US20100305246A1 - Propylene polymers with improved properties - Google Patents

Propylene polymers with improved properties Download PDF

Info

Publication number
US20100305246A1
US20100305246A1 US12/857,341 US85734110A US2010305246A1 US 20100305246 A1 US20100305246 A1 US 20100305246A1 US 85734110 A US85734110 A US 85734110A US 2010305246 A1 US2010305246 A1 US 2010305246A1
Authority
US
United States
Prior art keywords
propylene
compounds
nucleated
propylene polymers
cycloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/857,341
Inventor
James McGoldrick
Franz Ruemer
Stefan Schiesser
Siegfried Liedauer
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 Technology Oy
Original Assignee
Borealis Technology Oy
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 Technology Oy filed Critical Borealis Technology Oy
Priority to US12/857,341 priority Critical patent/US20100305246A1/en
Publication of US20100305246A1 publication Critical patent/US20100305246A1/en
Priority to US13/477,682 priority patent/US8461267B2/en
Assigned to BOREALIS AG reassignment BOREALIS AG CHANGE OF ADDRESS Assignors: BOREALIS AG
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083Nucleating agents promoting the crystallisation of the polymer matrix
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04Monomers containing three or four carbon atoms
    • C08F10/06Propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04Monomers containing three or four carbon atoms
    • C08F110/06Propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C08F297/083Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04Monomers containing three or four carbon atoms
    • C08F210/06Propene

