2 , or of general formula
  • R 3 and R 4 can be the same or different a represent a hydrocarbon group having 1 to 12 carbon atoms.
  • R 3 and R 4 are independently selected from the group consisting of linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, branched aliphatic hydrocarbon group having 1 to 12 carbon atoms and cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms.
  • R 3 and R 4 are independently selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, octyl, decanyl, iso-propyl, iso-butyl, iso-pentyl, tert.-butyl, tert.- amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyl.
  • both R 3 and R 4 are the same, yet more preferably both R 3 and R 4 are an ethyl group.
  • Especially preferred external donors are the pentyl dimethoxy silane donor (D-donor) or the cyclohexylmethyl dimethoxy silane donor (C-Donor).
  • co-catalyst is preferably a compound of group 13 of the periodic table (IIIPAC), e.g. organo aluminum, such as an aluminum compound, like aluminum alkyl, aluminum halide or aluminum alkyl halide compound.
  • IIIPAC periodic table
  • organo aluminum such as an aluminum compound, like aluminum alkyl, aluminum halide or aluminum alkyl halide compound.
  • the co-catalyst (Co) is a trialkylaluminium, like triethylaluminium (TEAL), dialkyl aluminium chloride or alkyl aluminium dichloride or mixtures thereof.
  • the co- catalyst (Co) is triethylaluminium (TEAL).
  • the triethyl aluminium has a hydride content, expressed as AIH3, of less than 1.0 wt.% with respect to the triethyl aluminium (TEAL). More preferably, the hydride content is less than 0.5 wt.%, and most preferably the hydride content is less than 0.1 wt.%.
  • the ratio between the co-catalyst (Co) and the external donor (ED) [Co/ED] and/or the ratio between the co-catalyst (Co) and the transition metal (TM) [Co/TM] should be carefully chosen.
  • the mole ratio of co-catalyst (Co) to external donor (ED) [Co/ED] must be in the range of 5 to 45, preferably is in the range of 5 to 35, more preferably is in the range of 5 to 25; and optionally the mole ratio of co-catalyst (Co) to titanium compound (TC) [Co/TC] must be in the range of above 80 to 500, preferably is in the range of 100 to 350, still more preferably is in the range of 120 to 300.
  • the Ziegler-Natta catalyst (ZN-C) is preferably modified by the so-called BNT-technology during the above described pre-polymerization step in order to introduce the polymeric nucleating agent, preferably a vinyl compound. Details of such a modification can further be found in EP 1183307 and EP 3 184 587.
  • Propylene homopolymer (PP-H) is preferably modified by the so-called BNT-technology during the above described pre-polymerization step in order to introduce the polymeric nucleating agent, preferably a vinyl compound. Details of such a modification can further be found in EP 1183307 and EP 3 184 587.
  • PP-H Propylene homopolymer
  • the propylene homopolymer (PP-H) according to the present invention is used in an amount of from 1 to 30 wt.-%, preferably from 5 to 20 wt.-%, based on the total weight of the polymer composition (C).
  • Addition of propylene homopolymer (PP-H) allows the polymer composition (C) to have improved optical properties, as it allows the amorphous ethylene-propylene elastomer (EPR) to be dispersed within the crystalline matrix in fine particles, because of a favorable viscosity ratio between matrix (PP-H) and the dispersed amorphous ethylenepropylene elastomer (EPR)
  • the melt flow rate (MFR2) of the propylene homopolymer (PP-H) as determined at 230 °C under a load of 2.16 kg in accordance with ISO 1133 is from 0.01 to 5.0 g/10 min, preferably from 0.01 to 3.0 g/10 min, more preferably from 0.1 to 1.0 g/10 min.
  • Addition of the high molar mass (low MFR2) PP-H also may act as nucleating agent during sheet extrusion, which decreases size of crystalline supramolecular structures (spherulites), further improving the transparency and optical quality.
  • the polypropylene homopolymer (PP-H) according to the present invention preferably has a pentad isotacticity (mmmm), as determined in accordance with 13 C NMR analysis as described herein, of from 70 to 99%, more preferably from 85 to 95%.
