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WO2009078854A1 - Tuyaux en polyoléfine - Google Patents

Tuyaux en polyoléfine Download PDF

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Publication number
WO2009078854A1
WO2009078854A1 PCT/US2007/087624 US2007087624W WO2009078854A1 WO 2009078854 A1 WO2009078854 A1 WO 2009078854A1 US 2007087624 W US2007087624 W US 2007087624W WO 2009078854 A1 WO2009078854 A1 WO 2009078854A1
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WO
WIPO (PCT)
Prior art keywords
propylene
copolymer
pipe
olefm
composition
Prior art date
Application number
PCT/US2007/087624
Other languages
English (en)
Inventor
Trazollah Ouhadi
Original Assignee
Advanced Elastomer Systems, L.P.
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 Advanced Elastomer Systems, L.P. filed Critical Advanced Elastomer Systems, L.P.
Priority to PCT/US2007/087624 priority Critical patent/WO2009078854A1/fr
Publication of WO2009078854A1 publication Critical patent/WO2009078854A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers

Definitions

  • the present invention relates in general to pipes made from polyolefm compositions, and more particularly relates to polypropylene-based pipes suitable as a pipe (channel/conduit) for transporting liquids, gases, and/or flowable solid.
  • a propylene random copolymer is typically more resistant to heat and pressure environments, but lacks formability, such as to form "U" shaped bends (and other types of forming) suitable for in-floor heating coils and is still too rigid and fragile. What is needed is a pipe composition that is cost effective, strong enough to meet current regulations (e.g. flexural modulus (23 0 C) less than 650 MPa, an Izod Impact (23 0 C) greater than 30 kJ/m 2 , and a Vicat Softening Temperature greater than HO 0 C) and allow for formability.
  • current regulations e.g. flexural modulus (23 0 C) less than 650 MPa, an Izod Impact (23 0 C) greater than 30 kJ/m 2 , and a Vicat Softening Temperature greater than HO 0 C
  • a pipe comprising a composition of one or more propylene- ⁇ -olefm copolymers comprising propylene-derived units and from 5 to 35 wt%, by weight of the propylene- ⁇ -olefm copolymer, of ethylene-derived units and/or C 4 to C 10 ⁇ -olefm-derived units, and having (i) a density from 0.850 to 0.920 g/cm 3 ; (ii) an H f of less than 75 J/g; and (iii) a T m of less than 105 0 C; and at least one additional component selected from the group consisting of propylene random copolymers having a comonomer content of less than 5 wt%, a propylene block copolymer, propylene homopolymer and combinations thereof; wherein the pipe composition possesses a Flexural Modulus (23 0 C) less than 650 MPa, an Izod Impact (23
  • a method of forming a pipe comprising melt-blending one or more propylene- ⁇ -olefm copolymers comprising propylene-derived units and from 5 to 35 wt%, by weight of the propylene- ⁇ -olefm copolymer, of ethylene-derived units and/or C 4 to C 10 ⁇ -olefin- derived units, and having (i) a density from 0.850 to 0.920 g/cm ; (ii) an H f of less than 75 J/g; (iii) a T m of less than 105 0 C; and at least one additional component selected from the group consisting of propylene random copolymers having a comonomer content of less than 5 wt%, a propylene block copolymer, propylene homopolymer and combinations thereof; followed by extruding the blend of propylene- ⁇ -olefm copolymers and additional component through a pipe- forming die; and
  • pipe refers to a cylindrical channel (or conduit) having a circular, ellipsoidal, square or other suitable cross-section, and having a certain wall thickness, and capable of transporting liquid and/or gas and/or flowable solid.
  • the inside of the wall makes contact with the substance to be conveyed in one embodiment, or is a layer of a multi-layer pipe (thus contacting another layer of pipe material) in another embodiment.
  • the pipe can be of any desirable length and made by any suitable means known in the art.
  • a "pipe composition” is a combination of two or more components defined herein that is used to form the pipe, or at least a section or layer of the pipe.