Definitions

  • the invention relates to propylene polymers with improved properties as well as to a process for producing them.
  • Propylene polymer compositions from common propylene polymers and ⁇ -nucleating agents are known.
  • ⁇ -Nucleating agents are useful in compositions for forming unstretched films which can be made porous by extraction of ⁇ -spherulites and stretching the films (disclosed for example in U.S. Pat. No. 4,386,129; U.S. Pat. No. 4,975,469).
  • thermoformability Another effect of ⁇ -nucleating agents in propylene compositions is the improved thermoformability.
  • melting point of the ⁇ -form of the spherulites of polypropylene based resins is generally about 144 to 148° C., contrasted with the typical melting point range of ⁇ -form spherulites of about 159 to 163° C., melt forming from these compositions is possible at lower temperatures and higher production rates (WO 93/12 262).
  • Conventional polypropylene homopolymers usually show high stiffness, but poor impact strength.
  • Conventional ⁇ -nucleated polypropylenes usually have improved impact strength but also exhibit reduced stiffness.
  • propylene polymers with improved properties comprising propylene homopolymers with melt indices of 0.05 to 15 g/10 min at 230° C./2.16 kg or propylene block copolymers with 90.0 to 99.9 wt % propylene and 0.1 to 10 wt % ⁇ -olefins with 2 or 4 to 18 carbon atoms with melt indices of 0.05 to 20 9/10 min at 230° C./2.16 kg, or mixtures thereof, wherein the propylene homopolymers or propylene block copolymers are ⁇ -nucleated propylene polymers, whereby the ⁇ -nucleated propylene homopolymers have an IR ⁇ 0.98, a tensile modulus of ⁇ 1500 MPa at +23° C.
  • the ⁇ -nucleated propylene block copolymers are polymers having an IR ⁇ of the propylene homopolymer block of ⁇ 0.98, a tensile modulus of 1100 MPa at +23° C. and a Charpy impact strength, of 6 kJ/m 2 at ⁇ 20° C., using notched test specimens.
  • ⁇ -nucleated propylene polymers are isotactic propylene polymers composed of chains in a 3 1 helical conformation having an internal microstructure of ⁇ -form spherulites being composed of radial arrays of parallel stacked lamellae. This microstructure can be realized by the addition of ⁇ -nucleating agents to the melt and subsequent crystallization. The presence of the ⁇ -form can be detected through the use of wide angle X-ray diffraction (Moore, J., Polypropylene Handbook, p. 134-135, Hanser Publishers Kunststoff 1996).
  • the IR ⁇ of the propylene polymers is measured and calculated as described in EP 0 277 514 A2 on page 5 (column 7, line 53 to column 8, line 11).
  • the ⁇ -nucleated propylene homopolymers or the propylene homopolymer block of the ⁇ -nucleated propylene block copolymers have an IR ⁇ of ⁇ 20.985.
  • the propylene homopolymers according to the present invention have melt indices of 0.05 to 15 g/10 min at 230° C./2.16 kg, preferably 0.1 to 8 g/10 min at 230° C./2.16 kg, most preferably 0.2 to 5 g/10 min at 230° M. 16 kg.
  • the propylene copolymers according to the present invention have melt indices of 0.05 to 20 g/10 min at 230° C./2.16 kg, preferably 0.1 to 8 g/10 min at 230° C./2.16 kg, most preferably 0.2 to 5 g/10 min at 230° C./2.16 kg.
  • the propylene homopolymers show a tensile modulus ⁇ 1500 MPa, preferably ⁇ 1600 MPa and the propylene copolymers show a tensile modulus ⁇ 1100 MPa, preferably ⁇ 1300 MPa and most preferably ⁇ 1500 MPa.
  • the propylene homopolymers according to the present invention have a Charpy impact strength of ⁇ 3 kJ/m 2 at ⁇ 20° C., preferably 4 to 10 kJ/m 2 at ⁇ 20° C., most preferably 5 to 10 kJ/m 2 at ⁇ 20° C.
  • the propylene copolymers according to the present invention have a Charpy impact strength of ⁇ 6 kJ/m 2 at ⁇ 20° C., preferably ⁇ 9 kJ/m 2 at ⁇ 20° C., most preferably ⁇ 10 kJ/m 2 at ⁇ 20° C. Charpy impact strength of up to at least 60 kJ/m 2 is possible for copolymers according to the invention.
  • the ⁇ -nucleated propylene polymers with an IR ⁇ 0.98 being propylene polymers obtained by polymerization with a Ziegler-Natta catalyst system comprising titanium-containing solid components, an organo alumina, magnesium or titanium compound as cocatalyst and an external donor according to the formula
  • R and R′ are identical or different and are branched or cyclic aliphatic or aromatic hydrocarbon residues, and y and x independently from each other are O or 1, provided that x+y are 1 or 2.
  • propylene polymers with high IRE obtained by polymerization with a Ziegler-Natta catalyst system, for example by slurry, bulk or gas phase polymerization, are propylene polymers as described in EP-A-0,790, 262, WO 99/24,478 and WO 99/16,797.
  • a preferred external donor of the Ziegler-Natta catalyst system is dicyclopentyldimethoxysilane.
  • B-nucleated propylene polymer contains 0.01 to 2.0 wt %, in each case based on the propylene polymers used, of
  • N,N′-di-C 5 -C 8 -cyclo alkyl-2,6-naphthalene dicarboxamide compounds are N,N′-dicyclohexyl-2,6-naphthalene dicarboxamide and N,N′-dicyclooctyl-2,6-naphthalene dicarboxamide.
  • N,N′-di-C 5 -C 8 -cycloalkyl-4,4-biphenyldicarboxamide compounds are N,N′-dicyclohexyl-4,4-biphenyldicarboxamide and N. N′-dicyclopentyl-4,4-biphenyldicarboxamide.
  • N,N′-di-C 5 -C 8 -cycloalkylterephthalamide compounds are N,N′-dicyclohexylterephthalamide and N,N′-dicyclopentylterephthalamide.
  • N,N′-di-C 5 -C 8 -cycloalkyl-1,4-cyclohexanedicarboxamide compounds are N,N′-dicyclohexyl-1,4-cyclohexanedicarboxamide and N,N′-dicyclohexyl-1,4-cyclopentanedicarboxanaide.
  • N,N′-di-C 6 -C 12 -aryl-Cs-C-diamide compounds are N,N′-bis(p-methylphenyl)-hexanediamide, N,N′-bis(4-cyclohexylphenyl)hexanediamide, N,N′-diphenylhexanediamide, N,N′-diphenyloctanediamide and N,N′-bis(p-ethylphenyl)hexanediamide.
  • N,N′-C 6 -C 12 -arylene-bis-benzamide compounds are N,N′-p-phenylene-bis-benzamide and N,N′-1,5-naphthalene-bis-benzamide.
  • N,N′-C 5 -C 8 -cycloalkyl-bis-benzamide compounds are N,N′-1,4-cyclopentane-bis-benzamide and N,N′-1,4-cyclohexane-bis-benzamide.
  • N,N′-p-C 6 -C 12 -arylene-bis-C 5 -C 8 -cycloalkylcarboxamide compounds are N,N′-1,5-naphthalene-bis-cyclohexanecarboxamide and N,N′-1,4-phenylene-bis-cyclohexanecarboxamide.
  • N,N′-C 5 -C 8 -cycloalkyl-bis-cyclohexanecarboxamide compounds are N,N′-1,4-cyclopentane-bis-cyclohexanecarboxamide and N,N′-1,4-cyclohexane-bis-cyclohexanecarboxamide.
  • the ⁇ -nucleated propylene polymer contains 0.0001 to 2.0 wt % of quinacridone type compounds, especially quinacridone, dimethylquinacridone and/or dimethoxyquinacridone; quinacridonequinone type compounds, especially quinacridonequinone, a mixed crystal of 5,12-dihydro(2,3b)acridine-7,14-dione with quino(2,3b)acridine-6,7,1 3,14-(5H, 12H)-tetrone as disclosed in EP-B 0 177 961 and/or dimethoxyquinacridonequinone; and/or dihydroquinacridone type compounds, especially dihydroquinacridone, di-methoxydihydroquinacridone and/or dibenzodihydroquinacridone, as ⁇ -nucleating agent.
  • quinacridone type compounds especially quinacridone, dimethylquinacridone and/or dimethoxyquinacridone
  • the ⁇ -nucleated propylene polymer contains 0.01 to 2.0 wt % of dicarboxylic acid salts of metals from group Ha of periodic system, especially pimelic acid calcium salt and/or suberic acid calcium salt; and/or mixtures of dicarboxylic acids and salts of metals from group Ha of periodic system, as ⁇ -nucleating agent.
  • the p-nucleated propylene polymer contains 0.01 to 2.0 wt % of salts of metals from group Ha of periodic system and imido acids of the formula
  • x 1 to 4; R ⁇ H, —COOH, C 1 -C 12 -alkyl, C 5 -C 8 -cycloalkyl or C 6 -C 12 -aryl, and Y ⁇ C 1 -C 12 -alkyl, C 5 -C 8 -cycloalkyl or C 6 -C 12 -aryl-substituted bivalent C 6 -C 12 -aromatic residues, especially calcium salts of phthaloylglycine, hexahydrophthaloylglycine, N-phthaloylalanine and/or N-4-methylphthaloylglycine, as ⁇ -nucleating agent.
  • the inventive propylene polymers with improved properties may contain usual auxiliary materials such as 0.01 to 2.5 wt % stabilizers, and/or 0.01 to 1 wt % processing aids, and/or 0.1 to 1 wt % antistatic agents and/or 0.2 to 3 wt % pigments, in each case based on the propylene polymers used.
  • auxiliary materials such as 0.01 to 2.5 wt % stabilizers, and/or 0.01 to 1 wt % processing aids, and/or 0.1 to 1 wt % antistatic agents and/or 0.2 to 3 wt % pigments, in each case based on the propylene polymers used.
  • the stabilizers, contained in the inventive propylene polymers preferably are mixtures of 0.01 to 0.6 wt % phenolic antioxidants, 0.01 to 0.6 wt % 3-arylbenzofuranones, 0.01 to 0.6 wt % processing stabilizers based on phosphites, 0.01 to 0.6 wt % high temperature stabilizers based on disulfides and thioethers and/or 0.01 to 0.8 wt % statically hindered amines (HALS).
  • HALS statically hindered amines
  • a further object of the present invention is a process for producing propylene polymers with an improved property spectrum from propylene homopolymers with melt indices of 0.05 to 15 9/10 min at 230° C./2.16 kg and/or block copolymers from 90.0 to 99.9 wt % of propylene and 0.1 to 10 wt % of ⁇ -olefins with 2 or 4 to 18 carbon atoms with melt indices of 0.05 to 20 9/10 min at 230° C./2.16 kg, wherein ⁇ -nucleated propylene homopolymers have an IR ⁇ 20.98, a tensile modulus of ⁇ 1500 MPa at +23° C.
  • the ⁇ -nucleating agents may be introduced into the propylene polymers as master batch for example from 0.05 to 25 parts by weight of ⁇ -nucleating agent and 75 to 99.95 parts by weight of propylene polymer.
  • Preferred applications of the propylene polymers with improved properties as well as of mixtures with conventional propylene homopolymers and/or propylene copolymers are molded parts in a pipe system, such as pipes and fittings, inspection chambers, pipe ducting systems, extrusion or compression molded sheets and the like.
  • a further object of the invention is to provide articles with an improved balance of stiffness and impact strength at low temperatures.
  • propylene block copolymers with 90.0 to 99.9 wt % propylene and 0.1 to 10 wt % ⁇ -olefins with 2 or 4 to 18 carbon atoms with melt indices of 0.05 to 20 g/10 min at 230° C./2.16 kg, which propylene block copolymers are ⁇ -nucleated, where the ⁇ -nucleated propylene block copolymers have an IR ⁇ of the propylene homopolymer block of ⁇ 0.98, for producing these articles.
  • Articles with a tensile modulus of ⁇ 1100 MPa at +23° C. and a Charpy impact strength, of ⁇ 6 kJ/m 2 at ⁇ 20° C., using notched test specimens, can be produced by using the aforementioned propylene block copolymers.
  • a propylene block copolymer obtained by combined bulk and gas phase polymerization using a Ziegler-Natta catalyst system with dicyclopentyldimethoxysilane as external donor, having an ethylene content of 8.3 wt %, an IR ⁇ of the propylene homopolymer block of 0.98, and a melt index of 0.30 g/10 min at 230° C./2.16 kg, 10 wt % of a master batch comprising 99 parts by weight of a propylene block copolymer having an ethylene content of 8.3 wt %, an IR ⁇ of the propylene homopolymer block of 0.985 and a melt index of 0.30 g/10 min at 230° C./2.16 kg, and 1 part by weight of pimelic acid calcium salt and 0.1 wt % calcium stearate, 0.1 wt % tetrakis[methylene(3,5-di-t-butylhydroxyhydrocinnam
  • the resulting polypropylene polymer has a melt index of 0.32 9/10 min at 230° C./2.16 kg, a tensile modulus of 1290 MPa and a Charpy impact strength, notched, of 39 kJ/m 2 at ⁇ 20° C.
  • a propylene homopolymer obtained by bulk polymerization using a Ziegler-Natta catalyst system with dicyclopentyldimethoxysilane as external donor, having an IR ⁇ of 0.985 and a melt index of 1.1 g/10 min at 230° C./2.16 kg, 6 wt % of a master batch comprising 98.8 parts by weight of a propylene block copolymer having an ethylene content of 8.3 wt %, an IR ⁇ of the propylene homopolymer block of 0.985 and a melt index of 0.30 g/10 min at 230° C./2.16 kg, and 0.2 parts by weight of a mixed crystal of 5,12-dihydro(2,3b) acridine-7,14-dione with quino(2,3b)acridine-6,7,13,14-(5H,12H)-tetrone and 0.05 wt % calcium stearate, 0.1
  • the resulting polypropylene polymer has a melt index of 1.0 g/10 min at 230° C./2.16 kg, a tensile modulus of 1500 MPa and a Charpy impact strength, notched, of 11 kJ/m 2 at ⁇ 20° C.
  • a propylene block copolymer obtained by combined bulk and gas phase polymerization using a Ziegler-Natta catalyst system with dicyclopentyldimethoxysilane as external donor, having an ethylene content of 8.3 wt %, an IR ⁇ of the propylene homopolymer block of 0.985 and a melt index of 0.30 g/10 min at 230° C./2.16 kg, 25 wt % of a master batch comprising 99.5 parts by weight of a propylene block copolymer having an ethylene content of 8.3 wt %, an IR ⁇ of the propylene homopolymer block of 0.987 and a melt index of 0.30 g/10 min at 230° C./2.16 kg, and 0.5 parts by weight of hexahydrophthaloylglycine calcium salt and 0.1 wt % calcium stearate, 0.1 wt % tetrakis[methylene(3,5-di-
  • the resulting polypropylene polymer has a melt index of 0.32 WI 0 min at 230° C./2.16 kg, a tensile modulus of 1310 MPa and a Charpy impact strength, notched, of 37 kJ/m 2 at 20° C.
  • a propylene homopolymer obtained by bulk phase polymerization using a Ziegler-Natta catalyst system with dicyclopentyldimethoxysilane as external donor, having an IR ⁇ of 0.987, and a melt index of 1.1 g/10 min at 230° C./2.16 kg, 5 wt % of a master batch comprising 97.5 parts by weight of a propylene homopolymer having an IR ⁇ of 0.987 and a melt index of 4.2 g/10 min at 230° C./2.16 kg, and 2.5 parts by weight of N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide and 0.05 wt % calcium stearate, 0.1 wt % tetrakis[methylene(3,5-di-t-butylhydroxyhydrocinnamate)]methane and 0.1 wt % tris-(2,4-di-t-butylpheny
  • the resulting polypropylene polymer has a melt index of 1.2 g/10 min at 230° C./2.16 kg, a tensile modulus of 1765 MPa and a Charpy impact strength, notched, of 5.5 kJ/m 2 at ⁇ 20° C.
  • the resulting polypropylene polymer has a melt index of 0.3 9/10 min at 230° C./2.16 kg, a tensile modulus of 1750 MPa and a Charpy impact strength, notched, of 8.4 kJ/m 2 at 20° C.