  • mmmm pentad isotacticity
  • the polypropylene homopolymer (PP-H) according to the present invention has a melt flow rate (MFR 2 ) as determined at 230 °C under a load of 2.16 kg in accordance with ISO 1133, of from 0.01 to 3.0 g/10 min, more preferably of from 0.1 to 1.0 g/10 min and a pentad isotacticity (mmmm), as determined in accordance with 13 C NMR analysis as described herein, of from 70 to 99%, more preferably from 85 to 95%.
  • MFR 2 melt flow rate
  • mmmm pentad isotacticity
  • HDPE High density polyethylene
  • the high-density polyethylene (HDPE) according to the present invention is preferably used in an amount of from 0 to 20 wt.-%, more preferably from 2 to 10 wt.-%, based on the total weight of the polymer composition (C).
  • the high-density polyethylene (HDPE) has a density of from 940 to 985 kg/m 3 , preferably of from 950 to 975 kg/m 3 .
  • HDPE high-density polyethylene
  • the high density-polyethylene has a melt flow rate (MFR 2 ) as determined at 190 °C under a load of 2.16 kg in accordance with ISO 1133 ranging from 10 to 100 g/10 min, more preferably from 30 to 80 g/10 min.
  • MFR 2 melt flow rate
  • HDPE high-density polyethylene
  • EPR ethylene-propylene elastomer
  • the present invention further relates to an article, preferably a film comprising the polymer composition (C) as mentioned herein. It is preferred that the article comprises the polymer composition (C) in an amount of at least 90 wt.-%, more preferably at least 95 wt.-% based on the total weight of the article. It is the most preferred that the article consists of the polymer composition (C).
  • the film may be a cast film or a blown film, while the cast film is more preferred.
  • the film, more preferably the cast film may be a monolayer film or a single layer film within a structure of multilayer film.
  • the thickness of the film preferably ranges from 100 to 700 pm, more preferably from 200 to 500 pm.
  • the article more preferably the film according to the present invention, has at least one or more, preferably all of the following properties:
  • tensile modulus in machine direction measured on 400 pm cast film in accordance with ISO 527-3, of from 200 to 1000 MPa, more preferably from 400 to 950 MPa,
  • tensile modulus in transverse direction measured on 400 pm cast film in accordance with ISO 527-3, of from 200 to 1000 MPa, more preferably from 400 to 850 MPa,
  • haze measured on 400 pm cast film in accordance with ASTM D1003-00, of from 5 to 40%, more preferably from 10 to 30%.
  • the article may preferably have at least one or more of the properties as listed above, it is the most preferred when it has all the mentioned properties.
  • the article more preferably the film according to the present invention, has at least one or more, preferably all of the following properties:
  • an elongation at break in transverse direction measured on 400 pm cast film at 0 °C in accordance with ISO 527-3, of from 200 to 850%, more preferably from 300 to 800%.
  • the article more preferably the film according to the present invention, may preferably have at least one or more of the properties as listed above, it is the most preferred when it has all the mentioned properties.
  • the present invention further relates to a use of the article, more preferably film disclosed herein in a packaging applications.
  • Heterophasic propylene-ethylene copolymer (HECO) HECO as used in the examples was produced using a Ziegler-Natta catalyst as used in the inventive examples of WO 2016/066446 A1 and pre-polymerized with vinylcyclohexene to achieve nucleation with poly(vinylcyclohexene). Nucleation by prepolymerization with vinylcyclohexane is described in EP 2 960256 B1 and EP 2 960279 B1 in detail. Dicyclopentyl dimethoxy silane (donor D) was used as external donor and triethyl aluminium (TEAL) was used as co-catalyst.
  • donor D Dicyclopentyl dimethoxy silane
  • TEAL triethyl aluminium
  • Cast films having 400 pm thickness were produced from the polymer compositions (C) as presented in Table 3, on a Collin lab scale cast film line, with a melt temperature of 250 °C, chill temperature of 60 °C and output rate of 8 kg/h.
  • the morphology of the cast films made of inventive and comparative examples have been analysed using AFM, as provided in Figures 1-4.
  • Fig. 1 shows the image of films made on CE1
  • Fig. 2 shows CE2
  • Fig.3 shows IE1
  • Fig. 4 shows IE2.
  • addition of PP-H has resulted in the particles of EPR to be dispersed into smaller particles.
  • HDPE is also added to the polymer composition (C)
  • the EPR particle size is even more decreased.