  • the pipe compositions include one or more propylene- ⁇ -olefm copolymers and at least one additional component selected from the group consisting of propylene random copolymers having a comonomer content of less than 5 wt%, a propylene block copolymer, propylene homopolymer and combinations thereof.
  • the pipes herein consist essentially of one or more propylene- ⁇ -olefm copolymers and at least one additional component selected from the group consisting of propylene random copolymers having a comonomer content of less than 5 wt%, a propylene block copolymer, propylene homopolymer and combinations thereof.
  • the properties e.g., Vicat Softening Temperature, HDT, Tensile, Izod, Elongation, etc.
  • the properties e.g., Vicat Softening Temperature, HDT, Tensile, Izod, Elongation, etc.
  • the "propylene- ⁇ -olefm copolymers" described herein are copolymers of propylene- derived units and one or more units derived from ethylene and/or a C 4 -C 10 ⁇ -olefm and optionally one or more diene-derived units.
  • Preferred ⁇ -olefms are ethylene, 1-butene, 1-hexene and 1-octene.
  • the propylene- ⁇ -olefin copolymers consist of propylene - derived units and from 5 to 35 wt%, by weight of the propylene- ⁇ -olefm copolymer, of ethylene- derived units and/or C 4 to C 10 ⁇ -olefm-derived units.
  • Typical comonomer content of the copolymer is from 5 to 35 wt% in one embodiment.
  • the comonomer content is adjusted so that the copolymer preferably has a molecular weight distribution ("MWD", Mw/Mn) of from 1.5 to 20, more preferably from 1.5 to 5, a heat of fusion (H f ) less than or equal to 75 J/g and a melting temperature (T m ) less than or equal to 105 0 C.
  • MWD molecular weight distribution
  • H f heat of fusion
  • T m melting temperature
  • the amount of a particular comonomer may be less than 5 wt%, but the combined comonomer content is preferably greater than 5 wt%.
  • the total weight percent of the ethylene or C 4 -C 10 ⁇ -olefm-derived units is preferably from 5 to 35 wt%, more preferably from 7 to 32 wt%, more preferably from 8 to 25 wt%, more preferably from 8 to 20 wt%, and more preferably from 8 to 18 wt%.
  • Particular embodiments of copolymers having more than one ⁇ -olefm include propylene- ethylene-octene, propylene-ethylene-hexene and propylene-ethylene -butene polymers. These copolymers may further comprise a diene as described below.
  • the propylene- ⁇ -olefm copolymer comprises propylene derived units and ethylene derived units.
  • the propylene-ethylene copolymer can comprise from 5 to 25 wt% ethylene-derived units, preferably from 5 to 20 wt%, more preferably from 5 to 16 wt%, and more preferably from 6 to 18 wt% ethylene.
  • the propylene-ethylene copolymer comprises greater than 11 wt% ethylene, the remainder of the copolymer comprising propylene derived units.
  • the propylene- ⁇ -olefm copolymer, a propylene-ethylene copolymer in one embodiment, may optionally comprise less than or equal to 10 wt% diene derived units (or "diene"), preferably less than or equal to 5 wt% diene, more preferably less than or equal to 3 wt% diene, preferably from 0.1 to 3 or 4 or 5 or 6 wt%, more preferably from 0.1 to 2 wt%, and more preferably from 0.1 to 1 wt% diene.
  • diene derived units or "diene”
  • Suitable dienes useful as co-monomers are, for example: 1 ,4-hexadiene, 1,6-octadiene, 5-methyl-l,4-hexadiene, 3,7-dimethyl-l,6-octadiene, dicyclopentadiene (DCPD), ethylidiene norbornene (ENB), norbornadiene, 5-vinyl-2-norbornene (VNB), and combinations thereof.
  • the diene, if present, is most preferably ENB.
  • the propylene- ⁇ -olefm copolymer can have a triad tacticity of three propylene units, as measured by 13 C NMR, of 75% or greater, 80% or greater, 82% or greater, 85% or greater, or 90% or greater. Preferred ranges include from 50 to 99%, more preferably from 60 to 99%, more preferably from 75 to 99% and more preferably from 80 to 99%; and in other embodiments from 60 to 97%. Triad tacticity was determined as follows: The tacticity index, expressed herein as
  • m/r is determined by 13 C nuclear magnetic resonance (NMR).
