WO2004060994A1 - Melanges elastiques comprenant un polymere cristallin elastique et des polymeres cristallisables d'ethylene - Google Patents

Melanges elastiques comprenant un polymere cristallin elastique et des polymeres cristallisables d'ethylene Download PDF

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Publication number
WO2004060994A1
WO2004060994A1 PCT/US2003/039907 US0339907W WO2004060994A1 WO 2004060994 A1 WO2004060994 A1 WO 2004060994A1 US 0339907 W US0339907 W US 0339907W WO 2004060994 A1 WO2004060994 A1 WO 2004060994A1
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Prior art keywords
ethylene
component
polymer
composition
propylene
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PCT/US2003/039907
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English (en)
Inventor
Andy H. Tsou
Srivatsan Srinivas
Andrew J. Peacock
Bryan R. Chapman
Sudhin Datta
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Exxonmobil Chemical Patents Inc.
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Priority to AU2003297134A priority Critical patent/AU2003297134A1/en
Publication of WO2004060994A1 publication Critical patent/WO2004060994A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins

Definitions

  • Embodiments of our invention relate to a blend of at least two polymeric components differing in their crystallinity type.
  • the blend may be a hetero phase morphology composition comprising at least one copolymer of propylene and one or more of ethylene, and/or C4-C20 ⁇ -olefins and at least one copolymer of ethylene and one or more of C3-C20 ⁇ -olefins, and/or at least one propylene polymer or combinations thereof.
  • U.S. Patent No. 6,231,936 suggests a blend of polypropylene with an ethylene ⁇ -olefm polymer for articles such as packaging materials and medical devices that require radiation and/or heat resistance for their applications.
  • the propylene may be a homopolymer or copolymer, produced with a Ziegler-Natta or metallocene catalyst, and be relatively low in crystallinity.
  • the propylene polymer is described as having a heptane insolubles content of from 88 to 99%.
  • the propylene polymers may have a comonomer of a C2 to C20 ⁇ -olefin, and/or a diene.
  • the propylene polymers may have a molecular weight distribution (M D) of from 1 to 9.
  • M D molecular weight distribution
  • the ethylene polymers are generally described as being produced with a metallocene catalyst and exhibit densities of from 0.85 to 0.965 g/cc, a MWD of from 1 to 4 and a CDBI greater than 45%.
  • the ethylene polymer may generally be in the blend in the range of from 1 to 50 wt%.
  • WO Publication No 98/21275 suggests a metallocene catalyzed ethylene copolymer blended with an impact copolymer polypropylene (ICP) for impact modification of the polypropylene.
  • ICP impact copolymer polypropylene
  • the 1% secant modulus of the blend is generally above 140,000 psi (966 MPa).
  • the rubber is present in the ICP in an amount of from 4-20 wt% and the rubber portion contains ethylene in an amount of from 30 to 65 wt%.
  • the ethylene polymer is a copolymer of ethylene and an ⁇ -olefin having from 4-10 carbon atoms, with a density from 0.88-0.925 g/cc.
  • the ethylene polymer is present in the blend in an amount of from 5 to 40 wt%.
  • compositions comprising at least one propylene polymer or polymers as at least one first component with other polymers as at least one second component, where the at least one first component or components and the at least one second component, have different crystallinity
  • such compositions may generally be heterophase compositions, and may have resistance to elastic deformation (permanent set) when articles made from such compositions are extended or elongated.
  • hetero phase compositions refers to the presence of at least two phases: a continuous or matrix phase and a discontinuous or disperse phase distributed within the matrix phase.
  • Each phase can itself be a blend, as long as the crystallinity of the matrix phase and discontinuous phase or phases are different, as herein defined.
  • a two or more phase system may be co-continuous, that is the two or more phases are still divided, but an observer cannot tell, based on the amounts of each phase, which is the continuous phase and which is the dispersed phase.
  • Such systems, while still hetero phase are said to be co- continuous, and are contemplated as embodiments of our invention.
  • compositions substantially devoid of compatibilizer, comprising at least one first component and at least one second component, wherein: a) the composition comprises a ratio of the at least one first component to the at least one second component, in the range of 1 :99 to 99:1, based on the total polymer content of the blend, and crystallinity of the at least one first component being propylene crystallinity;
  • Figure 1 is a graphical representation of the ratio of 500% tensile modulus of a composition as herein described, to the 500% tensile modulus of the at least one first component (unblended), versus permanent set.
  • hetero phase compositions comprised of at least one first component of a propylene rich polymer, and at least one second component
  • this at least one second component may be one or more of i) generally an ethylene rich polymer or ii) generally a propylene rich polymer, where the crystallinity of the at least one first component and crystallinity of the at least one second component, differ in crystallinity type and may also differ in amount of crystallinity.