Abstract

The invention relates to novel propylene polymers with improved properties especially with improved stiffness and impact strength comprising propylene homopolymers or propylene block copolymers with 90.0 to 99.9 wt % propylene and 0.1 to 10 wt % α-olefins with 2 or 4 to 18 carbon atoms, or mixtures thereof, wherein the propylene homopolymers or propylene block copolymers are β-nucleated propylene polymers, whereby the β-nucleated propylene homopolymers have an IRτ≧0.98, a tensile modulus ≧1500 MPa at +23° C. and a Charpy impact strength, ≧3 kJ/m2 at −20° C. using notched test specimens, and the β-nucleated propylene block copolymers are polymers having an IRτ of the propylene homopolymer block of ≧0.98, a tensile modulus ≧1100 Mpa at +23° C. and a Charpy impact strength of ≧6 kJ/m2 at −20° C. using notched test specimens. The propylene polymers with an improved property spectrum are suitable for producing molded parts in a pipe system, such as pipes and fittings, inspection chambers, pipe ducting systems, extrusion or compression molded sheets and the like.

Description

    REFERENCE TO RELATED APPLICATION
  • This is a continuation application of Ser. No. 10/478,549, filed Feb. 25, 2004, which is currently pending. The subject matter of the aforementioned prior application is hereby incorporated herein by reference.
  • FIELD OF THE INVENTION
  • The invention relates to propylene polymers with improved properties as well as to a process for producing them.
  • BACKGROUND OF THE INVENTION
  • Propylene polymer compositions from common propylene polymers and β-nucleating agents are known. β-Nucleating agents are useful in compositions for forming unstretched films which can be made porous by extraction of β-spherulites and stretching the films (disclosed for example in U.S. Pat. No. 4,386,129; U.S. Pat. No. 4,975,469).
  • Another effect of β-nucleating agents in propylene compositions is the improved thermoformability. As the melting point of the β-form of the spherulites of polypropylene based resins is generally about 144 to 148° C., contrasted with the typical melting point range of α-form spherulites of about 159 to 163° C., melt forming from these compositions is possible at lower temperatures and higher production rates (WO 93/12 262).
  • The disadvantage of these compositions having good impact properties is that they show unsatisfactory strength.
  • Conventional polypropylene homopolymers usually show high stiffness, but poor impact strength. Conventional β-nucleated polypropylenes usually have improved impact strength but also exhibit reduced stiffness.
  • OBJECT OF THE INVENTION
  • Therefore it is the object of the present invention to provide propylene polymers with improved properties characterized in having high stiffness and good impact properties simultaneously.
  • BRIEF DESCRIPTION OF THE INVENTION
  • According to the present invention, this object is achieved by propylene polymers with improved properties comprising propylene homopolymers with melt indices of 0.05 to 15 g/10 min at 230° C./2.16 kg or propylene block copolymers with 90.0 to 99.9 wt % propylene and 0.1 to 10 wt % α-olefins with 2 or 4 to 18 carbon atoms with melt indices of 0.05 to 20 9/10 min at 230° C./2.16 kg, or mixtures thereof, wherein the propylene homopolymers or propylene block copolymers are β-nucleated propylene polymers, whereby the β-nucleated propylene homopolymers have an IRτ≧0.98, a tensile modulus of ≧1500 MPa at +23° C. and a Charpy impact strength of ≧3 kJ/m2 at −20° C. using notched test specimens, and the β-nucleated propylene block copolymers are polymers having an IRτ of the propylene homopolymer block of ≧0.98, a tensile modulus of 1100 MPa at +23° C. and a Charpy impact strength, of 6 kJ/m2 at −20° C., using notched test specimens.
  • DETAILED DESCRIPTION OF THE INVENTION
  • β-nucleated propylene polymers are isotactic propylene polymers composed of chains in a 31 helical conformation having an internal microstructure of β-form spherulites being composed of radial arrays of parallel stacked lamellae. This microstructure can be realized by the addition of β-nucleating agents to the melt and subsequent crystallization. The presence of the β-form can be detected through the use of wide angle X-ray diffraction (Moore, J., Polypropylene Handbook, p. 134-135, Hanser Publishers Munich 1996).
  • The IRτ of the propylene polymers is measured and calculated as described in EP 0 277 514 A2 on page 5 (column 7, line 53 to column 8, line 11).
  • According to a preferred embodiment the β-nucleated propylene homopolymers or the propylene homopolymer block of the β-nucleated propylene block copolymers have an IRτ of ≧20.985. The difference of 0.005 in IRτ, IRτ being a measure for isotacticity, encompasses a significant increase in mechanical polymer properties, especially in stiffness.
  • The propylene homopolymers according to the present invention have melt indices of 0.05 to 15 g/10 min at 230° C./2.16 kg, preferably 0.1 to 8 g/10 min at 230° C./2.16 kg, most preferably 0.2 to 5 g/10 min at 230° M. 16 kg. The propylene copolymers according to the present invention have melt indices of 0.05 to 20 g/10 min at 230° C./2.16 kg, preferably 0.1 to 8 g/10 min at 230° C./2.16 kg, most preferably 0.2 to 5 g/10 min at 230° C./2.16 kg.
  • According to the present invention the propylene homopolymers show a tensile modulus ≧1500 MPa, preferably ≧1600 MPa and the propylene copolymers show a tensile modulus ≧1100 MPa, preferably ≧1300 MPa and most preferably ≧1500 MPa.
  • The propylene homopolymers according to the present invention have a Charpy impact strength of ≧3 kJ/m2 at −20° C., preferably 4 to 10 kJ/m2 at −20° C., most preferably 5 to 10 kJ/m2 at −20° C.
  • The propylene copolymers according to the present invention have a Charpy impact strength of ≧6 kJ/m2 at −20° C., preferably ≧9 kJ/m2 at −20° C., most preferably ≧10 kJ/m2 at −20° C. Charpy impact strength of up to at least 60 kJ/m2 is possible for copolymers according to the invention.
  • According to an advantageous feature of the present invention the β-nucleated propylene polymers with an IRτ≧0.98 being propylene polymers obtained by polymerization with a Ziegler-Natta catalyst system comprising titanium-containing solid components, an organo alumina, magnesium or titanium compound as cocatalyst and an external donor according to the formula