  • NMR nuclear magnetic resonance
  • the tacticity index m/r is calculated as defined by H. N. Cheng in 17 MACROMOLECULES 1950 (1984).
  • the designation "m” or “r” describes the stereochemistry of pairs of contiguous propylene groups, "m” referring to meso and “r” to racemic.
  • An m/r ratio of 1.0 generally describes a syndiotactic polymer, and an m/r ratio of 2.0 an atactic material.
  • An isotactic material theoretically may have a ratio approaching infinity, and many by-product atactic polymers have sufficient isotactic content to result in ratios of greater than 50.
  • Embodiments of the propylene- ⁇ -olefm copolymer have a tacticity index m/r ranging from a lower limit of 4 or 6 to an upper limit of 8 or 10 or 12.
  • the propylene- ⁇ -olefm copolymer has an H f , determined according to the Differential Scanning Calorimetry (DSC) procedure described herein, greater than or equal to 0.5 or 1 or 5 J/g, and is less than or equal to 80 J/g, preferably less than or equal to 70 J/g, more preferably less than or equal to 50 J/g, more preferably less than or equal to 35 J/g.
  • DSC Differential Scanning Calorimetry
  • the Hf ranges from a lower limit of 1.0, or 1.5, or 3.0, or 4.0, or 6.0, or 7.0 J/g to an upper limit of 30, or 35, or 40, or 50, or 60 or 70, or 80
  • the propylene- ⁇ -olefm copolymer, a propylene-ethylene copolymer in one embodiment has a percent crystallinity of from 0.5 to 40%, preferably 1 to 30%, and more preferably 5 to 25% wherein "percent crystallinity" is determined according to the DSC procedure described herein.
  • the thermal energy for the highest order of polypropylene is estimated at 189 J/g (i.e., 100% crystallinity is equal to 189 J/g).
  • the propylene-ethylene copolymer of the present disclosure preferably has a crystallinity of less than 40%, preferably from 0.25 to 25%, more preferably from 0.5 to 22%, and most preferably from 0.5 to 20%.
  • the procedure for DSC determinations is as follows. About 0.5 grams of polymer was weighed out and pressed to a thickness of about 15-20 mils (about 381-508 microns) at about 140°C-150°C, using a "DSC mold" and Mylar as a backing sheet. The pressed pad was allowed to cool to ambient temperature by hanging in air (the Mylar was not removed). The pressed pad was annealed at room temperature (about 23-25 0 C) for about 8 days. At the end of this period, an about 15-20 mg disc was removed from the pressed pad using a punch die and was placed in a 10 microliter aluminum sample pan.
  • the sample was placed in a differential scanning calorimeter (Perkin Elmer Pyris 1 Thermal Analysis System) and was cooled to about -100 0 C.
  • the sample was heated at about 10°C/min to attain a final temperature of about 165°C.
  • the thermal output recorded as the area under the melting peak of the sample, is a measure of the heat of fusion and can be expressed in Joules per gram (J/g) of polymer and was automatically calculated by the Perkin Elmer System. Under these conditions, the melting profile shows two (2) maxima, the maxima at the highest temperature was taken as the melting point within the range of melting of the sample relative to a baseline measurement for the increasing heat capacity of the polymer as a function of temperature.
  • the propylene-ethylene copolymer preferably has a single broad melting transition.
  • the "T m " is defined as the temperature of the greatest heat absorption within the range of melting of the sample.
  • the propylene-ethylene copolymer may show secondary melting peaks adjacent to the principal peak, but for purposes herein, such secondary melting peaks are considered together as a single melting point, with the highest of these peaks being considered the T m of the propylene-ethylene copolymer.
  • the propylene-ethylene copolymer preferably has a T m of from 25 to 105 0 C, preferably from 25 to 85°C, more preferably from 25 to 75°C, more preferably from 25 to 65°C, more preferably from 30 to 80 0 C, more preferably from 30 to 70 0 C and more preferably from 30 to 60 0 C.