  • propylene or ethylene rich we intend that > 50 weight percent of the polymer be the rich monomer.
  • hetero phase compositions may include a homogeneous macromolecular copolymer structure as the at least one first component, and at least one homopolymer or copolymer of ethylene and at least one ⁇ -olefin as the at least one second component.
  • Embodiments of our invention are directed to hetero phase morphology compositions where at least one first component may be a copolymer of propylene and at least one C2, C4-C20 ⁇ -olefins and at least one second component may be a copolymer of ethylene and at least one C3-C20 ⁇ - olefin.
  • At least one first component selected from propylene rich polymers, may be present in the composition in a ratio of at least one first component to at least one second component of 1:99 to 99:1, or 95:5 to 5:95, or 10:90 to 90:10, or 15:85 to 85:15, or
  • Embodiments of our invention include blend compositions where the two major components may have different crystallinity.
  • Ethylene and propylene or isotactic and syndiotactic are examples of differing crystallinities of the two major composition components. By differing crystallinities we intend:
  • crystallinity and its amount may be determined by using either differential scanning calorimetry (DSC) or wide angle x-ray scattering (WAXS). Further, the crystallinity type may be determined by 13C NMR (Nuclear Magnetic Resonance) or Fourier Transform Infrared Spectroscopy (FTIR) as being ethylene crystallinity, propylene crystallinity, and if propylene crystallinity the type of crystallinity (syndiotactic, isotactic).
  • DSC differential scanning calorimetry
  • WAXS wide angle x-ray scattering
  • FTIR Fourier Transform Infrared Spectroscopy
  • a ratio of the 500% tensile modulus of the composition, to the 500% tensile modulus of the at least one first component, unblended may be used.
  • this ratio may be ⁇ 1.6, or ⁇ 1.5, or ⁇ 1.45, or ⁇ 1.4, or ⁇ 1.35, or ⁇ 1.30.
  • This ratio may be achieved generally at a tension set of the composition of ⁇ 98% or ⁇ 95% or ⁇ 90% or ⁇ 88%, or ⁇ 85%, or ⁇ 82%, or ⁇ 80%.
  • compositions of embodiments of our invention may generally be devoid of compatibilizer.
  • Compatibilizers are known by those of skill in the art to be those polymers that are compatible with both the continuous and disperse phases. By devoid, we intend that no polymer that acts in a compatibilizing way or other compatibilizing agent is added. And this may generally mean ⁇ 1.0 wt.%, or ⁇ 0.5 wt.%, or ⁇ 0.1 wt.%, of any such material or materials may be present, or none detectable by current analytical techniques. Further, no compatibilizing agent or polymer may be intentionally added.
  • the 1% secant (flexural) modulus of the composition may be ⁇ 140,000 psi, or ⁇ 130,000 psi, or ⁇ 125,000 psi, or ⁇ 120,000 psi, or ⁇ 115,000 psi, or ⁇ 105,000 psi, or ⁇ 100,000 psi, or ⁇ 90,000 psi, or ⁇ 80,000 psi.
  • additives may be part of the compositions of embodiments of our invention.
  • Additives which may be incorporated comprise, for example, fire retardants, antioxidants, plasticizers, pigments, vulcanizing or curative agents, vulcanizing or curative accelerators, retarders, processing aids, flame retardants, tackifying resins, dyes, waxes, heat stabilizers, light stabilizers, anti-block agents, processing aids, or combinations thereof.
  • These compounds may include fillers, reinforcing materials (including granular, fibrous, or powder-like) or combinations thereof. These fillers comprise carbon black, clay, talc, calcium carbonate, mica, silica, silicate, and combinations thereof. Lubricants, mold release agents, nucleating agents, or combinations may also be employed.
  • the at least one first component comprises from a lower limit of > 5% or > 6% or > 8% or > 10% by weight to an upper limit of ⁇ 20% or ⁇ 25% by weight ethylene and/or at least one ⁇ -olefin-derived unit, and from a lower limit of > 75% or > 80% by weight to an upper limit of ⁇ 95% or ⁇ 94% or ⁇ 92% or ⁇ 90% by weight propylene-derived units, the percentages by weight are based on the total weight of propylene and ethylene and/or at least one ⁇ -olefin- derived unit comprising the at least one first component.
  • ethylene can be replaced or added to in such polymers with one or more C4 - C20 or C4-C12 ⁇ - olefins, such as, for example, one or more of 1-butene, 1-hexene or 1-octene or 1- decene.
