US20100305246A1 - Propylene polymers with improved properties - Google Patents
Propylene polymers with improved properties Download PDFInfo
- 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
Links
- 0 *C(CC(=O)O)N1C(=O)[Y]C1=O.C.C Chemical compound *C(CC(=O)O)N1C(=O)[Y]C1=O.C.C 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular 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
- C08F297/08—Macromolecular 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
- C08F297/083—Macromolecular 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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
- 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.
- 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 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.
- 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.
- 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.
- 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
- 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.
- 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
- 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.
- 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.
- 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.
- 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.
- 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′
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
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.
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)
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)
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)
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 |
-
2001
- 2001-05-21 EP EP01112367A patent/EP1260529A1/en not_active Withdrawn
-
2002
- 2002-05-21 ES ES02750958T patent/ES2268063T3/en not_active Expired - Lifetime
- 2002-05-21 CN CNB028141970A patent/CN1235923C/en not_active Expired - Lifetime
- 2002-05-21 AT AT02750958T patent/ATE333476T1/en not_active IP Right Cessation
- 2002-05-21 EP EP02750958A patent/EP1401894B1/en not_active Expired - Lifetime
- 2002-05-21 US US10/478,549 patent/US20040158002A1/en not_active Abandoned
- 2002-05-21 HU HU0400072A patent/HU228329B1/en not_active IP Right Cessation
- 2002-05-21 RU RU2003136748/04A patent/RU2279444C2/en not_active IP Right Cessation
- 2002-05-21 WO PCT/EP2002/005548 patent/WO2002094894A1/en active IP Right Grant
- 2002-05-21 AU AU2002338995A patent/AU2002338995B2/en not_active Ceased
- 2002-05-21 DE DE60213243T patent/DE60213243T2/en not_active Expired - Lifetime
-
2010
- 2010-08-16 US US12/857,341 patent/US20100305246A1/en not_active Abandoned
-
2012
- 2012-05-22 US US13/477,682 patent/US8461267B2/en not_active Expired - Lifetime
Patent Citations (11)
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 |