  • the propylene- ⁇ -olefm copolymer can have a density of 0.850 to 0.920 g/cm 3 , more preferably, 0.870 to 0.900 g/cm 3 , more preferably 0.880 to 0.890 g/cm 3 at room temperature as measured per the ASTM D-1505 test method.
  • the propylene- ⁇ -olefm copolymer can have a melt flow rate ("MFR", ASTM D1238, 2.16 kg, 23O 0 C), equal to or greater than 0.2 dg/min.
  • MFR melt flow rate
  • ASTM D1238, 2.16 kg, 23O 0 C melt flow rate
  • the MFR is from 0.5 to 5000 dg/min and more preferably from 1 to 2500 dg/min.
  • the propylene- ⁇ -olefm copolymer has an MFR of 0.5 to 1500 dg/min, from 2 to 1000 dg/min in another embodiment, and from 5 to 500 dg/min in yet another embodiment, and from 10 to 250 dg/min in yet another embodiment, and from 10 to 100 dg/min in yet another embodiment, and from 2 to 40 dg/min in yet another embodiment, and from 2 to 30 dg/min in yet another embodiment, and from 0.5 to 10 dg/min in yet another embodiment.
  • the propylene- ⁇ -olefm copolymers, propylene-ethylene copolymers in one embodiment may have a Mooney viscosity [ML (1+4) @ 125°C] as determined according to ASTM D 1646, of less than 150, more preferably less than 100, even more preferably less than, most preferably less than 60.
  • the propylene- ⁇ -olefm copolymer can have a Mw of 40,000 to 5,000,000 g/mole, more preferably a Mw of 50,000 to 1,000,000, and more preferably a Mw of 70,000 to 400,000.
  • the propylene- ⁇ -olefm copolymer can have a Mn of 20,000 to 2,500,000 g/mole, more preferably a Mn of 40,000 to 350,000, and more preferably a Mn of 60,000 to 200,000.
  • the propylene- ⁇ -olefm copolymer can have a Mz of 50,000 to 7,000,000 g/mole, more preferably a Mz of 80,000 to 700,000, and more preferably a Mz of 100,000 to 500,000.
  • the molecular weight distribution (MWD) of the propylene-ethylene copolymer is from 1.5 to 20 in one embodiment, and from 1.5 to 15 in another embodiment, and more preferably 1.5 to 5, more preferably 1.8 to 5 and most preferably 1.8 to 4 or 3.
  • Techniques for determining the molecular weight (Mn, Mz and Mw) and molecular weight distribution (MWD) are as follows, and as in Verstate et al.
  • the propylene- ⁇ -olefm copolymers can include copolymers prepared according to the procedures in WO 02/36651, US 6,992,158, and/or WO 00/01745. Preferred methods for producing the propylene- ⁇ -olefm copolymers are found in US Patent Application Publication 2004/0236042 and US 6,881,800.
  • Preferred propylene- ⁇ -olef ⁇ n copolymers are available commercially under the trade names VistamaxxTM (ExxonMobil Chemical Company, Houston, TX, USA) and VersifyTM (The Dow Chemical Company, Midland, Michigan, USA), certain grades of TafmerTM XM or NotioTM (Mitsui Company, Japan) or certain grades of SoftelTM (Basell Polyolefins of the Netherlands).
  • the pipe of the present invention also includes an additional component selected from the group consisting of propylene homopolymers, propylene random copolymers, propylene block copolymers, and combinations thereof.
  • the propylene homopolymer has a MFR (23O 0 C, 2.16 kg) of from 0.05 to 10 dg/min in one embodiment, and from 0.1 to 5 dg/min in another embodiment, and from 0.1 to 2 dg/min in yet another embodiment.
  • the propylene homopolymer is an isotactic propylene homopolymer.
  • the "propylene random copolymer” is a polymer comprising propylene-derived units and from less than 5 wt% comonomer-derived units in one embodiment. Suitable comonomers include ethylene-derived units and/or units selected from C 4 to C 10 ⁇ -olefm derived units. In a particular embodiment, the propylene random copolymer is a propylene-ethylene random copolymer.