  • Other olefinic monomers may comprise the at least one first component, these include linear, branched, or ring-containing C3 to C30 olefms or combinations thereof, capable of insertion polymerization.
  • Branched ⁇ -olefins include 4-methyl-l-pentene, 3 -methyl- 1-pentene, and 3,5,5-trimethyl-l-hexene.
  • Ring-containing olefinic monomers contain up to 30 carbon atoms and comprise for example, cyclopentene, vinylcyclohexane, vinylcyclohexene, norbornene, methyl norbornene, and combinations thereof.
  • Aromatic-group-containing monomers may contain up to 30 carbon atoms. Suitable aromatic-group-containing monomers comprise at least one aromatic structure, or from one to three, or may be a phenyl, indenyl, fluorenyl, or naphthyl moiety. The aromatic-group-containing monomer further comprises at least one polymerizable double bond such that after polymerization, the aromatic structure may be pendant from the polymer backbone.
  • Aromatic-group-containing monomers may contain at least one aromatic structure appended to a polymerizable olefinic moiety.
  • the polymerizable olefinic moiety may be linear, branched, cyclic-containing, or a mixture of these structures. When the polymerizable olefinic moiety contains a cyclic structure, the cyclic structure and the aromatic structure may share 0, 1, or 2 carbons.
  • the polymerizable olefinic moiety and/or the aromatic group may also have from one to all of the hydrogen atoms substituted with linear or branched alkyl groups containing from 1 to 4 carbon atoms.
  • Aromatic monomers contemplated include styrene, alpha-methylstyrene, vinyltoluenes, vinylnaphthalene, allyl benzene, indene or combinations thereof.
  • features of the at least one first component comprise one or more of the following characteristics, where ranges from any recited upper limit to any recited lower limit are contemplated.
  • the at least one first component may have a single, dual or multiple melting points.
  • the at least one first component may be a random copolymer of ethylene and/or one or more ⁇ -olefins and propylene, having at least one melting point (Tm) by Differential Scanning Calorimetry (DSC) ranging from an upper limit of less than 110 °C, or less than 90 °C, or less than 80 °C, or less than 70 °C; to a lower limit of greater than 25 °C, or greater than 35 °C, or greater than 40°C or greater than 45°C.
  • DSC Differential Scanning Calorimetry
  • a heat of fusion as determined by DSC, ranging from a lower limit of greater than 1.0 joule per gram (J/g), or greater than 1.5 J/g, or greater than 4.0 J/g, or greater than 6.0 J/g, or greater than 7.0 J/g, to an upper limit of less than 125 J/g, or less than 100 J/g, or less than 75 J/g, or less than 60 J/g, or less than 50 J/g, or less than 40 J/g, or less than 30 J/g.
  • the crystallinity of the first component arises from stereo regular propylene sequences and such first components may be said to be crystalline if they show a Tm. By crystalline we intend that under certain conditions (i.e.
  • crystallinity may be determined by DSC and/or WAXS. If a polymer meets such a test, that is having crystallinity under any conditions of temperature and/ or stress, it is said to be crystalline. The amount of crystallinity is not addressed by such a statement, (iii) A triad tacticity, as determined by carbon- 13 nuclear magnetic resonance ( I3 C NMR), of greater than 75 %, or greater than 80 %, or greater than 85 %, or greater than 90 %.
  • I3 C NMR carbon- 13 nuclear magnetic resonance
  • At least 75% by weight, or at least 80% by weight, or at least 85% by weight, or at least 90% by weight, or at least 95% by weight, or at least 97% by weight, or at least 99% by weight of the at least one first component may be soluble in a single temperature fraction, or in two adjacent temperature fractions, with the balance of the at least one first component in immediately preceding or succeeding temperature fractions.
  • These percentages are fractions, for instance in hexane, beginning at 23 °C, and the subsequent fractions are in approximately 8°C increments above 23°C. Meeting such a fractionation requirement means that polymers have statistically insignificant intermolecular differences in tacticity or composition distribution.
  • each of these fractions may have a composition (wt% ethylene and /or ⁇ -olefin content) with a difference of less than 1.5 wt. % (absolute) or less than 1.0 wt. % (absolute), or less than 0.8 wt. % (absolute) of the average wt. % ethylene content of the whole at least one first component.
  • Meeting such a fractionation requirement means that a polymer has statistically insignificant intermolecular differences of composition, which is the ratio of propylene to ethylene and/or ⁇ -olefin.
  • the at least one first component may have a weight average molecular weight (Mw) of from 15,000 to 5,000,000, or from 20,000 to 1,000,000 and a molecular weight distribution (MWD) Mw/Mn ranging from a lower limit of 1.5 or 1.8 to an upper limit of 40, or 20, or 10, or 5, or 4.5.