  • RxR′ySi(MeO)4-x-y′
  • wherein R and R′ are identical or different and are branched or cyclic aliphatic or aromatic hydrocarbon residues, and y and x independently from each other are O or 1, provided that x+y are 1 or 2.
  • Examples of propylene polymers with high IRE obtained by polymerization with a Ziegler-Natta catalyst system, for example by slurry, bulk or gas phase polymerization, are propylene polymers as described in EP-A-0,790, 262, WO 99/24,478 and WO 99/16,797.
  • A preferred external donor of the Ziegler-Natta catalyst system is dicyclopentyldimethoxysilane.
  • According to a preferred embodiment the, B-nucleated propylene polymer contains 0.01 to 2.0 wt %, in each case based on the propylene polymers used, of
      • dicarboxylic acid derivative type diamide compounds from C5-C8-cycloalkyl monoamines or C6-C12-aromatic monoamines and C5-C8-aliphatic, C5-C8-cycloaliphatic or C6-C12-aromatic dicarboxylic acids, preferably N,N′-di-C5-C8-cycloalkyl-2,6-naphthalene dicarboxamide compounds, N,N′-di-C5-C8-cycloalkyl-4,4-biphenyidicarboxamide compounds, N,N′-di-C5-C8-cycloalkylterephthalamide compounds, N. N′-di-C5-C8-cycloalkyl-1,4-cyclohexanedicarbox-amide compounds and/or N,N′-di-C6-C12-aryl-C5-C8-diamide compounds; and/or diamine derivative type diamide compounds from C5-C8-cycloalkyl monocarboxylic acids or C6-C12-aromatic monocarboxylic acids and C5-C8-cycloaliphatic or C6-C12-aromatic diamines, preferably N,N′-C6-C12-arylene-bis-benzamide compounds, N,N′-C5-C8-cycloalkyl-bis-benzamide compounds, N,N′-p-C6-C12-arylene-bis-C5-C8-cycloalkylcarboxamide compounds and/or N,N′-C5-C8-cycloalkyl-bis-cyclohexanecarboxamide compounds; and/or
      • amino acid derivative type diamide compounds from amidation reaction of C5-C8-alkyl-, C5-C8-cycloalkyl- or C6-C12-arylamino acids, C5-C8-alkyl-, C5-C8-cycloalkyl- or C6-C12-aromatic monocarboxylic acid chlorides and C5-C8-alkyl-, C5-C8-cycloalkyl- or C6-C12-aromatic mono-amines, preferably N-phenyl-5-(N-benzoylamino)pentaneamide and/or N-cyclohexyl-4-N-cyclohexylcarbonylamino) benzamide, as p-nucleating agent.
  • Examples of N,N′-di-C5-C8-cyclo alkyl-2,6-naphthalene dicarboxamide compounds are N,N′-dicyclohexyl-2,6-naphthalene dicarboxamide and N,N′-dicyclooctyl-2,6-naphthalene dicarboxamide.
  • Examples of N,N′-di-C5-C8-cycloalkyl-4,4-biphenyldicarboxamide compounds are N,N′-dicyclohexyl-4,4-biphenyldicarboxamide and N. N′-dicyclopentyl-4,4-biphenyldicarboxamide.
  • Examples of N,N′-di-C5-C8-cycloalkylterephthalamide compounds are N,N′-dicyclohexylterephthalamide and N,N′-dicyclopentylterephthalamide.
  • Examples of N,N′-di-C5-C8-cycloalkyl-1,4-cyclohexanedicarboxamide compounds are N,N′-dicyclohexyl-1,4-cyclohexanedicarboxamide and N,N′-dicyclohexyl-1,4-cyclopentanedicarboxanaide.
  • Examples of N,N′-di-C6-C12-aryl-Cs-C-diamide compounds are N,N′-bis(p-methylphenyl)-hexanediamide, N,N′-bis(4-cyclohexylphenyl)hexanediamide, N,N′-diphenylhexanediamide, N,N′-diphenyloctanediamide and N,N′-bis(p-ethylphenyl)hexanediamide.
  • Examples of N,N′-C6-C12-arylene-bis-benzamide compounds are N,N′-p-phenylene-bis-benzamide and N,N′-1,5-naphthalene-bis-benzamide.
  • Examples of N,N′-C5-C8-cycloalkyl-bis-benzamide compounds are N,N′-1,4-cyclopentane-bis-benzamide and N,N′-1,4-cyclohexane-bis-benzamide.
  • Examples of N,N′-p-C6-C12-arylene-bis-C5-C8-cycloalkylcarboxamide compounds are N,N′-1,5-naphthalene-bis-cyclohexanecarboxamide and N,N′-1,4-phenylene-bis-cyclohexanecarboxamide.
  • Examples of N,N′-C5-C8-cycloalkyl-bis-cyclohexanecarboxamide compounds are N,N′-1,4-cyclopentane-bis-cyclohexanecarboxamide and N,N′-1,4-cyclohexane-bis-cyclohexanecarboxamide.
  • According to a further preferred embodiment the β-nucleated propylene polymer contains 0.0001 to 2.0 wt % of quinacridone type compounds, especially quinacridone, dimethylquinacridone and/or dimethoxyquinacridone; quinacridonequinone type compounds, especially quinacridonequinone, a mixed crystal of 5,12-dihydro(2,3b)acridine-7,14-dione with quino(2,3b)acridine-6,7,1 3,14-(5H, 12H)-tetrone as disclosed in EP-B 0 177 961 and/or dimethoxyquinacridonequinone; and/or dihydroquinacridone type compounds, especially dihydroquinacridone, di-methoxydihydroquinacridone and/or dibenzodihydroquinacridone, as β-nucleating agent.
  • According to a further preferred embodiment the β-nucleated propylene polymer contains 0.01 to 2.0 wt % of dicarboxylic acid salts of metals from group Ha of periodic system, especially pimelic acid calcium salt and/or suberic acid calcium salt; and/or mixtures of dicarboxylic acids and salts of metals from group Ha of periodic system, as β-nucleating agent.
  • According to a further preferred embodiment the p-nucleated propylene polymer contains 0.01 to 2.0 wt % of salts of metals from group Ha of periodic system and imido acids of the formula
  • Figure US20100305246A1-20101202-C00001
  • wherein x=1 to 4; R═H, —COOH, C1-C12-alkyl, C5-C8-cycloalkyl or C6-C12-aryl, and Y═C1-C12-alkyl, C5-C8-cycloalkyl or C6-C12-aryl-substituted bivalent C6-C12-aromatic residues, especially calcium salts of phthaloylglycine, hexahydrophthaloylglycine, N-phthaloylalanine and/or N-4-methylphthaloylglycine, as β-nucleating agent.
  • The inventive propylene polymers with improved properties may contain usual auxiliary materials such as 0.01 to 2.5 wt % stabilizers, and/or 0.01 to 1 wt % processing aids, and/or 0.1 to 1 wt % antistatic agents and/or 0.2 to 3 wt % pigments, in each case based on the propylene polymers used.
  • The stabilizers, contained in the inventive propylene polymers, preferably are mixtures of 0.01 to 0.6 wt % phenolic antioxidants, 0.01 to 0.6 wt % 3-arylbenzofuranones, 0.01 to 0.6 wt % processing stabilizers based on phosphites, 0.01 to 0.6 wt % high temperature stabilizers based on disulfides and thioethers and/or 0.01 to 0.8 wt % statically hindered amines (HALS).
  • A further object of the present invention is a process for producing propylene polymers with an improved property spectrum from propylene homopolymers with melt indices of 0.05 to 15 9/10 min at 230° C./2.16 kg and/or block copolymers from 90.0 to 99.9 wt % of propylene and 0.1 to 10 wt % of α-olefins with 2 or 4 to 18 carbon atoms with melt indices of 0.05 to 20 9/10 min at 230° C./2.16 kg, wherein β-nucleated propylene homopolymers have an IRτ≧20.98, a tensile modulus of ≧1500 MPa at +23° C. and a Charpy impact strength of 3 kJ/m2 at −20° C. using notched test specimens, respectively, β-nucleated propylene block copolymers having an IRτ of the propylene homopolymer block of 0.98, a tensile modulus of ≧1100 MPa at +23° C. and a Charpy impact strength, ≧6 kJ/m2 at −20° C. using notched test specimens, are produced by melt mixing of propylene homopolymers having an IRτ≧0.98, respectively propylene block copolymers having an IRτ of the propylene homopolymer block of ≧0.98, with 0.0001 to 2.0 wt %, based on the polypropylenes used, of β-nucleating agents at temperatures from 175 to 250° C.
  • For the melt mixing of the propylene polymers and the β-nucleating agents, conventional compounding extruders are used.
  • In producing the inventive propylene polymers the β-nucleating agents may be introduced into the propylene polymers as master batch for example from 0.05 to 25 parts by weight of β-nucleating agent and 75 to 99.95 parts by weight of propylene polymer.
