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WO2018147944A1 - Polypropylènes à haute résistance à l'état fondu présentant une aptitude au traitement améliorée - Google Patents

Polypropylènes à haute résistance à l'état fondu présentant une aptitude au traitement améliorée Download PDF

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Publication number
WO2018147944A1
WO2018147944A1 PCT/US2018/012140 US2018012140W WO2018147944A1 WO 2018147944 A1 WO2018147944 A1 WO 2018147944A1 US 2018012140 W US2018012140 W US 2018012140W WO 2018147944 A1 WO2018147944 A1 WO 2018147944A1
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Prior art keywords
polypropylene
range
branched
molecular weight
low molecular
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PCT/US2018/012140
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English (en)
Inventor
Sasha L. SCHMITT
George J. Pehlert
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Exxonmobil Chemical Patents Inc.
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Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to JP2019542421A priority Critical patent/JP7604095B2/ja
Priority to EP18751546.5A priority patent/EP3580275B1/fr
Priority to US16/477,463 priority patent/US11572462B2/en
Priority to KR1020197022892A priority patent/KR102257918B1/ko
Priority to CN201880010332.4A priority patent/CN110248995A/zh
Publication of WO2018147944A1 publication Critical patent/WO2018147944A1/fr

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    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present disclosure relates to improved processing of branched polypropylene, and in particular to blends of a branched polypropylene and low molecular weight polyolefin.
  • Described herein is a process to produce a polypropylene composition
  • a process to produce a polypropylene composition comprising (or consisting of, or consisting essentially of) combining a branched polypropylene with a low molecular weight polyolefin having a melt flow rate (ASTM D1238, 230°C/2.16 kg) of at least 50 g/10 min to obtain a polypropylene composition.
  • Described more particularly is a process to produce a polypropylene composition
  • a process to produce a polypropylene composition comprising (or consisting of, or consisting essentially of) combining a linear polypropylene having a melt strength within a range from 10 to 40 cN (190°C) with an organic peroxide to obtain a branched polypropylene having a melt strength within a range from 20 to 80 cN (190°C), wherein the melt strength of the branched polypropylene is greater than the melt strength of the linear polypropylene; and combining the branched polypropylene having a melt flow rate within a range of 0.1 to 20 g/10 min and an Mw/Mn of at least 5 within a range from 5 to 40 wt%, by weight of the branched polypropylene and polypropylene homopolymer, of a polypropylene homopolymer having a melt flow rate of at least 50 g/10 min and an Mw/Mn of less than 5
  • a polypropylene composition comprising (or consisting essentially of) a branched polypropylene and a low molecular weight polyolefin having a melt flow rate of at least 50 g/10 min.
  • a foamed, thermoformed, and/or extruded article comprising (or consisting essentially of) a polypropylene composition comprising (or consisting essentially of) within a range from 95 to 60 wt%, by weight of the branched polypropylene and polypropylene homopolymer, of a branched polypropylene having a melt strength within a range from 20 to 80 cN (190°C), and a melt flow rate within a range of 0.1 to 20 g/10 min; and within a range from 5 to 40 wt%, by weight of the branched polypropylene and polypropylene homopolymer, of a polypropylene homopolymer having a melt flow rate of at least 50 g/10
  • Fig. 1 is extensional rheology traces of a comparative and two inventive blends giving viscosity as a function of time at l 1 sec rate.
  • Fig. 2 is extensional rheology traces of a comparative and two inventive blends giving viscosity as a function of time at 5 "1 sec rate.
  • Fig. 3 is extensional rheology traces of a comparative and two inventive blends giving viscosity as a function of time at 10 "1 sec rate.
  • Fig. 4 is SAOS traces of a comparative and two inventive blends giving angular frequency as a function of shear viscosity.
  • linear polypropylene refers to a reactor grade polypropylene homopolymer or copolymer that is useful in forming the "branched polypropylene” having a branching index g'(vis) of greater than 0.98.
  • the linear polypropylene that is most preferred in any embodiment of the invention has the properties described herein, and can be made by any means known to those of skill in the art, but most preferably is produced using a Ziegler-Natta succinate-containing catalyst.
  • the properties referred to here are those of the reactor-grade material prior to melt blending or after melt blending with non-peroxide "additives” such as antioxidants, alkyl-radical scavengers, etc.
  • the desirable linear polypropylene is a homopolymer of propylene-derived units, or is a copolymer comprising within a range of from 0.20 or 0.40 or 0.80 wt% to 1.0 or 2.0 or 4.0 or 6.0 wt%, by weight of the linear polypropylene, of ethylene or C 4 to Ci 2 a-olefin derived units, most preferably ethylene, 1-butene or 1-hexene derived units, the remainder being propylene-derived units.
  • Ziegler-Natta catalysts suitable to produce the useful linear polypropylenes include solid titanium supported catalyst systems described in US 4,990,479 and US 5,159,021, and WO 00/63261, and others.
  • the Ziegler-Natta catalyst can be obtained by: (1) suspending a dialkoxy magnesium compound in an aromatic hydrocarbon that is liquid at 20- 25 °C; (2) contacting the dialkoxy magnesium hydrocarbon composition with a titanium halide and with a diester of an aromatic dicarboxylic acid; and (3) contacting the resulting functionalized dialkoxy magnesium-hydrocarbon composition of step (2) with additional titanium halide.
  • the "catalyst system” typically includes solid titanium catalyst component comprising titanium as well as magnesium, halogen, at least one non-aromatic "internal” electron donor, and at least one, preferably two or more "external” electron donors.
  • the solid titanium catalyst component also referred to as a Ziegler-Natta catalyst, can be prepared by contacting a magnesium compound, a titanium compound, and at least the internal electron donor. Examples of the titanium compound used in the preparation of the solid titanium catalyst component include tetravalent titanium compounds having the formula (I):
  • R is a hydrocarbyl radical
  • X is a halogen atom
  • n is from 0 to 4.