  • Mw weight average molecular weight
  • Mw/Mn molecular weight distribution
  • the at least one first component may have predominantly (> 50 %, or > 60%, or > 70%) isotactic or syndiotactic sequences, but not both.
  • the presence of isotactic or syndiotactic sequences can be determined by NMR measurements showing two or more propylene derived units arranged isotactically (or syndiotactically).
  • the isotactic (or syndiotactic) sequences may be interrupted by units which are not isotactically (or syndiotactically) arranged or by units that otherwise disturb the crystallinity derived from the isotactic (or syndiotactic) sequences.
  • the at least one first component may contain small quantities of a non-conjugated diene.
  • the amount of diene may be ⁇ 10 wt. % or ⁇ 5 wt. %.
  • the diene may be selected from one or more of those which are used for the vulcanization of ethylene propylene rubbers such as ethylidene norbornene, vinyl norbornene or dicyclopentadiene.
  • the at least one first component may comprise a heptane insoluble fraction of ⁇ 88 %, or ⁇ 86%, or ⁇ 84%, or ⁇ 82%, or ⁇ 80%, or ⁇ 75%, or ⁇ 70%, or
  • Heptane insolubility is a measure of the portion of a finely divided polypropylene sample which is insoluble in boiling heptane (1.5 hour boiling time). As the insolubility approaches 100%, the crystallinity of the resin approaches a maximum level in commercially available polypropylenes.
  • Additional polymer or polymers may be included in the at least one first component, each of which would qualify as at least one first component, as long as the crystallinity type of the at least one first component blend remains the same and comprises propylene crystallinity, that is, if the primary first component contains for instance, isotactic sequences, the other member or members of the at least one first component may also have isotactic sequences, or in the alternative, all would comprise syndiotactic sequences. There may be one, two, three, four or more other components of this first component, all having the same type of crystallinity, but having the same or different amount of crystallinity, and the same or different.
  • the major olefinic monomer in the at least one second component may be ethylene.
  • the at least one second component may be polyethylene homopolymers, polyethylene copolymers or combinations thereof. If a copolymer, other olefinic monomers may be included, these include linear, branched, or ring-containing C3 to C30 olefms or combinations thereof, capable of insertion polymerization or these olefinic monomers may be C3 to C20 linear or branched ⁇ -olefins, or C3 to C8 ⁇ -olefms, or propylene, 1-butene, 1-hexene, and 1-octene.
  • Branched ⁇ -olefins include 4-methyl-l-pentene, 3 -methyl- 1-pentene, and 3,5,5-trimethyl-l-hexene and combinations thereof.
  • Ring-containing olefinic monomers may contain up to 30 carbon atoms and comprise cyclopentene, vinylcyclohexane, vinylcyclohexene, norbornene, methyl norbornene and combinations thereof.
  • Aromatic-group-containing monomers may contain up to 30 carbon atoms. Suitable aromatic-group-containing monomers comprise at least one aromatic structure, or from one to three, or may comprise a phenyl, indenyl, fluorenyl, naphthyl moieties or combinations thereof. The aromatic-group-containing monomer may further comprise at least one polymerizable double bond, such that after polymerization, the aromatic structure may be pendant from the polymer backbone. [0029] Aromatic-group-containing monomers may contain at least one aromatic structure appended to a polymerizable olefinic moiety. The polymerizable olefinic moiety may be linear, branched, cyclic-containing, or a mixture of these structures.
  • the cyclic structure and the aromatic structure may share 0, 1, or 2 carbons.
  • the polymerizable olefinic moiety and/or the aromatic group may also comprise from one to all of the hydrogen atoms substituted with linear . or branched alkyl groups containing from 1 to 4 carbon atoms.
  • Styrene, alpha-methylstyrene, vinyltoluenes, vinylnaphthalene, allyl benzene, indene or combinations thereof are examples of suitable aromatic monomers.
  • the at least one polyethylene copolymer or at least one polyethylene homopolymer, or combinations thereof may be a polymer having a melting point, as determined by DSC, of 20°C or more, 40°C or more, 50°C or more, or 60°C or more, or 65°C or more, or 70°C or more.
  • the polyethylene copolymer may have melting points of 125°C or less, or 120°C or less, or 130°C or less, or 140°C or less. Such melting points are determinative of crystallinity.
  • the average ethylene content may be > 40 mole %, or ⁇ 50 mole %, or > 60 mole %, or > 70 mole %, or > 80 mole %, or >84 mole %, or > 87 mole %, or > 89 mole %.
  • the average ethylene content may be ⁇ 100 mole %, or ⁇ 98 mole %.