  • Preferred applications of the propylene polymers with improved properties as well as of mixtures with conventional propylene homopolymers and/or propylene copolymers are molded parts in a pipe system, such as pipes and fittings, inspection chambers, pipe ducting systems, extrusion or compression molded sheets and the like.
  • A further object of the invention is to provide articles with an improved balance of stiffness and impact strength at low temperatures.
  • It has been found that this object is achieved by using propylene homopolymers with melt indices of 0.05 to 15 g/10 min at 230° C./2.16 kg, which propylene homopolymers are β-nucleated, where the β-nucleated propylene homopolymers have an IRτ≧20.98, for producing these articles. Articles with a tensile modulus of ≧1500 MPa at +23° C. and a Charpy impact strength of ≧3 kJ/m2 at −20° C., using notched test specimens, can be produced by using the aforementioned propylene homopolymers.
  • It has been found that this object is also achieved by using propylene block copolymers with 90.0 to 99.9 wt % propylene and 0.1 to 10 wt % α-olefins with 2 or 4 to 18 carbon atoms with melt indices of 0.05 to 20 g/10 min at 230° C./2.16 kg, which propylene block copolymers are β-nucleated, where the β-nucleated propylene block copolymers have an IRτ of the propylene homopolymer block of ≧0.98, for producing these articles. Articles with a tensile modulus of ≧1100 MPa at +23° C. and a Charpy impact strength, of ≧6 kJ/m2 at −20° C., using notched test specimens, can be produced by using the aforementioned propylene block copolymers.
  • EXAMPLES
  • The following tests were made using injection molded samples prepared according to ISO 1873
  • Tensile modulus according to ISO 527 (cross head speed 1 mm/min) at +23° C. Charpy impact strength using notched specimens, according to ISO 179/1 eA
  • Example 1
  • A mixture of
  • 90 wt % of a propylene block copolymer, obtained by combined bulk and gas phase polymerization using a Ziegler-Natta catalyst system with dicyclopentyldimethoxysilane as external donor, having an ethylene content of 8.3 wt %, an IRτ of the propylene homopolymer block of 0.98, and a melt index of 0.30 g/10 min at 230° C./2.16 kg, 10 wt % of a master batch comprising 99 parts by weight of a propylene block copolymer having an ethylene content of 8.3 wt %, an IRτ of the propylene homopolymer block of 0.985 and a melt index of 0.30 g/10 min at 230° C./2.16 kg, and 1 part by weight of pimelic acid calcium salt and 0.1 wt % calcium stearate, 0.1 wt % tetrakis[methylene(3,5-di-t-butylhydroxyhydrocinnamate)]methane and 0.1 wt % tris-(2,4-di-t-butylphenyl)phosphite, based on the sum of the propylene polymers used, is melted in a twin screw extruder with a temperature profile of 100/145/185/210/220/200/185° C., homogenized, discharged and pelletized.
  • The resulting polypropylene polymer has a melt index of 0.32 9/10 min at 230° C./2.16 kg, a tensile modulus of 1290 MPa and a Charpy impact strength, notched, of 39 kJ/m2 at −20° C.
  • Example 2
  • A mixture of
  • 94 wt % of a propylene homopolymer, obtained by bulk polymerization using a Ziegler-Natta catalyst system with dicyclopentyldimethoxysilane as external donor, having an IRτ of 0.985 and a melt index of 1.1 g/10 min at 230° C./2.16 kg, 6 wt % of a master batch comprising 98.8 parts by weight of a propylene block copolymer having an ethylene content of 8.3 wt %, an IRτ of the propylene homopolymer block of 0.985 and a melt index of 0.30 g/10 min at 230° C./2.16 kg, and 0.2 parts by weight of a mixed crystal of 5,12-dihydro(2,3b) acridine-7,14-dione with quino(2,3b)acridine-6,7,13,14-(5H,12H)-tetrone and 0.05 wt % calcium stearate, 0.1 wt % tetrakis[methylene(3,5-di-t-butylhydroxyhydrocinnamate)]methane and 0.1 wt % tris-(2,4-di-t-butyl-phenyl)-phosphite, based on the sum of the propylene polymers used is melted in a twin screw extruder with a temperature profile of 100/145/190/215/225/205/190° C., homogenized, discharged and pelletized.
  • The resulting polypropylene polymer has a melt index of 1.0 g/10 min at 230° C./2.16 kg, a tensile modulus of 1500 MPa and a Charpy impact strength, notched, of 11 kJ/m2 at −20° C.
  • Example 3
  • A mixture of
  • 75 wt % of a propylene block copolymer, obtained by combined bulk and gas phase polymerization using a Ziegler-Natta catalyst system with dicyclopentyldimethoxysilane as external donor, having an ethylene content of 8.3 wt %, an IRτ of the propylene homopolymer block of 0.985 and a melt index of 0.30 g/10 min at 230° C./2.16 kg, 25 wt % of a master batch comprising 99.5 parts by weight of a propylene block copolymer having an ethylene content of 8.3 wt %, an IRτ of the propylene homopolymer block of 0.987 and a melt index of 0.30 g/10 min at 230° C./2.16 kg, and 0.5 parts by weight of hexahydrophthaloylglycine calcium salt and 0.1 wt % calcium stearate, 0.1 wt % tetrakis[methylene(3,5-di-t-butylhydroxyhydrocinnamate)]methane and 0.1 wt % tris-(2,4-di-t-butylphenyl)phosphite, based on the sum of the propylene polymers used, is melted in a twin screw extruder with a temperature profile of 100/145/185/210/220/200/185° C., homogenized, discharged and pelletized.
  • The resulting polypropylene polymer has a melt index of 0.32 WI 0 min at 230° C./2.16 kg, a tensile modulus of 1310 MPa and a Charpy impact strength, notched, of 37 kJ/m2 at 20° C.
  • Example 4
  • A mixture of
  • 95 wt % of a propylene homopolymer, obtained by bulk phase polymerization using a Ziegler-Natta catalyst system with dicyclopentyldimethoxysilane as external donor, having an IRτ of 0.987, and a melt index of 1.1 g/10 min at 230° C./2.16 kg, 5 wt % of a master batch comprising 97.5 parts by weight of a propylene homopolymer having an IRτ of 0.987 and a melt index of 4.2 g/10 min at 230° C./2.16 kg, and 2.5 parts by weight of N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide and 0.05 wt % calcium stearate, 0.1 wt % tetrakis[methylene(3,5-di-t-butylhydroxyhydrocinnamate)]methane and 0.1 wt % tris-(2,4-di-t-butylphenyl)-phosphite, based on the sum of the propylene polymers used, is melted in a twin screw extruder with a temperature profile of 100/145/190/215/225/205/190° C., homogenized, discharged and pelletized.
  • The resulting polypropylene polymer has a melt index of 1.2 g/10 min at 230° C./2.16 kg, a tensile modulus of 1765 MPa and a Charpy impact strength, notched, of 5.5 kJ/m2 at −20° C.
  • Example 5
  • A mixture of 95 wt % of a propylene homopolymer, obtained by bulk phase polymerization using a Ziegler-Natta catalyst system with dicyclopentyldimethoxysilane as external donor, having i an IRτ of 0.987, and a melt index of 0.3 g/10 min at 230° C./2.16 kg, 5 wt % of a master batch comprising 97.5 parts by weight of a propylene homopolymer having an IRτ of 0.987 and a melt index of 0.3 g/10 min at 230° C./2.16 kg, and 2.5 parts by weight of N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide and 0.05 wt % calcium 3 stearate, 0.1 wt % tetrakis[methylene(3,5-di-t-butylhydroxyhydrocinnamate)]methane and 0.1 wt % tris-(2,4-di-t-butylphenyl)-phosphite, based on the sum of the propylene polymers used, is melted in a twin screw extruder with a temperature profile of 100/145/190/215/225/205/190° C., homogenized, discharged and pelletized.
  • The resulting polypropylene polymer has a melt index of 0.3 9/10 min at 230° C./2.16 kg, a tensile modulus of 1750 MPa and a Charpy impact strength, notched, of 8.4 kJ/m2 at 20° C.