  • hydrocarbyl radical is defined to be Ci to C20 radicals, or Ci to C10 radicals, or C 6 to C20 radicals, or C7 to C20 radicals that may be linear, branched, or cyclic where appropriate (aromatic or non-aromatic); and includes hydrocarbyl radicals substituted with other hydrocarbyl radicals and/or one or more functional groups comprising elements from Groups 13 - 17 of the periodic table of the elements.
  • two or more such hydrocarbyl radicals may together form a fused ring system, including partially or fully hydrogenated fused ring systems, which may include heterocyclic radicals.
  • the halogen-containing titanium compound is a titanium tetrahalide, or titanium tetrachloride.
  • the titanium compounds may be used singly or in combination with each other.
  • the titanium compound may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.
  • Non-limiting examples include titanium tetra-halides such as TiCl 4 , TiBr 4 , and/or Til 4 ; alkoxy titanium trihalides including Ti(OCH 3 )Cl 3 , Ti(OC 2 H 5 )Ci3, Ti(0 n-C 4 H 9 )Cl 3 , Ti(OC 2 H 5 )Br 3 , and/or Ti(0-iso-C 4 H 9 )Br 3 ; dialkoxytitanium dihalides including Ti(OCH 3 ) 2 Cl 2 , Ti(OC 2 H 5 ) 2 Cl 2 , Ti(0-n-C 4 H 9 ) 2 Cl 2 and/or Ti(OC 2 H 5 ) 2 Br 2 ; trialkoxytitanium monohalides including Ti(OCH 3 ) 3 Cl, Ti(OC 2 H 5 ) 3 Cl, Ti(0-n-C 4 H 9 ) 3 Cl and/or Ti(OC2Hs)3Br; and/or tetraalkoxy titaniums including
  • the magnesium compound to be used in the preparation of the solid titanium catalyst component includes a magnesium compound having reducibility and/or a magnesium compound having no reducibility.
  • Suitable magnesium compounds having reducibility may, for example, be magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond.
  • Suitable examples of such reducible magnesium compounds include dimethyl magnesium, diethyl-magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, magnesium ethyl chloride, magnesium propyl chloride, magnesium butyl chloride, magnesium hexyl chloride, magnesium amyl chloride, butyl ethoxy magnesium, ethyl butyl magnesium, and/or butyl magnesium halides. These magnesium compounds may be used singly or they may form complexes with the organoaluminum co-catalyst as described herein. These magnesium compounds may be a liquid or a solid.
  • Suitable examples of the magnesium compounds having no reducibility include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; alkoxy magnesium halides, such as magnesium methoxy chloride, magnesium ethoxy chloride, magnesium isopropoxy chloride, magnesium phenoxy chloride, and magnesium methylphenoxy chloride; alkoxy magnesiums, such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, and 2-ethylhexoxy magnesium; aryloxy magnesiums such as phenoxy magnesium and dimethylphenoxy magnesium; and/or magnesium carboxylates, such as magnesium laurate and magnesium stearate.
  • magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride
  • alkoxy magnesium halides such as magnesium methoxy chloride, magnesium ethoxy chloride, magnesium isopropoxy chloride, magnesium phenoxy chloride, and magnesium methylphenoxy chloride
  • Non-reducible magnesium compounds may be compounds derived from the magnesium compounds having reducibility, or may be compounds derived at the time of preparing the catalyst component.
  • the magnesium compounds having no reducibility may be derived from the compounds having reducibility by, for example, contacting the magnesium compounds having reducibility with polysiloxane compounds, halogen-containing silane compounds, halogen-containing aluminum compounds, esters, alcohols, and the like.
  • the magnesium compounds having reducibility and/or the magnesium compounds having no reducibility may be complexes of the above magnesium compounds with other metals, or mixtures thereof with other metal compounds. They may also be mixtures of two or more types of the above compounds. Further, halogen-containing magnesium compounds, including magnesium chloride, alkoxy magnesium chlorides and aryloxy magnesium chlorides may be used.
  • Supported Ziegler-Natta catalysts may be used in combination with a co-catalyst, also referred to herein as a Ziegler-Natta co-catalyst.
  • a co-catalyst also referred to herein as a Ziegler-Natta co-catalyst.
  • Compounds containing at least one aluminum-carbon bond in the molecule may be utilized as the co-catalysts, also referred to herein as an organoaluminum co-catalyst.
  • Suitable organoaluminum compounds include organoaluminum compounds of the general formula (II):
  • R 1 and R 2 are identical or different, and each represents a hydrocarbyl radical containing from 1 to 15 carbon atoms, or 1 to 4 carbon atoms;
  • organoaluminum compounds include complex alkylated compounds of metals of Group I (Periodic Table, lithium, etc.) and aluminum represented by the general formula (III):
  • M 1 is the Group I metal such as Li, Na, or K and R 1 is as defined in formula (II).
  • Suitable examples of the organoaluminum compounds include trialkyl aluminums such as trimethyl aluminum, triethyl aluminum and tributyl aluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkyl aluminum alkoxides such as diethyl- aluminum ethoxide and dibutyl aluminum ethoxide; alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesqui-butoxide; partially alkoxylated alkyl aluminums having an average composition represented by the general formula R 1 2.5Al(OR 2 )o.5 ; partially halogenated alkyl aluminums, for example, alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; partially hydrogenated alkyl aluminums, for example, alkyl aluminum dihydrides such as ethyl aluminum dihydride and propyl aluminum dihydride; and
  • Electron donors are present with the metal components described above in forming the catalyst suitable for producing the linear polypropylenes described herein. Both “internal” and “external” electron donors are desirable for forming the catalyst suitable for making the linear polypropylene described herein. More particularly, the internal electron donor may be used in the formation reaction of the catalyst as the transition metal halide is reacted with the metal hydride or metal alkyl. Examples of suitable internal electron donors include amines, amides, ethers, esters, ketones, nitriles, phosphines, stilbenes, arsines, phosphoramides, thioethers, thioesters, aldehydes, alcoholates, and salts of organic acids.