  • the balance of the copolymer may be one or more of the olefinic monomers discussed above, and optionally minor amounts of one or more diene monomers.
  • the density of the polyethylene copolymers or homopolymers, in g/cc may be >0.860, or >0.865, or >0.870, or >0.880, or > 0.890, or > 0.900, or ⁇ 0.970, or ⁇ 0.960, or ⁇ 0.950 or ⁇ 0.940, or ⁇ 0.930, or have a range of >0.865- ⁇ 0.900 or > 0.900- ⁇ 0.930, or > 0.930- ⁇ 0.950, or > 0.950- ⁇ 0.970.
  • the weight average molecular weight (Mw) of the polyethylene copolymer or homopolymer may typically be 30,000 or more, or 50,000 or more, or 80,000 or more.
  • the Mw of the polyethylene copolymer or homopolymer may typically be 500,000 or less, or 300,000 or less, or 200,000 or less.
  • Polyethylene homopolymers and copolymers suitable for use in embodiments of our invention may be produced using Ziegler-Natta or metallocene catalyst systems or may be combinations of polyethylenes produced by each.
  • Polyethylene copolymers or homopolymers produced with metallocene catalysts may display narrow molecular weight distribution, meaning that the ratio of the weight average molecular weight to the number average molecular weight may be equal to or below 4, or in the range of from 1.7 - 4.0, or from 1.8 - 2.8.
  • polyethylene homopolymers or copolymers may be made in a variety of processes (including slurry, solution, high pressure or gas phase) employing metallocene catalysts.
  • Processes for making a variety of polyethylene materials with metallocene catalyst systems are well known. See, for example, U.S. Patent Nos. 5,017,714, 5,026,798, 5,055,438, 5,057,475, 5,096,867, 5,153,157, 5,198,401, 5,240,894, 5,264,405, 5,278,119, 5,281,679, 5,324,800, 5,391,629, 5,420,217, 5,504,169, 5,547,675, 5,621,126, 5,643,847, and 5,801,113, U.S.
  • Polyethylene copolymers produced with metallocene catalysts may also display narrow composition distribution, meaning that the fractional comonomer content from molecule to molecule will be similar. This can be measured by FTIR analysis of discrete ranges of number or weight average molecular weights (Mn or Mw) as identified with Gel Permeation Chromatography (GPC-FTIR), and in limited cases, composition distribution breadth index or solubility distribution breadth index may also be used to measure comonomer distribution.
  • Mn or Mw number or weight average molecular weights
  • GPC-FTIR Gel Permeation Chromatography
  • One contemplated polyethylene copolymer has a comonomer distribution when measured by GPC-FTIR, such that the comonomer content of any discrete molecular weight range comprising 10 weight % or more of the total eluted copolymer may be within ⁇ 30% of the weight average comonomer content of the polyethylene copolymer, where the average equates to 100%), or within ⁇ 20%), or within ⁇ 10%.
  • the SDBI of the polyethylene copolymer may be less than 35°C, generally in the range of 10° to 25°C, or in the range of 15° to 20°C, or in the range of 15° to 18° C.
  • the CDBI of the polyethylene copolymer may be greater than 40%), or greater than 50%, or greater than 60%.
  • the polyethylene copolymer may have a narrow composition distribution if it meets the GPC-FTIR, CDBI, or SDBI criteria as outlined above.
  • the at least one second component can itself be a combination of two or more ethylene polymers, as long as each of the polymers in the at least one second component individually qualify as at least one second component, that is, that the crystallinity of the at least one second component be different from the crystallinity of the first component. If two or more polymers are a part of the at least one second component, they may be the same or different in other micro and/or macro properties, but in combinations they comprise different crystallinity than the at least one first component.
  • the at least one second component can be at least a propylene rich polymer, and if so, its crystallinity as determined by WAXS/NMR may be different propylene crystallinity than that of the at least one first component.
  • Three or more part blends are also contemplated, as long as the physical parameters discussed herein apply and as long as the crystallinity of the at least one second component is different from the at least one first component or components.
  • the at least one first component of isotactic crystallinity the at least one second component may be an ethylene crystallinity and/or syndiotactic crystallinity.
  • the at least one first component of syndiotactic crystallinity the at least one second component may be an ethylene crystallinity and/or isotactic crystallinity.
  • Process oil may be optionally added to the compositions of embodiments of the present invention.
  • the addition of process oil in moderate amounts may lower the viscosity and flexibility of the composition while improving the properties of the composition at temperatures near and below 0°C.
  • the process oils may comprise hydrocarbons comprising of carbon and hydrogen with traces of hetero atoms such as oxygen or comprising carbon, hydrogen and at least one hetero atom such as dioctyl phthalate, ethers and polyethers.