Claims (16)

1. Propylene polymers comprising propylene homopolymers having melt indices of 0.05 to 15 g/10 min at 230° C./2.6 kg or propylene block copolymers of 90.0 to 99.9 wt % propylene and 0.1 to 10 wt % α-olefins of 2 or 4 to 18 carbon atoms having melt indices of 0.05 to 20 g/10 min at 230° C./2.16 kg, or mixtures thereof, wherein the propylene homopolymers or propylene block copolymers are β-nucleated, the β-nucleated propylene homopolymers having an IRτ≧0.98, a tensile modulus of ≧1500 MPa at +23° C. and a Charpy impact strength of kJ/m2 at −20° C. using notched test specimens, and the β-nucleated propylene block copolymers are polymers having an IRτ of the propylene homopolymer block of ≧0.98, a tensile modulus of ≧1100 MPa at +23° C. and a Charpy impact strength of ≧6 kJ/m2 at −20° C. using notched test specimens.
2. Propylene polymers according to claim 1 wherein the melt indices at 230° C./2.6 kg of the propylene homopolymers and the propylene block copolymers are 0.1 to 8 g/10 min, the β-nucleated propylene homopolymers have a tensile modulus of ≧1600 MPa at +23° C. and a Charpy impact strength of 4 to 10 kJ/m2 at −20° C. using notched test specimens, and the β-nucleated propylene block copolymers have a tensile modulus of ≧1300 MPa at +23° C. and a Charpy impact strength of ≧9 kJ/m2 at −20° C. using notched test specimens.
3. Propylene polymers according to one of the claim 1 or 2, wherein the β-nucleated propylene homopolymers and propylene block copolymers are obtained by polymerization with a Ziegler-Natta catalyst system comprising titanium-containing solid components, an organoalumina, magnesium or titanium compound as cocatalyst and an external donor according to the formula

RxR′ySi(MeO)4-x-y′
wherein R and R′ are identical or different and are branched or cyclic aliphatic or aromatic hydrocarbon residues, and y and x independently from each other are 0 or 1, provided that x+y are 1 or 2.
4. Propylene polymers according to claim 3, wherein the external donor is dicyclopentyldimethoxysilane.
5. Propylene polymers according to claim 1 or 2, wherein the β-nucleated propylene polymers contain 0.01 to 2.0 wt %, in each case based on the propylene polymers, dicarboxylic acid derivative diamide compounds from C5-C8-cycloalkyl monoamines or C6-C12-aromatic monoamines and C5-C8-aliphatic, C5-C8-cycloaliphatic or C6-C12-aromatic dicarboxylic acids; and/or
diamine derivative diamide compounds from C5-C8-cyeloalkyl monocarboxylic acids or C6-C12-aromatic monocarboxylic acids and C5-C8-cycloaliphatic or C6-C12-aromatic diamines; and/or
amino acid derivative diamide compounds from amidation reaction of C5-C8-alkyl-, C5-C8-cycloalkyl- or C8-C12-arylamino acids, C5-C8-alkyl-, C5-C8-cycloalkyl- or C6-C12-aromatic monocarboxylic acid chlorides and C5-C8-alkyl-, C5-C8-cycloalkyl- or C6-C12-aromatic mono-amines, as β-nucleating agent.
6. Propylene polymers according to claim 1 or 2, wherein the β-nucleated propylene polymers contain 0.0001 to 2.0 wt % quinacridone compounds, quinacridonequinone compounds, and/or dihydroquinacridone compounds, as β-nucleating agent.
7. Propylene polymers according to claim 1 or 2, wherein the β-nucleated propylene polymers contain 0.01 to 2.0 wt % dicarboxylic acid salts of metals from group IIa of periodic system, and/or mixtures of dicarboxylic acids and metals from group IIa of the periodic system, as β-nucleating agent.
8. Propylene polymers according to claim 1 or 2, wherein the β-nucleated propylene polymers contain 0.01 to 2.0 wt % of salts of metals from group IIa of the periodic system and imido acids of the formula
Figure US20100305246A1-20101202-C00002
wherein x=1 to 4; R═H, —COOH, C1-C12-alkyl, C5-C8-cycloalkyl or C6-C12-aryl, and Y═C1-C12-alkyl, C5-C8-cycloalkyl or C6-C12-aryl-substituted bivalent C6-C12-aromatic residues, as β-nucleating agent.
9. A process for producing the propylene polymers according to claim 1 comprising melt mixing said propylene homopolymers having an IRτ≧0.98, or said propylene block copolymers having an IRτ of the propylene homopolymer block of ≧0.98, with 0.0001 to 2.0 wt %, based on the propylene polymers, of β-nucleating agents, said melt mixing occurring at temperatures from 175 to 250° C.
10. Molded articles comprising the propylene polymers according to claim 1 or 2.
11. Molded articles comprising the propylene homopolymers according to claim 1.
12. Molded articles comprising propylene block copolymers of 90.0 to 99.9 wt % propylene and 0.1 to 10 wt % α-olefins of 2 or 4 to 18 carbon atoms having melt indices of 0.05 to 20 g/10 min at 230° C./2.16 kg which propylene block copolymers are β-nucleated, where the β-nucleated propylene block copolymers have an IRτ of the propylene homopolymer block of ≧0.98, the molded articles having a tensile modulus of ≧1100 MPa at +23° C. and a Charpy impact strength of ≧kJ/m2 at −20° C. using notched test specimens.
13. Propylene polymers according to claim 5, wherein the dicarboxylic acid derivative diamide compounds are N,N′-di-C5-C8-cycloalkyl-2,6-naphthalene dicarboxamide compounds, N,N′-di-C5-C8-cycloalkyl-4,4-biphenyldicarboxamide compounds, N,N′-di-C5-C8-cycloalkylterephthalamide compounds, N,N-di-C5-C8-cycloalkyl-1,4-cyclohexanedicarboxamide compounds and/or N,N′-di-C6-C12-aryl-C5-C8-diamide compounds, the diamine derivative diamide compounds are N,N′-C6-C12-arylene-bis-benzamide compounds, N,N-p-C6-C12-arylene-bis-C5-C8-cycloalkyl-bis-benzamide compounds, N,N′-p-C6-C12-arylene-bis-C5-C8-cycloalkylcarboxamide compounds and/or N,N-C5-C8-cycloalkyl-bis-cyclohexanecarboxamide compounds, and the amino acid derivative diamide compounds are N-phenyl-5-(N-benzoylamino) pentaneamide and/or N-cyclohexyl-4-(N-cyclohexylcarbonylamino) benzamide.
14. Propylene polymers according to claim 6, wherein the quinacridone compounds are quinacridone, dimethylquinacridone and/or dimethoxyquinacridone, the quinacridonequinone compounds are quinacridonequinone, a mixed crystal of 5,12-dihydro(2,3b)acridine-7,14-dione with quino(2,3b)acridine-6,7,13,14-(5H,12H)-tetrone and/or dimethoxyquinacridonequinone, and the dihydroquinacridone compounds are dihydroquinacridone, dimethoxydihydroquinacridone and/or dibenzodihydroquinacridone.
15. Propylene polymers according to claim 7, wherein the dicarboxylic acid salts of metals from group IIa of the periodic system are pimelic acid calcium salt and/or suberic acid calcium salt.
16. Propylene polymers according to claim 8, wherein the salts of metals from group Ha of the periodic system and said amido acids are calcium salts of phthaloylglycine, hexahydrophthaloylglycine, N-phthaloylalanine and/or N-4-methylphthaloylglycine.
US12/857,341 2001-05-21 2010-08-16 Propylene polymers with improved properties Abandoned US20100305246A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US12/857,341 US20100305246A1 (en) 2001-05-21 2010-08-16 Propylene polymers with improved properties
US13/477,682 US8461267B2 (en) 2001-05-21 2012-05-22 Propylene polymers with improved properties