  • the propylene random copolymer comprises from 0.1 to 5 wt% of comonomer-derived units, and from 0.2 to 4 wt% in another embodiment, and from 0.3 to 2 wt% in yet another embodiment.
  • the propylene random copolymer has an MFR (23O 0 C, 2.16 kg) of from less than 5 dg/min, and from 0.05 to 5 dg/min in another embodiment, and from 0.1 to 3 dg/min in yet another embodiment.
  • the propylene random copolymer has a melt temperature (T m ) of greater than 135 0 C, and greater than 14O 0 C in another embodiment, and greater than 15O 0 C in yet another embodiment.
  • the propylene random copolymer has a Flexural Modulus (23 0 C) of greater than 650 MPa, and greater than 700 MPa in another embodiment, and greater than 750 MPa in yet another embodiment.
  • the "propylene block copolymer” is a reactor made blend of at least one propylene homopolymer with at least one propylene-ethylene random copolymer containing less than 50 weight % propylene-ethylene random copolymer.
  • the propylene block copolymer comprises from 1 to 50 wt% of propylene-ethylene random copolymer, and from 0.2 to 30 wt% in another embodiment, and from 0.3 to 20 wt% in yet another embodiment.
  • the propylene block copolymer has an MFR (23O 0 C, 2.16 kg) of from less than 5 dg/min, and from 0.05 to 5 dg/min in another embodiment, and from 0.1 to 3 dg/min in yet another embodiment.
  • the propylene block copolymer has a melt temperature (T m ) of greater than 135 0 C, and greater than 14O 0 C in another embodiment, and greater than 15O 0 C in yet another embodiment.
  • the propylene block copolymer has a Flexural Modulus (23 0 C) of greater than 650 MPa, and greater than 700 MPa in another embodiment, and greater than 750 MPa in yet another embodiment.
  • the propylene homopolymer, propylene random copolymer, or propylene block copolymer are present in the pipe compositions, individually, from 60 to 95 wt% of the composition in one embodiment, and from 65 to 90 wt% of the composition in another embodiment, and from 68 to 75 wt% of the composition in yet another embodiment.
  • a mixture of two or more of the propylene homopolymer, propylene random copolymer, and propylene block copolymer are present from 60 to 95 wt% of the composition in one embodiment, and from 65 to 90 wt% of the composition in another embodiment, and from 68 to 75 wt% of the composition in yet another embodiment.
  • the pipe compositions of the present invention can include one or more plastomers.
  • a "plastomer” comprises ethylene-derived units and at least one of C3 to Cs ⁇ -olefm derived units from 1 wt% to 40 wt% of the plastomer in one embodiment, and from 5 to 35 wt% of the plastomer in another embodiment, and from 5 to 30 wt% of the plastomer in yet another embodiment. More particularly, a plastomer is a copolymer of ethylene-derived units and at least one of non-cyclic mono-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 4-methyl-l-pentene.
  • cyclic mono-olefins and both linear and cyclic dienes can also be used in copolymerization with ethylene to form the plastomer. It is desirable in some applications to use ethylene- ⁇ -olefm-diene terpolymers.
  • the plastomer is a copolymer of ethylene derived units and 1-hexene or 1-octene derived units, wherein the 1-hexene or 1-octene derived units are present from 5 to 40 wt% of the plastomer in one embodiment, from 5 to 30 wt% of the plastomer in another embodiment, and from 10 to 28 wt% in another embodiment, and from 15 to 27 wt% in yet another embodiment.
  • the plastomer has a density in the range of 0.856 to 0.915 g/cm , and a density of from 0.880 to 0.915 g/cm 3 in another embodiment, and from 0.865 to 0.915 g/cm in one embodiment, and in the range of from 0.870 to 0.910 g/cm in another embodiment, and in the range of 0.880 to 0.908 g/cm in yet another embodiment, and in the range of 0.880 to 0.906 g/cm in yet another embodiment.