  • the process oils may have a boiling point to be substantially involatile at 200°C. These process oils are commonly available either as neat solids or liquids or as physically absorbed mixtures of these materials on an inert support (e.g.
  • the process oils may comprise mixtures of a large number of chemical compounds which may consist of linear, acyclic but branched, cyclic and aromatic carbonaceous structures.
  • Another family of process oils are certain low to medium molecular weight (Molecular weight (Mn) ⁇ 10,000) organic esters and alkyl ether esters.
  • Mn medium molecular weight
  • Examples of process oils are Sunpar® 150 and 220 from The Sun Manufacturing Company of Marcus Hook, PA, USA and Hyprene® N750 and Hyprene N1200 from Ergon, Post Office Box 1639, Jackson, MS 39215-1639, USA.
  • the addition of the process oils to the composition comprising the at least one first component and the at least one second component may be made by any of the conventional means known to the art. These include the addition of all or part of the process oil prior to recovery of the polymer as well as addition of the process oil, in whole or in part, to the polymer as part of compounding for the interblending of the at least one first component and the at least one second component.
  • the compounding step may be carried out in a batch mixer such as a mill or an internal mixer such as Banbury mixer.
  • the compounding operation may also be conducted in a continuous process such as a twin screw extruder.
  • the at least one first component and the at least one second component composition may include process oil in the range of from 1 to 200, or in the range of from 2 to 50 parts by weight of process oil per hundred parts of total polymer (at least one first component plus at least one second component). Test Methods
  • Tensile modulus was measured by ASTM method D-1708, if small amounts of sample were available (if sample amounts were below 70 grams), and/or by ASTM method D-412 if larger amounts of sample were available (if sample amount was larger than 70 gm).
  • MI Melt Index
  • MFR Melt Flow Rate
  • composition of ethylene propylene copolymers was measured as ethylene wt% according to ASTM D 3900.
  • the composition of the first component was measured as ethylene wt% according to the following technique.
  • a thin homogeneous film of the at least one first polymer component, pressed at a temperature of or greater than 150°C was mounted on a Perkin Elmer PE 1760 infra red spectrophotometer.
  • Comonomer content of discrete molecular weight ranges can be measured by Fourier Transform Infrared Spectroscopy (FTIR) in conjunction with samples collected by GPC.
  • FTIR Fourier Transform Infrared Spectroscopy
  • One such method is described in Wheeler and Willis (Applied Spectroscopy, 1993, vol. 47, pp. 1128-1130). Different but similar methods are equally functional for this purpose and well known to those skilled in the art.
  • Comonomer content and sequence distribution of the polymers may be measured by carbon 13 nuclear magnetic resonance (C-13 ⁇ MR), and such method is well known to those skilled in the art.
  • CDBI Composition Distribution Breadth Index
  • Solubility Distribution Breadth Index is a means to measure the distribution of comonomer within a copolymer having components of varying molecular weights and MWD's as described in U.S. Patent No. 5,008,204 and WO 93/03093.
  • the at least one first component propylene copolymers containing ethylene as a comonomer are shown below (Table 1). These copolymers were produced using a chiral metallocene catalyst known to favor statistically random incorporation of the ethylene comonomer and propylene addition to produce isotactic runs.
  • the copolymer is a thermoplastic elastomer with derived crystallinity resulting from isotactic polypropylene pentads. This copolymer was produced in accordance with the description in U.S. Patent Application Publication 2002/0004575, published January 10, 2002.
  • the at least one second component polymers were ethylene copolymers containing butene, hexene or octene as the comonomer, with the balance being ethylene. Any crystallinity in these copolymers results from crystalline sequences of ethylene as determined by WAXS.
  • the at least one second component ethylene copolymers are shown below (Table 2). Exceed and Exact are registered trademarks of, and are commercially available from, ExxonMobil Chemical Company, Houston, TX. Ethylene polymers called EO1, EO2 and EO3 in the table have been made according to the procedure described below: General Polymerization procedure
  • Ethylene and alpha-olefin feeds were combined into one stream and then mixed with a pre-chilled hexane stream.
  • a hexane solution of an alkyl aluminum scavenger was added to the combined solvent and monomer stream just before it entered the reactor to further reduce the concentration of any catalyst poisons.
  • a mixture of the catalyst components in toluene or toluene/solvent mixture was pumped separately to the reactor and entered through a separate port. The product of the reactor exited through a pressure control valve.
  • Polymer finishing included a concentration step, heat and vacuum stripping and pelletization.
  • a mixture of hexanes (64 Kg/h) and a scavenger solution of tri-n- octylaluminum in hexane were pumped into a 25 liter, liquid filled, stirred tank reactor for at least 20 min before monomers were introduced.