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP01112367.6 2001-05-21
EP01112367A EP1260529A1 (en) 2001-05-21 2001-05-21 Propylene polymers with improved properties
US10/478,549 US20040158002A1 (en) 2001-05-21 2002-05-21 Propylene polymers with improved properties
PCT/EP2002/005548 WO2002094894A1 (en) 2001-05-21 2002-05-21 Propylene polymers with improved properties
US12/857,341 US20100305246A1 (en) 2001-05-21 2010-08-16 Propylene polymers with improved properties

Related Parent Applications (3)

Application Number Title Priority Date Filing Date
PCT/EP2002/005548 Continuation WO2002094894A1 (en) 2001-05-21 2002-05-21 Propylene polymers with improved properties
US10478549 Continuation 2002-05-21
US10/478,549 Continuation US20040158002A1 (en) 2001-05-21 2002-05-21 Propylene polymers with improved properties

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/477,682 Continuation US8461267B2 (en) 2001-05-21 2012-05-22 Propylene polymers with improved properties

Publications (1)

Publication Number Publication Date
US20100305246A1 true US20100305246A1 (en) 2010-12-02

Family

ID=8177494

Family Applications (3)

Application Number Title Priority Date Filing Date
US10/478,549 Abandoned US20040158002A1 (en) 2001-05-21 2002-05-21 Propylene polymers with improved properties
US12/857,341 Abandoned US20100305246A1 (en) 2001-05-21 2010-08-16 Propylene polymers with improved properties
US13/477,682 Expired - Lifetime US8461267B2 (en) 2001-05-21 2012-05-22 Propylene polymers with improved properties

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US10/478,549 Abandoned US20040158002A1 (en) 2001-05-21 2002-05-21 Propylene polymers with improved properties

Family Applications After (1)

Application Number Title Priority Date Filing Date
US13/477,682 Expired - Lifetime US8461267B2 (en) 2001-05-21 2012-05-22 Propylene polymers with improved properties

Country Status (10)

Country Link
US (3) US20040158002A1 (en)
EP (2) EP1260529A1 (en)
CN (1) CN1235923C (en)
AT (1) ATE333476T1 (en)
AU (1) AU2002338995B2 (en)
DE (1) DE60213243T2 (en)
ES (1) ES2268063T3 (en)
HU (1) HU228329B1 (en)
RU (1) RU2279444C2 (en)
WO (1) WO2002094894A1 (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10261107A1 (en) * 2002-12-20 2004-07-01 Basell Polyolefine Gmbh Propylene (co)polymer molding composition, used for film, fiber or molding, especially pipe, has melt index in specified range and contains beta-crystallite fraction
US20050043447A1 (en) * 2003-04-16 2005-02-24 Mayzo, Inc. Beta nucleation concentrate
CN100560439C (en) * 2003-04-16 2009-11-18 美佐公司 The crystalline p p sheet of extruding that contains the β spherocrystal
US20070172613A1 (en) * 2004-08-17 2007-07-26 Philip Jacoby Beta-nucleation concentrates
US20060177632A1 (en) * 2005-02-08 2006-08-10 Philip Jacoby Beta-nucleation concentrates for film applications
AU2009253181B2 (en) * 2008-05-28 2012-09-20 Borealis Ag Propylene-hexene random copolymer produced in the presence of a Ziegler Natta catalyst
PL2344585T3 (en) * 2008-10-01 2018-10-31 Borealis Ag New sewage pipe material with improved properties
US20120095154A1 (en) 2009-04-09 2012-04-19 Klaus Bernreitner Thermoplastic polyolefin composition
ES2513829T3 (en) * 2009-11-19 2014-10-27 Omya International Ag Natural mineral acid modified filler to initialize polypropylene beta-nucleation
CN103483688B (en) * 2013-10-15 2016-01-06 重庆顾地塑胶电器有限公司 Beta-crystal polypropylene matrix material of shock resistance and stretch-proof and its preparation method and application
CN110023392A (en) * 2016-12-02 2019-07-16 巴斯夫欧洲公司 Reactive polyurethane-hot melt adhesive
CN109054171B (en) * 2018-06-28 2021-09-14 广东炜林纳新材料科技股份有限公司 Polypropylene toughening nucleating agent and preparation method thereof

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4386129A (en) * 1981-03-31 1983-05-31 Standard Oil Company (Indiana) Porous polymeric films
US4975469A (en) * 1989-03-20 1990-12-04 Amoco Corporation Oriented porous polypropylene films
US5231126A (en) * 1985-04-01 1993-07-27 Shi Guan Yi Beta-crystalline form of isotactic polypropylene and method for forming the same
US5681922A (en) * 1994-05-13 1997-10-28 Pcd Polymere Gesellschaft M.B.H. Process for increasing the proportion of the β-modification in polypropylene
US5716998A (en) * 1994-10-31 1998-02-10 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Pre-expanded particles of polypropylene resin and process of preparing the same
US6444301B1 (en) * 1997-03-18 2002-09-03 Hoechst Trespaphan Gmbh Labels
US20040157019A1 (en) * 2001-05-21 2004-08-12 Mcgoldrick James Industrial polyolefin piping system
US20040170790A1 (en) * 2001-05-21 2004-09-02 Carl-Gustaf Ek Polyolefin multilayer pipe
US20050025922A1 (en) * 2001-05-21 2005-02-03 Cecilia Rydin Polyolefin coated steel pipes
US20050277720A1 (en) * 2002-05-21 2005-12-15 Carl-Gustaf Ek Polypropylene compositions especially for pipes