  • the I 2 (ASTM D-1238, 19O 0 C, 2.16 kg) of the plastomer is in the range of from 0.10 to 40 dg/min in one embodiment, and from 0.5 to 10 dg/min in another embodiment, and from 1.0 to 6.0 dg/min in another embodiment, and from 1.5 to 5.0 dg/min in yet another embodiment.
  • Desirable plastomers are sold, for example, under the trademark ExactTM (ExxonMobil Chemical Company, Houston, Texas), such as Exact 0203.
  • the invention can also be practiced using EngageTM polymers (also AffinityTM and VersifyTM; Dow Chemical Company, Midland, Michigan) and TafmerTM (Mitsui Petrochemical Co.).
  • the propylene-based polymer VistamaxxTM (ExxonMobil Chemical Co.) may also be used as the one or more plastomers.
  • the plastomer can be present in an amount of from 0.5 to 20 wt% of the pipe composition in one embodiment, and from 1 to 15 wt% in another embodiment, and from 2 to 12 wt% in yet another embodiment.
  • the composition that is used to form the pipe is blended with from 1 to 40 wt% of a filler, and from 2 to 30 wt% in another embodiment, and from 3 to 20 wt% in yet another embodiment.
  • Fillers that can be included in the pipe composition include those reinforcing and non-reinforcing fillers or extenders that are conventionally employed in the compounding of polymeric materials.
  • Useful fillers include carbon black, calcium carbonate, clays, silica, fumed silica, talc, and titanium dioxide.
  • Useful fillers also include nano fillers such as nano clay, nano talc, wollastonite, kaolin and titanium dioxide.
  • the filler can be surface treated with a silane derivative such as aminosilane, or other, for better dispersion into polymer phase.
  • a functionalized polypropylene like maleic anhydride grafted polypropylene can be used as compatibilizer between mineral filler and polymer phase.
  • the pipe composition may contain stabilizers, nucleating agents, UV stabilizers, antioxidants, slip agents, pigments, etc.
  • the pipe composition can also include these minor components up to 1 or 2 or 3 or 4 wt% based on the weight of the composition.
  • the pipe compositions have a MFR (23O 0 C, 2.16 kg) from 0.1 to 10 dg/min in one embodiment, and from 0.2 to 5 dg/min in another embodiment, and from 0.3 to 3 dg/min in yet another embodiment.
  • the pipe compositions can have a Flexural Modulus (23 0 C, ISO 178) from less than
  • MPa in yet another embodiment and greater than 100 MPa in yet another embodiment.
  • the pipe compositions can have an Izod Impact (23 0 C, ISO 180) from greater than 30 kJ/m 2 in one embodiment, and greater than 35 kJ/m 2 in another embodiment, and greater than 40 kJ/m 2 in yet another embodiment, and less than 100 kJ/m 2 in yet another embodiment, and less than 80 kJ/m 2 in yet another embodiment.
  • Izod Impact 23 0 C, ISO 180
  • the pipe compositions can have an Charpy Impact (23 0 C, ISO 179) from greater than
  • the pipe compositions can have a Vicat Softening Temperature (ISO 306) greater than 110 0 C in one embodiment, and greater than 115 0 C in another embodiment, and greater than
  • the pipe compositions can have a heat deflection temperature ("HDT", ISO 75) from
  • the pipe composition described herein can be used to make single- or multilayer pipes. Further, the pipe composition can be used to make up one or more layers of a pipe, the other layer(s) being formed from other synthetic, metal or allow materials. Conventional extruders are suitable for producing the single-or multilayer propylene pipe composition.
  • extruders with short compression screws or 3 -zone screws with L/D 20 to 40 are suitable for melting the propylene-based polymers and, when present, plastomer, pursuant to the inventive method.
  • Preferably, 5 -zone screws with a feed zone, compression zone, shear zone, decompression zone and homogenizing zone are preferred. Screws with cutting depths of 1 :2.5 to 1 :3.5 are particularly suitable.
  • Extruders equipped with a grooved barrel section are also suitable.
  • a melt pump and/or a static mixer can be used additionally between the extruder and the ring die head. Ring shaped dies with diameters ranging from approximately 16 to 2000 mm and greater are possible.