  • improved optics were obtained for IE1 and IE2, which can be seen in Table 4.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention divulgue une composition polymère (C) comprenant : a) un copolymère de propylène-éthylène hétérophasique (HECO) ayant un indice de fluidité (MFR2) tel que déterminé à 230 °C sous une charge de 2,16 kg conformément à la norme ISO 1133 de 0,1 à 15,0 g/10 min, en une quantité de 50 à 99 % en poids sur la base du poids total de la composition de polymère (C), comprenant : a1) une matrice cristalline qui est un homopolymère de propylène ou un copolymère de propylène et d'éthylène et/ou d'alpha-oléfines en C3-C12 ; a2) un élastomère de propylène-éthylène amorphe (EPR) ; le copolymère de propylène-éthylène hétérophasique (HECO) étant en outre caractérisé par sa fraction cristalline (CF) et sa fraction soluble (SF) telles que déterminées par analyse CRYSTEX QC, la fraction soluble (SF) ayant une teneur en éthylène de 10 à 50 % en poids sur la base du poids total de la fraction soluble (SF ; b) un homopolymère de propylène (PP-H) ayant un indice de fluidité (MFR2) tel que déterminé à 230 °C sous une charge de 2,16 kg conformément à la norme ISO 1133 de 0,01 à 5,0 g/10 min, en une quantité de 1 à 30 % en poids sur la base du poids total de la composition polymère (C) ; et c) éventuellement, un polyéthylène haute densité (HDPE) ayant une densité de 940 à 985 kg/m3, en une quantité de 0 à 20 % en poids sur la base du poids total de la composition polymère (C).
EP24722243.3A 2023-05-24 2024-04-26 Composition polymère Pending EP4720188A1 (fr)

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EP23175058 2023-05-24
PCT/EP2024/061510 WO2024240445A1 (fr) 2023-05-24 2024-04-26 Composition polymère

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FI86867C (fi) 1990-12-28 1992-10-26 Neste Oy Flerstegsprocess foer framstaellning av polyeten
FI111848B (fi) 1997-06-24 2003-09-30 Borealis Tech Oy Menetelmä ja laitteisto propeenin homo- ja kopolymeerien valmistamiseksi
FI991057A0 (fi) 1999-05-07 1999-05-07 Borealis As Korkean jäykkyyden propeenipolymeerit ja menetelmä niiden valmistamiseksi
ES2335420T3 (es) 2005-12-22 2010-03-26 Borealis Technology Oy Composiciones poliolefinas.
EP2415790B1 (fr) 2010-07-13 2014-09-24 Borealis AG Composant de catalyseur
ES2397547T3 (es) * 2010-08-27 2013-03-07 Borealis Ag Composición de polipropileno rígido con excelente alargamiento de rotura
EP2543684B1 (fr) 2011-07-07 2016-12-21 Borealis AG Procédé de fabrication de polypropylène isotactique
ES2727405T3 (es) 2011-12-30 2019-10-16 Borealis Ag Preparación de catalizadores de ZN PP libres de ftalato
EP2610272B1 (fr) 2011-12-30 2017-05-10 Borealis AG Composant de catalyseur
EP2610270B1 (fr) 2011-12-30 2015-10-07 Borealis AG Composant de catalyseur
TR201809062T4 (tr) 2014-06-27 2018-07-23 Borealis Ag Çekirdekli polipropilen bileşiği.
ES2676219T3 (es) 2014-06-27 2018-07-17 Borealis Ag Componente de catalizador para la preparación de poliolefinas nucleadas
EP3015503A1 (fr) 2014-10-27 2016-05-04 Borealis AG Polypropylène hétérophasique avec un équilibre amélioré en termes de rigidité/impact
WO2016070416A1 (fr) * 2014-11-07 2016-05-12 Borouge Compounding Shanghai Co., Ltd. Composition de polypropylène présentant une résistance améliorée aux rayures, une résistance aux chocs et une rigidité équilibrées
EP3184587B1 (fr) 2015-12-21 2020-03-18 Borealis AG Articles extrudés avec des propriétés optiques améliorées
EP3315551B1 (fr) 2016-10-25 2021-03-03 Borealis AG Composition de polypropylène hétérophasique présentant de meilleures propriétés mécaniques et optiques

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