  • the one or more internal donors are non-aromatic.
  • the non- aromatic internal electron donor may comprise an aliphatic amine, amide, ester, ether, ketone, nitrile, phosphine, phosphoramide, thioethers, thioester, aldehyde, alcoholate, carboxylic acid, or a combination thereof.
  • the non-aromatic internal electron donor(s) comprises a Ci to C20 diester of a substituted or unsubstituted C2 to C10 dicarboxylic acid.
  • the non-aromatic internal electron donor(s) may be one or more succinate compounds according to formula (IV):
  • R 1 and R 2 are independently Ci to C20 linear or branched alkyl, alkenyl, or cycloalkyl hydrocarbyl radicals; and R 3 to R 6 are independently, hydrogen, halogen, or Ci to C20 linear or branched alkyl, alkenyl, or cycloalkyl hydrocarbyl radicals, wherein the R 3 to R 6 radicals are not joined together, wherein at least two of the R 3 to R 6 radicals are joined to form a cyclic divalent radical, or a combination thereof.
  • R 3 to R 5 groups of formula (IV) may be hydrogen and R 6 may be a radical selected from the group consisting of a primary branched, secondary or tertiary alkyl, or cycloalkyl radical having from 3 to 20 carbon atoms.
  • the internal donor may be a monosubstituted non-aromatic succinate compound. Suitable examples include diethyl-secbutylsuccinate, diethylhexylsuccinate, diethyl- cyclopropylsuccinate, diethyl-trimethylsilylsuccinate, diethyl-methoxysuccinate, diethyl- cyclohexylsuccinate, diethyl-(cyclohexylmethyl) succinate, diethyl-t-butylsuccinate, diethyl- isobutylsuccinate, diethyl-isopropylsuccinate, diethyl-neopentylsuccinate, diethyl- isopentylsuccinate, diethyl-(l,l,l-trifluoro-2-propyl) succinate, diisobutyl-sec-butylsuccinate, diisobutylhexylsuccinate,
  • the internal electron donor having a structure consistent with formula (IV) may comprise at least two radicals from R 3 to R 6 , which are different from hydrogen and are selected from Ci to C20 linear or branched alkyl, alkenyl, and/or cycloalkyl hydrocarbyl groups, which may contain heteroatoms. Two radicals different from hydrogen may be linked to the same carbon atom.
  • Suitable examples include 2,2-disubstituted succinates including diethyl-2,2- dimethylsuccinate, diethyl-2-ethyl-2-methylsuccinate, diethyl-2-(cyclohexylmethyl)-2- isobutylsuccinate, diethyl-2-cyclopentyl-2-n-propylsuccinate, diethyl-2,2-diisobutylsuccinate, diethyl-2-cyclohexyl-2-ethylsuccinate, diethyl-2-isopropyl-2-methylsuccinate, diethyl-2,2- diisopropyl-diethyl-2-isobutyl-2-ethylsuccinate, diethyl-2-(l,l,l-trifluoro-2-propyl)-2- methylsuccinate, diethyl-2-isopentyl-2-isobutylsuccinate, diisobutyl-2,2-dimethyls
  • the at least two radicals different from hydrogen may be linked to different carbon atoms between R 3 and R 6 in formula (IV).
  • examples include R 3 and R 5 or R 4 and R 6 .
  • Suitable non-aromatic succinate compounds such as this include: diethyl-2,3-bis(trimethylsilyl) succinate, diethyl-2,2-sec-butyl-3-methylsuccinate, diethyl-2-(3,3,3-trifluoropropyl)-3- methylsuccinate, diethyl-2,3-bis(2-ethylbutyl) succinate, diethyl-2,3-diethyl-2- isopropylsuccinate, diethyl-2,3-diisopropyl-2-methylsuccinate, diethyl-2,3-dicyclohexyl-2- methylsuccinate, diethyl-2,3-diisopropylsuccinate, diethyl-2,3-bis(cyclohexylmethyl
  • the electron donor according to formula (IV) may include two or four of the radicals R 3 to R 6 joined to the same carbon atom which are linked together to form a cyclic multivalent radical.
  • suitable compounds include l-(ethoxycarbonyl)-l- (ethoxyacetyl)-2,6-dimethylcyclohexane, l-(ethoxycarbonyl)-l-(ethoxyacetyl)-2,5-dimethyl- cyclopentane, l-(ethoxycarbonyl)-l-(ethoxyacetylmethyl)-2-methylcyclohexane, and/or 1- (ethoxycarbonyl)-l-(ethoxy (cyclohexyl) acetyl) cyclohexane.
  • the internal electron donor may be selected from the group consisting of diethyl-2,3-diisopropylsuccinate, diisobutyl-2,3-diisopropylsuccinate, di-n-butyl-2,3- diisopropylsuccinate, diethyl-2,3-dicyclohexyl-2-methylsuccinate, diisobutyl-2,3- dicyclohexyl-2-methylsuccinate, diisobutyl-2,2-dimethylsuccinate, diethyl-2,2- dimethylsuccinate, diethyl-2-ethyl-2-methylsuccinate, diisobutyl-2-ethyl-2-methylsuccinate, diethyl-2-(cyclohexylmethyl)-3-ethyl-3-methylsuccinate, diisobutyl-2-(cyclohexylmethyl)-3-ethyl-3-methylsuccinate, diisobutyl-2-(cyclo
  • two or more external electron donors may also use in combination with a catalyst.
  • the external electron donors may comprise an organic silicon compound of the general formula (V):
  • R 1 and R 2 independently represent a hydrocarbyl radical and n is 1, 2, or 3.