  • Advantageous die temperatures for discharging the melt are 190 to 240 0 C. After leaving the ring-shaped die, the polypropylene pipes are taken off over a vacuum calibrating sleeve, and cooled.
  • the pipe compositions can be intimately melt-blended prior to formation of the pipe, or the components can be combined and melt-blended in the same apparatus that is used to make the pipe.
  • the pipe compositions can be formed into pipes of any diameter, preferably between 1 cm and 10 cm, with a wall thickness of from 2 to 8 mm.
  • Such pipes are particularly suitable for in-floor heating systems and can be advantageously heat-bent into a "U" shape to make a continuous flow of heated water through the floor in which it is installed.
  • Preferred applications of the propylene polymer pipes the conveyance of fluids and pressurized fluids such as natural gas and water and the like at service temperatures at or above room temperature, but also below room temperature and even the freezing point of water when applicable.
  • the pipe composition comprises 70-80 wt% of a propylene random copolymer and 10-20 wt% of a propylene- ⁇ -olefm, based on the weight of the composition.
  • the pipe composition comprises 60-70 wt% of a propylene random copolymer, and 20-30 wt% of the propylene- ⁇ -olefm.
  • the pipe composition comprises 70-80 wt% of a propylene homopolymer and 10-20 wt% of a propylene- ⁇ -olefm.
  • the pipe composition comprises 60-70 wt% of a propylene homopolymer, and 20-30 wt% of the propylene- ⁇ -olefm, by weight of the composition.
  • the pipe composition comprises 60-70 wt% of a propylene random copolymer, 10-20 wt% of a propylene- ⁇ -olefm and 5-15 wt% of a plastomer, by weight of the composition.
  • the pipe composition consists essentially of 70 to 80 wt% of a propylene random copolymer and 20 to 30 wt% of a propylene- ⁇ -olefm, and from 0.1 to 1 wt% of an additional additive such as a nucleator or stabilizer, by weight of the composition.
  • the data in Table 1 presents some of the basic properties of the propylene- ⁇ -olefm copolymers used in the Examples.
  • the MFR was determined according to ASTM D- 1238 (230 ⁇ C, 2.16 kg); the Flexural Modulus is the 1% secant, determined by ASTM D-790; the
  • the mixer settings were as follows: temperature profile (hopper to die in 0 C) 160 - 180 - 200 -
  • the die was a plate die with 2 round holes (3 mm diameter)
  • the propylene- ⁇ - olefin copolymer is described in Table 1; the stabilizer is Irganox 225 (Ciba Specialty Co.); the nucleating agent was Hyperform HPN 68 (Milliken); the hPP(l) is a propylene homopolymer having an MFR (23O 0 C, 2.16 kg) of 0.3 dg/min (Borealis); the hPP(2) is a propylene homopolymer PP 5341E1, having an MFR (23O 0 C, 2.16 kg) of 0.8 (ExxonMobil Chemical Co.); rPP is Beta-PPRTM R 7050 propylene random copolymer having an MFR (230 0 C, 2.16 Kg) of 0.3 dg/min, a modulus of Elasticity of 900 MPa (Borealis); and sample 11 is a comparative example of RA130E-1498,
  • test methods are as follows:
  • Hardness ISO 868, 15 sec delay, 2 mm/30 mm disk (shore D) (sample size in thickness/diameter).
  • MFR Melt flow Rate
  • a pipe comprising:
  • propylene- ⁇ -olefm copolymer is a propylene-ethylene copolymer comprising from 8 to 20 wt%, based on the weight of the copolymer, of ethylene derived units.
  • a method of forming a pipe of any of the preceding numbered embodiments comprising melt-blending the composition of the propylene- ⁇ -olefm copolymer and at least one additional component selected from the group consisting of propylene random copolymers having a comonomer content of less than 5 wt%, a propylene block copolymer, propylene homopolymer and combinations thereof; extruding the composition through a pipe-forming die; followed by isolating a pipe composition.