Family Cites Families (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3319515A1 (en) 1983-05-28 1984-11-29 kabelmetal electro GmbH, 3000 Hannover Pipeline for the transport of heated media
US4606953A (en) 1983-06-23 1986-08-19 Nippon Steel Corporation Polypropylene coated steel pipe
JPS6090229A (en) 1983-10-24 1985-05-21 Japan Styrene Paper Co Ltd Expanded particle of polyethylene based resin
JPS60110717A (en) 1983-11-21 1985-06-17 Nichias Corp Production of polyurethane foam
AT381110B (en) * 1984-10-11 1986-08-25 Danubia Petrochemie POLYPROPYLENE, CRYSTALLINE COPOLYMERS THEREOF, OR MIXTURES WITH OTHER POLYOLEFINS WITH A MAJOR POLYPROPYLENE PART WITH HIGH IMPACT RESISTANCE AND TENSION RESISTANCE AND USE THEREOF
ATE88196T1 (en) 1985-01-31 1993-04-15 Himont Inc FREE LONG CHAIN BRANCHING POLYPROPYLENE, PROCESS FOR PRODUCTION AND USE THEREOF.
CN1004076B (en) * 1985-04-01 1989-05-03 中国科学院上海有机化学研究所 Process for preparation of beta-crystalline polypropylene
JPH075668B2 (en) * 1987-02-04 1995-01-25 チッソ株式会社 Highly crystalline polypropylene
US5047485A (en) 1989-02-21 1991-09-10 Himont Incorporated Process for making a propylene polymer with free-end long chain branching and use thereof
IT1242305B (en) 1990-03-09 1994-03-04 Ausimont Srl COMPOSITIONS OF CROSS-LINKED POLYPROPYLENE SUITABLE FOR THE PREPARATION OF FOAMED MATERIALS
JPH0622991B2 (en) 1990-09-28 1994-03-30 新日本製鐵株式会社 Polyolefin coated steel pipe for high temperature buried piping
US6235823B1 (en) * 1992-01-24 2001-05-22 New Japan Chemical Co., Ltd. Crystalline polypropylene resin composition and amide compounds
US5310584B1 (en) 1992-04-14 1999-02-16 Amoco Corp Thermoformable polypropylene-based sheet
DE4219863A1 (en) 1992-06-17 1993-12-23 Basf Ag Maleic acid bisimide crosslinked, soft polyolefin mixtures
DE4219861A1 (en) 1992-06-17 1993-12-23 Basf Ag Olefin polymers partially crosslinked with bismaleimido compounds
US5508318A (en) 1993-07-15 1996-04-16 Montell North America Inc. Compositions of irradiated and non-irradiated olefin polymer materials with reduced gloss
JP3171422B2 (en) 1994-04-20 2001-05-28 日本原子力研究所 Method for producing modified polypropylene and molded article
JPH0873546A (en) 1994-06-23 1996-03-19 Basf Ag Synthetic resin material cross-linked partially with unsaturated ester
CA2162946C (en) * 1994-11-21 2004-01-06 Kazuyuki Watanabe Propylene block copolymer and process for producing the same
US5574816A (en) 1995-01-24 1996-11-12 Alcatel Na Cable Sytems, Inc. Polypropylene-polyethylene copolymer buffer tubes for optical fiber cables and method for making the same
JPH08300562A (en) 1995-04-28 1996-11-19 Nippon Steel Corp Polypropylene coated steel tube
JP3405621B2 (en) 1995-04-28 2003-05-12 新日本製鐵株式会社 Polyethylene coated steel pipe
US6005034A (en) * 1995-08-31 1999-12-21 Chisso Corpoation Propylene-ethylene copolymer composition and process for producing the same
CA2234167C (en) * 1995-10-10 2004-09-14 Henrik Andtsjo Process for making propylene homo or copolymers
CZ291241B6 (en) 1995-12-07 2003-01-15 Shell Internationale Research Maatschappij B.V: Polyether polyol for preparing solid polyurethane foams
JPH09227707A (en) 1996-02-23 1997-09-02 Tonen Chem Corp Production of polypropylene resin foam
EP0883769B1 (en) 1996-03-04 2003-05-02 Borealis A/S Method of preparing a multilayer pipe
JPH1076601A (en) 1996-09-06 1998-03-24 Nkk Corp Multiple coating metallic tube
CA2199556C (en) 1997-03-10 2006-10-03 James Arthur Auger Polyolefin pipe
WO1998043806A1 (en) 1997-03-29 1998-10-08 Hewing Gmbh Multi-layer plastic tube
FI980342A0 (en) 1997-11-07 1998-02-13 Borealis As Polymerroer och -roerkopplingar
DE19758124C1 (en) 1997-12-30 1999-11-18 Borealis Ag Polypropylene tube with high strength
US20030008091A1 (en) 1998-02-04 2003-01-09 Roland Konrad Pipe, especially pressure pipe
DE19815046A1 (en) 1998-04-03 1999-10-14 Borealis Ag Polyolefin films and polyolefin coatings on substrates
JP2000000838A (en) 1998-06-18 2000-01-07 Sumitomo Chem Co Ltd Resin injection molding with good appearance
EP0972801A1 (en) 1998-07-16 2000-01-19 KE-KELIT Kunststoffwerk Gesellschaft m.b.H. Resin for hot water installations
JP2000044909A (en) 1998-07-29 2000-02-15 Mitsubishi Chemicals Corp Adhesive resin composition
FI991057A0 (en) 1999-05-07 1999-05-07 Borealis As High stiffness propylene polymers and process for their preparation
JP4135844B2 (en) 1999-11-11 2008-08-20 東罐興業株式会社 Multipack
DE19957384A1 (en) 1999-11-29 2001-05-31 Targor Gmbh Propylene polymer, useful for the production of water pipes, has a Mw of 350,000-1,000,000 g/mol, Mw/Mn of 4-10, contains polymer fractions having a viscosity number of 500-1400 ml/g and 200-400 ml/g
EP1174261A1 (en) 2000-07-20 2002-01-23 Borcalis GmbH Single and multilayer polyolefin foam pipes
EP1339787B1 (en) 2000-11-10 2009-05-13 INEOS Manufacturing Belgium NV Tubes obtained from a propylene polymer composition
AU2002232207B2 (en) 2001-02-21 2007-03-22 New Japan Chemical Co., Ltd. Successively biaxial-oriented porous polypropylene film and process for production thereof
US6632850B2 (en) 2001-04-04 2003-10-14 3M Innovative Properties Company Microporous materials and methods of making the same
EP1260528A1 (en) 2001-05-21 2002-11-27 Borealis Technology OY Propylene polymer pipes for pipelines
JP3589225B2 (en) 2002-02-08 2004-11-17 セイコーエプソン株式会社 projector
DE602007003584D1 (en) * 2007-07-12 2010-01-14 Borealis Tech Oy β-nucleated polypropylene composition

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4386129A (en) * 1981-03-31 1983-05-31 Standard Oil Company (Indiana) Porous polymeric films
US5231126A (en) * 1985-04-01 1993-07-27 Shi Guan Yi Beta-crystalline form of isotactic polypropylene and method for forming the same
US4975469A (en) * 1989-03-20 1990-12-04 Amoco Corporation Oriented porous polypropylene films
US5681922A (en) * 1994-05-13 1997-10-28 Pcd Polymere Gesellschaft M.B.H. Process for increasing the proportion of the β-modification in polypropylene
US5716998A (en) * 1994-10-31 1998-02-10 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Pre-expanded particles of polypropylene resin and process of preparing the same
US6444301B1 (en) * 1997-03-18 2002-09-03 Hoechst Trespaphan Gmbh Labels
US20040157019A1 (en) * 2001-05-21 2004-08-12 Mcgoldrick James Industrial polyolefin piping system
US20040170790A1 (en) * 2001-05-21 2004-09-02 Carl-Gustaf Ek Polyolefin multilayer pipe
US20050025922A1 (en) * 2001-05-21 2005-02-03 Cecilia Rydin Polyolefin coated steel pipes
US20100071796A1 (en) * 2001-05-21 2010-03-25 Borealis Technology Oy Polyolefin multilayer pipe
US20050277720A1 (en) * 2002-05-21 2005-12-15 Carl-Gustaf Ek Polypropylene compositions especially for pipes

Also Published As

Publication number Publication date
DE60213243T2 (en) 2007-08-02
EP1401894A1 (en) 2004-03-31
WO2002094894A1 (en) 2002-11-28
EP1401894B1 (en) 2006-07-19
DE60213243D1 (en) 2006-08-31
ES2268063T3 (en) 2007-03-16
PL366946A1 (en) 2005-02-07
US8461267B2 (en) 2013-06-11
US20040158002A1 (en) 2004-08-12
CN1529722A (en) 2004-09-15
HU228329B1 (en) 2013-03-28
AU2002338995B2 (en) 2007-10-18
EP1260529A1 (en) 2002-11-27
RU2279444C2 (en) 2006-07-10
RU2003136748A (en) 2005-05-20
ATE333476T1 (en) 2006-08-15
US20120302680A1 (en) 2012-11-29
HUP0400072A2 (en) 2004-03-29
HUP0400072A3 (en) 2007-12-28
CN1235923C (en) 2006-01-11

Similar Documents

Publication Publication Date Title
US8461267B2 (en) Propylene polymers with improved properties
US8895123B2 (en) Polyolefin multilayer pipe
US8389089B2 (en) Propylene polymer pipes for pipelines
EP1509566B1 (en) Polypropylene compositions especially for pipes
RU2451698C2 (en) Beta-nucleated propylene copolymer
AU2002339000A1 (en) Polyolefin multilayer pipe
KR101650637B1 (en) Low filled polypropylene composition with balanced property profile
AU2002338995A1 (en) Propylene polymers with improved properties
AU2002338997A1 (en) Propylene polymer pipes for pipelines
PL203575B1 (en) Propylene polymers and the method of their production

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

AS Assignment

Owner name: BOREALIS AG, AUSTRIA

Free format text: CHANGE OF ADDRESS;ASSIGNOR:BOREALIS AG;REEL/FRAME:059219/0949

Effective date: 20220201