  • Examples of the suitable organic silicon compounds include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diiso-propyldiethoxysilane, t-butylmethyl- n-diethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o- tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p- tolyldimethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyl-d
  • Suitable examples of the organic silicon compounds in which n is 0, 1, or 3 include trimethylmethoxysilane, trimethylethoxysilane, methyl-phenyldimethoxysilane, methyltrimethoxysilane, t-butyl-methyldimethoxysilane, t-butylmethyldiethoxysilane, t- amylmethyldimethoxysilane, phenylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, decyl-trimethoxysilane, decyltriethoxysilane, phenyltri- methoxysilane,
  • the external electron donors are selected from any one or more of methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltributoxysilane and/or cyclohexyltrimethoxysilane.
  • the external electron donors act to control stereoregularity, which affects the amount of isotactic versus atactic polymers produced in a given system.
  • the more stereoregular isotactic polymer is more crystalline, which leads to a material with a higher flexural modulus.
  • Highly crystalline, isotactic polymers also display lower melt flow rates (MFR's), as a consequence of a reduced hydrogen response during polymerization.
  • MFR's melt flow rates
  • the stereoregulating capability and hydrogen response of a given external electron donor are typically directly and inversely related.
  • the above disclosed organic silicon compounds may be used such that a compound capable of being changed into such an organic silicon compound is added at the time of polymerizing or preliminarily polymerizing an olefin, and the organic silicon compound may be formed in situ during the polymerization or the preliminary polymerization of the olefin.
  • the production of the linear polypropylene may include the use of two external electron donors.
  • the two external electron donors may be selected from any of the external electron donors described herein.
  • the first external electron donor has the formula R 1 2Si(OR 2 )2, wherein each R 1 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms in which the carbon adjacent to the Si is a secondary or a tertiary carbon atom, and wherein each R 2 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms; and the second external electron donor has the formula R 3 n Si(OR 4 )4-n, wherein each R 3 and R 4 are independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms, and n is 1, 2, or 3; wherein the second external electron donor is different than the first external electron donor.
  • the first external electron donor and the second external electron donor may be selected from the group consisting of tetraethoxysilane, methylcyclohexyldimethoxysilane, propyltriethoxysilane, dicyclopentydimethoxysilane, and combinations thereof.
  • the Ziegler-Natta catalyst system may comprise 2.5 mol% to less than 50 mol% of the first external electron donor and greater than 50 mol% of a second external electron donor based on total mol% of external electron donors.
  • the method to make a linear polypropylene comprises contacting propylene monomers (and optionally comonomers) at propylene polymerization conditions such as described herein with a catalyst system to produce a linear polypropylene comprising at least 94.0, or 96.0, or 98.0, or 99.0, or 99.2, or 99.6, or 99.8 or 100 wt% propylene-derived units by weight of the linear polypropylene, an Mw/Mn greater than 5 (or as described herein) and a Melt Strength of at least 10 cN determined using an extensional rheometer at 190°C (described further below), wherein any co-monomers may be selected from ethylene, butene, hexene, octene, and combinations thereof.
  • the polymerization process may include a preliminary polymerization step.
  • the preliminary polymerization may include utilizing the Ziegler-Natta catalyst system comprising the non-aromatic internal electron donor in combination with at least a portion of the organoaluminum co-catalyst wherein at least a portion of the external electron donors are present wherein the catalyst system is utilized in a higher concentration than utilized in the subsequent "main" polymerization process.
  • the concentration of the catalyst system in the main and/or preliminary polymerization stages may be from 0.01 to 200 millimoles, or more preferably from 0.05 to 100 millimoles, calculated as a titanium atom, per liter of an inert hydrocarbon medium.
  • the organoaluminum co-catalyst may be present in an amount sufficient to produce from 0.1 to 500 g, or more preferably from 0.3 to 300 g, of a polymer per gram of the titanium catalyst present, and may be present at from 0.1 to 100 moles, or more preferably from 0.5 to 50 moles, per mole of the titanium atom present in the catalyst component.
  • the preliminary polymerization may be performed under mild conditions in an inert hydrocarbon medium in which an olefin and the catalyst components are present.
  • inert hydrocarbon medium examples include aliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons, such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons, such as benzene, toluene and xylene; halogenated hydrocarbons, such as ethylene chloride and chlorobenzene; and mixtures thereof.
  • Such inert hydrocarbons can be used in the main polymerization process as well.
  • the olefin(s) used in the preliminary polymerization may be the same as an olefin to be used in the main polymerization.
  • the reaction temperature for the preliminary polymerization may be a point at which the resulting preliminary polymerization does not dissolve substantially in the inert hydrocarbon medium, which may be from -20 to +100°C, or from -20 to +80°C, or from 0 to 40°C.
  • a molecular weight controlling agent such as hydrogen may be used.
  • the molecular weight controlling agent may desirably be used in such an amount that the polymer obtained by preliminary polymerization has properties consistent with the intended product.
  • the preliminary polymerization may be carried out so that from 0.1 to 1000 g, or more preferably from 0.3 to 300 g, of a polymer forms per gram of the titanium catalyst.
  • the main polymerization of the propylene and optional comonomers may be carried out in the gaseous phase, the liquid phase, bulk phase, slurry phase, or any combination thereof.
  • polymerization may be carried out by slurry polymerization wherein the inert hydrocarbon may be used as a reaction solvent, or an olefin liquid under the reaction conditions may be used as the solvent.
  • the polymerization process includes contacting the titanium catalyst component, the one or more internal electron donor, the organoaluminum co-catalyst, and the two external electron donors with each other at the time of the main polymerization, before the main polymerization, for example, at the time of the preliminary polymerization, or a combination thereof.
  • any two or more of these components may be freely selected and contacted. Two or more of the components may be contacted individually or partly and then contacted with each other in total to produce the catalyst system.
  • hydrogen may be used during polymerization to control the molecular weight and other properties of the resulting polymer.