  • a pipe in transporting liquids, heated water in one embodiment, the pipe comprising (consisting of in a particular embodiment) a composition possessing a Flexural Modulus (23 0 C) less than 650 MPa, an Izod Impact (23 0 C) greater than 30 kJ/m 2 , and a Vicat Softening Temperature greater than HO 0 C and comprising: (a) a propylene- ⁇ - olefm copolymer comprising propylene-derived units and from 5 to 35 wt%, by weight of the propylene- ⁇ -olefm copolymer, of ethylene-derived units or a C 4 to C 10 ⁇ -olefm-derived unit, and having: (i) a density from 0.850 to 0.920 g/cm 3 ; (ii) an H f of less than 75 J/g; and (iii) a T m of less than 105 0 C; and (b) at least one additional component

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Abstract

Sous l'un de ses aspects, l'invention porte sur un tuyau comprenant une composition d'un ou plusieurs copolymères de propylène-α-oléfine comprenant des unités issues du propylène et de 5 à 35 % en poids, par rapport au copolymère de propylène-α-oléfine, d'unités issues de l'éthylène et/ou d'une unité issue d'une α-oléfine en C4 à C10, et ayant (i) une masse volumique de 0,850 à 0,920 g/cm3; (ii) un Hf de moins de 75 J/g; et (iii) une Tm inférieure à 105 °C; et au moins un constituant supplémentaire choisi dans le groupe constitué par des copolymères statistiques du propylène ayant une teneur en comonomère de moins de 5 % en poids, un copolymère séquencé du polypropylène, un homopolymère du propylène et leurs combinaisons; la composition pour tuyau possédant un module de flexion (23° C) inférieur à 650 MPa, une résistance aux chocs Izod (23 °C) supérieure à 30 kJ/m2 et une température de ramollissement Vicat supérieure à 110 °C.
PCT/US2007/087624 2007-12-14 2007-12-14 Tuyaux en polyoléfine WO2009078854A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017076412A1 (fr) 2015-11-03 2017-05-11 National Oilwell Varco Denmark I/S Tuyau souple non collé
WO2018234235A1 (fr) 2017-06-19 2018-12-27 Plastiflex Group Composition comprenant du polypropylène, profilé et tuyau flexible fabriqués à partir de celle-ci
US11725098B2 (en) 2017-12-18 2023-08-15 Celanese International Corporation Thermoplastic vulcanizate conduits for transporting hydrocarbon fluids

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006065664A1 (fr) * 2004-12-17 2006-06-22 Exxonmobil Chemical Patents Inc. Films de melanges de polymeres
US20060173132A1 (en) * 2004-12-17 2006-08-03 Mehta Aspy K Heterogeneous polymer blends and molded articles therefrom
WO2006113132A1 (fr) * 2005-04-14 2006-10-26 Exxonmobil Chemical Patents Inc. Compositions de polyolefines transparentes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006065664A1 (fr) * 2004-12-17 2006-06-22 Exxonmobil Chemical Patents Inc. Films de melanges de polymeres
US20060173132A1 (en) * 2004-12-17 2006-08-03 Mehta Aspy K Heterogeneous polymer blends and molded articles therefrom
WO2006113132A1 (fr) * 2005-04-14 2006-10-26 Exxonmobil Chemical Patents Inc. Compositions de polyolefines transparentes

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017076412A1 (fr) 2015-11-03 2017-05-11 National Oilwell Varco Denmark I/S Tuyau souple non collé
US20180320803A1 (en) * 2015-11-03 2018-11-08 National Oilwell Varco Denmark I/S An unbonded flexible pipe
US11054067B2 (en) 2015-11-03 2021-07-06 NATIONAL OILWELL VARCO DENMARK l/S Unbonded flexible pipe
WO2018234235A1 (fr) 2017-06-19 2018-12-27 Plastiflex Group Composition comprenant du polypropylène, profilé et tuyau flexible fabriqués à partir de celle-ci
US11725098B2 (en) 2017-12-18 2023-08-15 Celanese International Corporation Thermoplastic vulcanizate conduits for transporting hydrocarbon fluids

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