  • Toluene solutions of catalyst and activator were pumped separately to the reactors as described above.
  • Octene was pumped to the solvent line as a liquid.
  • Ethylene was delivered as a gas in a controlled fashion through a mass flow meter/controller and dissolved in the solvent feed line before entering the reactor. After polymerization was established, reactor samples were collected every 2 to 4 hours for analysis and adjustments made to the process to achieve the desired product properties.
  • Reactor effluent was quenched, concentrated, stabilized, heated, and dried under vacuum in various finishing units. Finally, the product was pelletized and collected.
  • compositions of the at least one first component and the at least one second component and other components may be prepared by any procedure that provides an intimate mixture of the components.
  • the components can be combined by melt pressing the components together on a Carver press to a thickness of 0.5 millimeter (20 mils) and a temperature of 180°C, rolling up the resulting slab, folding the ends together, and repeating the pressing, rolling, and folding operation 10 times.
  • Internal mixers are particularly useful for melt blending. Blending at a temperature of between 180°C to 240°C in a Brabender Plastograph for between 1 to , 20 minutes has been found satisfactory.
  • Still another method that may be used for mixing the components involves blending the polymers in a Banbury internal mixer above the flux temperature of all of the components, e.g., 180°C, for 5 minutes.
  • a complete mixture of the polymeric components is indicated by the uniformity of the morphology of the dispersion of the at least one first component and the at least one second component.
  • Continuous mixing may also be used.
  • These processes are well known in the art and include single and twin screw mixing extruders, static mixers for mixing molten polymer streams of low viscosity, impingement mixers, as well as other machines and processes, designed to disperse the first polymer component and the second polymer component in intimate contact.
  • the components may be selected based on the morphology desired for a given application. Those skilled in the art can select the volume fractions of the two components to produce a dispersed at least one second component morphology in a continuous at least one first component matrix, based on the viscosity ratio of the components (see S. Wu, Polymer Engineering and Science, Nol. 27, Page 335, 1987).
  • Compositions were made by mixing all components, including the at least one first component, the at least one second component, the optional amounts of process oil and other ingredients in a Brabender intensive mixture for 3 minutes at a temperature controlled to be within 185°C and 220°C.
  • High shear roller blades were used for the mixing and approximately 0.4g of Irganox® -1076, an antioxidant available from the ⁇ ovartis Corporation, was added to the blend. At the end of the mixing, the mixture was removed and pressed out into a 6" x 6" mold into a pad 0.025" thick at 215°C for 3 to 5 minutes. Films of 0.004" thickness were pressed out in a 4" x 4" mold at 200 °C for 3 to 5 minutes. At the end of this period, the pad was cooled and removed and allowed to anneal for 14 days, at room temperature. Test specimens of the required dumbbell geometry were removed from this pad and evaluated on Instron 4465 or Instron 4505 testers to produce the mechanical deformation data. The Instron Tester and associated equipment is available from The Instron Corporation in Canton, MA. All data is reported in engineering stress and strain terms with values of the stress uncorrected for the contraction in the cross- section of the sample being tested.
  • Tension set was determined on the samples of the composition which had been extended on the Instron to 200% extension and then allowed to relax. The samples were removed and the length (L2) of the deformation zone, between the grips on the Instron, was measured after 10 minutes. The original distance between the grips was the original length (LI) of the deformation zone.
  • compositions of the at least one first component and the at least one second component were made in proportions shown below in the Tables, according to the procedure described above. Properties of the blends were measured as molded. [0073] In each of Tables 3-12 that follow, the 500% tensile modulus and tension set for compositions of the at least one first component and the at least one second component are shown in the respective Table. Examples 1-9: Table 3
  • compositions of first components with three different homopolypropylene samples PP 4292, PD 4443 and ACHIEVE® 3854, available from ExxonMobil Chemical Co., Houston TX, were made in compositions of Table 4, using the procedure described above.
  • Table 4
  • compositions of at least one first component with homopolypropylene PP 4292 available from ExxonMobil Chemical Co., Houston
  • TX were made as seen in Table 6, using the procedure as described above.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur des mélanges polymères ayant une phase continue d'un polymère riche en propylène et une phase dispersée d'un polymère d'éthylène, la phase dispersée pouvant être un autre polymère riche en propylène ou bien un mélange d'un mélange riche en éthylène et d'un polymère riche en propylène. La phase continue et les phases dispersées ont un type de cristallinité différent. Les mélanges présentent un rapport entre le module d'élasticité à 500 % du mélange et le module d'élasticité à 500 % du composant polymère riche en propylène (de la phase continue), non mélangé, = 1,6 à un ensemble de tensions = 98 %. Les mélanges peuvent présenter des propriétés d'un module d'élasticité en flexion faible, généralement = 140,000 psi. Le polymère riche en propylène de la phase continue peut également présenter un taux insoluble d'heptanes < 88 %. Les mélanges polymères de l'invention peuvent être utilisés notamment dans la fabrication de films, fibres, tissus et articles moulés.