  • the polymerization conditions include a polymerization temperature within a range from 20, or 40, or 60°C to 120, or 140, or 160, or 180, or 200°C, and a pressure from atmospheric pressure up to 100 kg/cm 2 , or more preferably within a range from 2, or 6 kg/cm 2 to 20, or 50, or 100 kg/cm 2 .
  • the polymerization process may be carried out batch-wise, semi-continuously, or continuously, and/or in two or more reactors in series. The conditions in each reactor if carried out in more than one reactor may be the same or different.
  • the reaction slurry (homopolymer granules in bulk propylene) may then be removed from the reactor and the polymer granules continuously separated from the liquid propylene.
  • the polymer granules may then be separated from the unreacted monomer to produce a granular product for compounding and/or mechanical properties.
  • the linear polypropylene has desirable properties as described herein.
  • the melt flow rate (MFR) of the linear polypropylene in any embodiment is within a range from 0.1, or 0.2, or 0.5 g/10 min to 4, or 8, or 10, or 20 g/10 min.
  • the weight average molecular weight (Mw) by GPC-3D analysis of the linear polypropylene is within a range of from 100,000 or 150,000 or 200,000 or 250,000 g/mole to 500,000 or 550,000 or 600,000 or 800,000 g/mole.
  • the linear polypropylene has a molecular weight distribution (Mw/Mn) of at least 5 or 6, or 8, or within a range of from 5 or 6 or 8 to 9 or 10 or 12 or 16.
  • Mw/Mn molecular weight distribution
  • the z-average molecular weight (Mz) by GPC-3D analysis of the desirable linear polypropylenes useful in the invention is within a range of from 800,000 or 1,000,000 or 1,100,000 g/mole to 1,300,000 or 1,400,000 or 1,500,000 or 1,800,000 or 2,000,000 g/mole, and the ratio of the z-average molecular weight and the weight average molecular weight (Mz/Mw) is greater than 2.8, or 2.9, or 3.0, or within a range of from 2.8 or 2.9 or 3.0 or 3.5 to 4.0 or 4.5 or 5.0, the values greater than 2.8 indicating a high-molecular weight portion to the linear polyethylene.
  • Useful linear polypropylenes may have other desirable properties.
  • the linear polypropylene has a tensile at yield (ASTM D638, with a crosshead speed of 50.8 rnm/min (2.0 in/min), and a gauge length of 50.8 mm (2.0 in), using an Instron Machine) within a range of from 20 or 25 or 30 or 25 MPa to 40 or 45 or 50 or 55 or 80 MPa.
  • the linear polypropylene has a 1% secant flexural modulus (ASTM D790A, using a crosshead speed of 1.27 rnm/min (0.05 in min), and a support span of 50.8 mm (2.0 in) using an Instron machine) within a range of from 1,800 or 1,900 or 2,000 MPa to 2,100 or 2,200 or 2,400 or 2,600 MPa.
  • the linear polypropylene has a melt strength of at least 10, or 15 or 20 cN, or within a range of from 10 or 15, or 20 or 30 cN to 35, or 40 cN at 190°C (determined by extensional rheology, described below).
  • the melt strength of the branched polypropylene described below is greater than the melt strength of the linear polypropylene, preferably by at least 5, or 10, or 15, or 20 cN.
  • branched polypropylene refers to a polypropylene homopolymer or copolymer having a branching index g'(vis) of 0.98, or 0.97, or 0.96 or less.
  • the branched polypropylene can be formed by any means such as by catalyst production to form a reactor grade branched polypropylene, or reactive extrusion, among other means.
  • the preferred branched polypropylene may have other features as further described below.
  • the branched polypropylene is formed by combining under suitable conditions the linear polypropylene and an organic peroxide, wherein the "organic peroxide” is any organic compound comprising at least one— (O)COO— group and/or— O— O— group, and preferably possesses a 1 hour half-life temperature CTm) of less than 100°C determined in an aromatic and/or halogenated aromatic hydrocarbon solvent, preferably a ( l Tm) within a range from 25, or 35, or 45°C to 65, or 75, or 85, or 100°C.
  • organic peroxide is any organic compound comprising at least one— (O)COO— group and/or— O— O— group, and preferably possesses a 1 hour half-life temperature CTm) of less than 100°C determined in an aromatic and/or halogenated aromatic hydrocarbon solvent, preferably a ( l Tm) within a range from 25, or 35, or 45°C to 65, or 75, or 85, or 100°C.
  • the organic peroxide is selected from compounds having one or more structures selected from (a) and (b):
  • each "R” group is independently selected from the group consisting of hydrogen, CI or C5 to C24 or C30 linear alkyls, CI or C5 to C24 or C30 secondary alkyls, CI or C5 to C24 or C30 tertiary alkyls, C7 to C34 alkylaryls, C7 to C34 arylalkyls, and substituted versions thereof.
  • the organic peroxide is selected from the structures represented by formula (a).
  • substituted what is meant are hydrocarbon "R” groups having substituents such as halogens, carboxylates, hydroxyl groups, amines, mercaptans, and phosphorous containing groups.
  • each "R" group is independently selected from C8 to C20 or C24 linear, secondary, or tertiary alkyls, such as octyl, decyl, lauryl, myristyl, cetyl, arachidyl, behenyl, erucyl and ceryl groups and linear, secondary or tertiary versions thereof.
  • suitable organic peroxides include di-sec -butyl peroxydicarbonate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di(4-tert- butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, dibutyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, didodecyl peroxydicarbonate, diicosyl peroxydicarbonate, and ditetracosyl peroxydicarbonate.
  • the formation of the branched polypropylenes described herein are effected in any embodiment by melt blending the linear polypropylene with the organic peroxide, especially through shear forces and applied radiative heating during blending/extrusion, to a melt temperature of at least the melting point of the linear polypropylene, such as at least 140, or 150, or 160°C, or within a range from 140, or 150, or 160°C to 180, or 200, or 220, or 240, or 260, or 280, or 300°C.
  • Suitable means include a single or twin screw extruder or Brabender- type apparatus.
  • organic peroxide is combined with the linear polypropylene, by weight of the organic peroxide and linear polypropylene.
  • the branched polypropylenes directly from the extrusion process, is formed into reactor flakes and/or granules, or extruded pellets without being treated under vacuum and/or solvent washing.
  • the peroxide melts before it reacts with the linear polypropylene so that the granules get evenly coated and the high specific surface area is utilized prior to the branching and/or cross-linking reactions.
  • reactor granules of the linear polypropylene used herein are preferred over extruded pellets.
  • Such linear polypropylene granules are preferably dry blended with the organic peroxide before "combining" as by, for example, melt blending in a single or twin screw extruder ("melt extrusion").
  • the product of the reaction between the organic peroxide and linear polypropylene may include decomposition products consisting of carbon dioxide and alcohol, preferably C8 to C24 alcohols, and most preferably an alcohol that is the hydroxylated equivalent of the organic peroxide use in the reaction.
  • the alcohol is typically present, if at all, at a level of less than 2, or 1 , or 0.5 wt% by weight of the branched polypropylenes. Described in this way, the branched polypropylene may have any of the properties described herein for the composition.
  • the branched polypropylenes described herein are ready to ship, transport, and/or store without further treatment, and be used in blending with the low molecular weight polyolefin to make any number of articles, both foamed and non-foamed.
  • a foaming agent may be added during the heating/extrusion process described above such that the agent is not activated until after shipping and ready to form into a foamed article.
  • the low molecular weight polyolefin is also blended with the branched polypropylene prior to foaming.
  • the composition may be later heated/extruded again to form articles and effect foaming, if so desired.
  • the branched polypropylene will have the same level of propylene and comonomer derived units as its precursor linear polypropylene.
  • diene monomers linear, branched or cyclic C4 to C20 alkenes having at least two conjugated or non-conjugated carbon-carbon double bonds
  • diene monomers such as butadiene, isoprene, norbornenes, and 1,9-decadiene are absent from the branched polypropylene and/or all process steps in forming the branched polypropylene.
  • the polypropylene useful in the inventive compositions can be characterized by any number of parameters as distinct from its linear polypropylene precursor.
  • the branched polypropylene has a melt strength of at least 20, or 30, or 40 cN, or within a range from 20, or 30, or 40, or 45 cN to 60, or 65, or 80 cN.
  • the branched polypropylene has a MFR within a range from 0.1, or 0.2, or 0.5 g/10 min to 4, or 8, or 10, or 20 g/10 min.
  • the branched polypropylenes have a number average molecular weight (Mn), by GPC-3D analysis, within a range from 18,000, or 20,000, or 24,000, or 28,000 g/mole to 40,000, or 44,000, or 48,000, or 50,000 g/mole.
  • Mn number average molecular weight
  • the polypropylenes have a weight average molecular weight (Mw), by GPC-4D analysis within a range from 250,000, or 300,000 or 350,000 g/mole to 450,000, or 500,000, or 550,000 or 600,000 g/mole.
  • the branched polypropylenes have a z-average molecular weight (Mz), by GPC-4D analysis within a range from 1,000,000, or 1,100,000, or 1,200,000 g/mole to 1,500,000, or 1,600,000, or 1,700,000, or 1,800,000 g/mole.
  • Mz z-average molecular weight
  • the branched polypropylenes has in any embodiment an Mz/Mw value of greater than 3.0, or 3.2, or 3.6, or within a range from 3.0, or 3.2, or 3.6 to 4.0 or 4.5 or 5.0 or 6.0.
  • the branched polypropylenes have an Mz/Mn of greater than 30 or 35 or 40, or within a range from 30, or 35, or 40 to 44, or 48, or 50, or 55, or 60. Also, the branched polypropylene as in any embodiment an Mw/Mn of at least 5, or 6 or 8, or 10, or within a range from 5, or 6, or 8, or 10 to 16, or 18 or 20.
  • the branched polypropylenes have improved strain hardening (relative to the linear polypropylene) as evidenced in the increased Peak Extensional Viscosity.
  • the branched polypropylenes have a Peak Extensional Viscosity (annealed) of greater than 50, or 55, or 60 kPa » s, or within a range from 50, or 55, or 60 kPa » s to 500, or 550, or 600 kPa » s at a strain rate of 0.01 /sec (190°C).
  • the branched polypropylenes have a Peak Extensional Viscosity (annealed) of greater than 500, or 550, or 600 kPa » s, or within a range from 500, or 550, or 600 kPa » s to 2,000, or 2,500, or 3,000 kPa » s at a strain rate of 0.01 /sec (190°C).
  • the polypropylene composition comprising (or consisting essentially of) the branched polypropylene such as described above and a low molecular weight polyolefin.
  • the composition comprises within a range from 5, or 10 wt% to 15, or 20, or 25, or 30, or 35, or 40 wt% of the low molecular weight polyolefin by weight of the low molecular weight polyolefin and branched polypropylene. Most preferably, the remainder of the composition is the branched polypropylene and additives.
  • the polypropylene composition exhibits at least 90%, or 95% of the strain hardening that is exhibited by the branched polypropylene alone as measured by extensional rheology at 190°C at the same strain rate. Also in any embodiment, the polypropylene composition exhibits at least 10%, or 5% lower complex viscosity at 500 rad/sec compared to the branched polypropylene alone as determined by small-amplitude oscillatory spectroscopy at 190°C. In any embodiment, the composition may be formed into a foamed, thermoformed, and/or extruded article. Desirable articles include cups, plates, food containers, and insulation containers.
  • the "low molecular weight polyolefin” is a polyolefin polymer having a weight average molecular weight of no more than 80,000, or 100,000 g/mole, preferably comprising ethylene and C4 to CIO derived units, most preferably comprising propylene and optionally ethylene derived units.
  • the low molecular weight polyolefin has a melt flow rate (230°C/2.16 kg) of at least 50, or 100, or 200, or 500 g/10 min, or within a range from 50, or 100, or 200, or 500 g/10 min to 1,500, or 2,000, or 5,000 g/10 min.
  • the low molecular weight polyolefin is selected from the group consisting of polypropylene homopolymers, polypropylene copolymers, polyethylene homopolymers, polyethylene copolymers, and blends thereof. Most preferably, the low molecular weight polyolefin is a polypropylene homopolymer, meaning that it comprises less than 1, or 2 wt% wt% ethylene or C4 to CIO derived units.
  • the low molecular weight polyolefin has an Mw/Mn of less than 5, or 4, or 3.
  • compositions are suitable for thermoformed articles, and especially foamed articles since they are more processable than the branched polypropylene alone, but maintain a desirable level of strain hardening for forming closed cell structures
  • a foamed, thermoformed, and/or extruded article comprising a polypropylene composition comprising within a range from 95 to 60 wt%, by weight of the branched polypropylene and polypropylene homopolymer, of a branched polypropylene and a minor amount of additives having a melt strength within a range from 20 to 80 cN (190°C), and a melt flow rate within a range of 0.1 to 20 g/10 min; and within a range from 5 to 40 wt%, by weight of the branched polypropylene and polypropylene homopolymer, of a polypropylene homopolymer having a melt flow rate of at least 50 g/10 min; wherein the polypropylene composition as a melt flow
  • the inventive process comprises combining a linear polypropylene with an organic peroxide to obtain a branched polypropylene; combining the branched polypropylene with a low molecular weight polyolefin to obtain a polypropylene composition. Desirably, within a range from 5, or 10 wt% to 15, or 20, or 25, or 30, or 35, or 40 wt% of the low molecular weight polyolefin by weight of the low molecular weight polyolefin and branched polypropylene is combined.
  • the remainder is the branched polypropylene with or without additives such as antioxidants, fillers, and other additives known in the art.
  • the components are most preferably melt blended using a single or double screw extruder operating at temperatures that melt the polymeric ingredients but lower than their decomposition temperature, preferably within a range from 190 to 260°C.
  • the low molecular weight polyolefin is combined with the other ingredients by directly feeding to an extruder, preferably in its solid form, or first forming a masterblend of the low molecular weight polyolefin with a higher molecular weight polyolefin.
  • a process to produce a polypropylene composition comprising combining a linear polypropylene having a melt strength within a range from 10 to 40 cN (190°C) with an organic peroxide to obtain a branched polypropylene having a melt strength within a range from 20 to 80 cN (190°C), wherein the melt strength of the branched polypropylene is greater than the melt strength of the linear polypropylene; and combining the branched polypropylene having a melt flow rate within a range of 0.1 to 20 g/10 min and an Mw/Mn of at least 5 with within a range from 5 to 40 wt%, by weight of the branched polypropylene and polypropylene homopolymer, of a polypropylene homopolymer having a melt flow rate of at least 50 g/10 min and an Mw/Mn of less than 5 to obtain a polypropylene composition; wherein the polypropylene composition as a melt flow rate
  • Molecular Weight Determinations using DRI (GPC-3D). This method describes the first of two different methods that were used to determine the moments of molecular weight of the polymer described herein, as indicated, the so-called “GPC-3D” method and the “GPC-4D” method, each based on Gel Permeation Chromatography (GPC) but using different detection methods.
  • GPC-3D method the number average molecular weight (Mn) values were determined by using a High Temperature Gel Permeation Chromatography (Agilent PL- 220), equipped with three in-line detectors, a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer.
  • DRI differential refractive index detector
  • LS light scattering
  • Polymer solutions were prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160°C with continuous shaking for about 2 hours. All quantities were measured gravimetrically.
  • the TCB densities used to express the polymer concentration in mass/volume units were 1.463 g/ml at 23°C and 1.284 g/ml at 145°C.
  • the injection concentration is from 0.5 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
  • Prior to running each sample the DRI detector and the viscometer were purged. Flow rate in the apparatus is then increased to 0.5 ml/minute, and the DRI is allowed to stabilize for 8 hours before injecting the first sample.
  • the LS laser is turned on at least 1 to 1.5 hours before running the samples.
  • the concentration "c" at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, IDRI, using the equation:
  • KDRI is a constant determined by calibrating the DRI
  • (dn/dc) is the refractive index increment for the system.
  • concentration is expressed in g/cm 3
  • molecular weight is expressed in g/mole
  • intrinsic viscosity is expressed in dL/g.
  • All the concentration is expressed in g/cm 3
  • molecular weight is expressed in g/mole
  • intrinsic viscosity is expressed in dL/g unless otherwise noted.
  • the TCB mixture is filtered through a 0.1 ⁇ Teflon filter and degassed with an online degasser before entering the GPC instrument.
  • the nominal flow rate is 1.0 niL/min and the nominal injection volume is 200 ⁇ .
  • the whole system including transfer lines, columns, detectors were contained in an oven maintained at 145 °C.
  • Given amount of polymer sample is weighed and sealed in a standard vial with 80 flow marker (heptane) added to it. After loading the vial in the autosampler, polymer is automatically dissolved in the instrument with 8 mL added TCB solvent. The polymer is dissolved at 160°C with continuous shaking for about 2 hours.
  • the TCB densities used in concentration calculation were 1.463 g/ml at 23 °C and 1.284 g/ml at 145°C.
  • the sample solution concentration is from 0.2 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
  • ⁇ is the mass constant determined with polypropylene standards.
  • the mass recovery is calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume.
  • the conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 g/mole to 10,000,000 g/mole.
  • PS monodispersed polystyrene
  • the MW at each elution volume is calculated with following equation: where the variables with subscript "PS” stands for polystyrene while those without a subscript are for the test samples.
  • GPC-3D and GPC- 4D values for Mn, Mw and Mz have an accuracy of ⁇ 10%.
  • a high temperature Viscotek Corporation viscometer equipped with four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, was used to determine specific viscosity of the eluting polymer from the GPC described above.
  • One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure.
  • the specific viscosity, %, for the solution flowing through the viscometer was calculated from their outputs.
  • the average intrinsic viscosity, [nj av g, of the sample was calculated by: UJavg
  • the branching index g'(vis) is then defined as: i' (vw) where M v is the viscosity-average molecular weight based on molecular weights determined by LS laser analysis.
  • SAOS Small Angle Oscillatory Spectroscopy The Small Angle Oscillatory Spectroscopy method was used to determine viscosity at low shear rates. Polymer samples were prepared using hot press (either a Carver Press or Wabash Press) to make disks of 25 mm in diameter and 2.5 mm in thickness. In order to characterize the shear thinning behavior, a rheometer ARES-G2 (TA Instruments) was used to conduct small angle oscillatory shear measurements at angular frequency ranging from 0.01 to 500 rad/s at temperature 190°C and at a fixed strain of 10%. The data was then converted into viscosity as a function of shear rate. To ensure that selected strain provides measurements within linear deformation range, the strain sweep measurements have been conducted (at angular frequency of 100 Hz). Data was processed using Trios software.
  • Extensional Rheology To characterize strain hardening behavior of the polypropylene, the annealed samples were tested using a DHR-3 rheometer (TA Instruments) with mounted SER fixture to measure stress in extension. The samples were prepared using procedure described above (SAOS) and later cut into a rectangular shape with dimensions near 18 mm long and 12.7 mm wide. The measurements were conducted at Hencky strain rates of 1, 5, and 10 s 1 at a temperature of 190°C. Data was processed using Trios software. Samples were annealed by heated to around 200°C for 3 min to melt the polypropylene pellets without pressure. Then 1500 psi pressure was applied while the sample was kept heated for another 3 min between two plates.
  • melt strength reported herein have an accuracy of ⁇ 10%.
  • the branched polypropylene (b-PP) was produced by melt extruding a Ziegler- Natta produced linear polypropylene homopolymer made as described above with 1.5 wt% Perkadox (Akzo Nobel) at a temperature within a range from 190 to 220 °C.
  • the b-PP has a g' (vis) of less than 0.98, a melt strength of 40 ⁇ 5 cN, an MFR of 2.09 g/10 min, an Mw/Mn of 15, and an Mz/Mw of 6.
  • the low molecular weight polyolefin was a polypropylene homopolymer (100 wt% propylene-derived units) with an MFR of 1550 g/10 min, and an Mw/Mn of 2.5 (GPC-3D).
  • Example 1 is an 85:15 blend of the branched polypropylene (a polypropylene homopolymer, 100 wt% propylene-derived units) and the LMW-PO, the blend had a melt strength of 17.5 cN with a draw ratio near 5.
  • Example 2 is a 50:50 blend of a branched polypropylene (100 wt% propylene-derived units) and was blended by a third party compounder, PolyOne; the blend had a melt strength of 2.5 cN with a draw ratio close to 12.
  • Example 3 is a 50:50 blend but the branched polypropylene has about 0.55 wt% ethylene derived units or less by weight of the polymer.
  • Example 4 is a 50:50 blend but the branched polypropylene is a polypropylene homopolymer with 100 wt% propylene-derived units.
  • the SAOS data in Figure 4 demonstrate that the viscosity, and hence processability, of the polypropylene compositions are improved over the branched polypropylene alone, but the data in Figures 1 to 3 demonstrate that the compositions still possess a desirable level of strain hardening from the branched polypropylenes.
  • the polypropylene composition exhibits at least 10% lower complex viscosity at 500 rad/sec compared to the branched polypropylene as determined by small-amplitude oscillatory spectroscopy at 190°C, while preferably the composition exhibits at least 90% the strain hardening that is exhibited by the branched polypropylene at the same strain rate.
  • the claimed polymer or polymer blend includes only the named components and no additional components that will alter its measured properties by any more than 10 or 20%; and most preferably means that additional components or "additives” are present to a level of less than 5, or 4, or 3, or 2 wt% by weight of the composition.
  • additives can include, for example, fillers, colorants, antioxidants, alkyl-radical scavengers, anti-UV additives, acid scavengers, slip agents, curatives and cross-linking agents, aliphatic and/or cyclic containing oligomers or polymers (also referred to as "hydrocarbon resins”), and other additives well known in the art.
  • the phrase "consisting essentially of means that there are no other process features that will alter the claimed properties of the polymer, polymer blend or article produced therefrom by any more than 10 or 20%.

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Abstract

L'invention concerne une composition de polypropylène appropriée pour le moussage, présentant une aptitude au traitement améliorée mais un durcissement par écrouissage maintenu, et le procédé en vue de produire la composition de polypropylène consistant à combiner un polypropylène linéaire présentant une résistance à l'état fondu comprise dans une plage de 10 à 40 cN (190 °C) avec un peroxyde organique en vue d'obtenir un polypropylène ramifié présentant une résistance à l'état fondu comprise dans une plage de 20 à 80 cN (190 °C), la résistance à l'état fondu du polypropylène ramifié étant supérieure à la résistance à l'état fondu du polypropylène linéaire ; et à combiner le polypropylène ramifié présentant un indice de fluidité compris dans une plage de 0,1 à 20 g/10 min et un rapport Mw/Mn d'au moins 5 compris dans une plage de 5 à 40 % en poids d'une polyoléfine de faible poids moléculaire présentant un indice de fluidité d'au moins 50 g/10 min et un rapport Mw/Mn inférieur à 5 en vue d'obtenir la composition de polypropylène.
PCT/US2018/012140 2017-02-07 2018-01-03 Polypropylènes à haute résistance à l'état fondu présentant une aptitude au traitement améliorée WO2018147944A1 (fr)

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US16/477,463 US11572462B2 (en) 2017-02-07 2018-01-03 High melt strength polypropylenes with improved processability
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