PCT/US2003/039907 2002-12-17 2003-12-16 Melanges elastiques comprenant un polymere cristallin elastique et des polymeres cristallisables d'ethylene WO2004060994A1 (fr)

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Cited By (18)

* Cited by examiner, † Cited by third party
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WO2006065649A1 (fr) 2004-12-17 2006-06-22 Exxonmobil Chemical Patents Inc. Melanges de polymeres heterogenes et articles moules realises avec ces melanges
US7238759B2 (en) 2001-11-06 2007-07-03 Dow Global Technologies Inc. Isotactic propylene copolymers, their preparation and use
US7319077B2 (en) 2004-12-17 2008-01-15 Exxonmobil Chemical Patents Inc. Polymer blends and nonwoven articles therefrom
US7619038B2 (en) 2004-12-17 2009-11-17 Exxonmobil Chemical Patents Inc. Homogeneous polymer blend and articles therefrom
US7655730B2 (en) 2005-04-14 2010-02-02 Exxonmobil Chemical Patents Inc. Transparent polyolefin compositions
US7683129B2 (en) 2004-12-17 2010-03-23 Exxonmobil Chemical Patents Inc. Films from polymer blends
US7745526B2 (en) 2004-11-05 2010-06-29 Exxonmobil Chemical Patents Inc. Transparent polyolefin compositions
WO2010077881A2 (fr) * 2008-12-15 2010-07-08 Exxonmobil Chemical Patents Inc. Mélanges en réacteur de polyoléfines thermoplastiques et articles moulés à base de ceux-ci
US7897679B2 (en) 2001-11-06 2011-03-01 Dow Global Technologies Inc. Isotactic propylene copolymers, their preparation and use
WO2011084468A1 (fr) * 2009-12-17 2011-07-14 Exxonmobil Chemical Patents, Inc. Composition de polypropylène incluant un plastifiant adaptée à des pellicules stérilisables
WO2011156262A1 (fr) * 2010-06-10 2011-12-15 Dow Global Technologies Llc Copolymères chocs de propylène à rigidité et résistance aux chocs élevées
US8093335B2 (en) 2008-12-15 2012-01-10 Exxonmobil Chemical Patents Inc. Thermoplastic polyolefin in-reactor blends and molded articles therefrom
US8106127B2 (en) 2008-12-15 2012-01-31 Exxonmobil Chemical Patents Inc. Heterogeneous in-reactor polymer blends
US8192813B2 (en) 2003-08-12 2012-06-05 Exxonmobil Chemical Patents, Inc. Crosslinked polyethylene articles and processes to produce same
US8227547B2 (en) 2008-12-15 2012-07-24 Exxonmobil Chemical Patents Inc. Foamable thermoplastic reactor blends and foam article therefrom
US8410217B2 (en) 2008-12-15 2013-04-02 Exxonmobil Chemical Patents Inc. Thermoplastic polyolefin blends
US8497325B2 (en) 2008-12-15 2013-07-30 Exxonmobil Chemical Patents Inc. Thermoplastic polyolefin blends and films therefrom
US8709560B2 (en) 2004-12-16 2014-04-29 Exxonmobil Chemical Patents Inc. Polymeric compositions including their uses and methods of production

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EP0550214A1 (fr) * 1991-12-20 1993-07-07 Exxon Research And Engineering Company Mélanges de polymères semi-cristallins présentant une résistance intersphérulitique et interlamellaire élevée
US20010039314A1 (en) * 1996-09-04 2001-11-08 Mehta Aspy K. Propylene polymers for films
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WO2000001766A1 (fr) * 1998-07-01 2000-01-13 Exxon Chemical Patents Inc. Melanges elastiques contenant un polymere cristallin et des polymeres de propylene cristallisables
WO2000070134A1 (fr) * 1999-05-13 2000-11-23 Exxon Chemical Patents Inc. Fibres elastiques et articles produits a l'aide de ces fibres, renfermant des polymeres de propylene cristallins et cristallisables
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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7238759B2 (en) 2001-11-06 2007-07-03 Dow Global Technologies Inc. Isotactic propylene copolymers, their preparation and use
US7897679B2 (en) 2001-11-06 2011-03-01 Dow Global Technologies Inc. Isotactic propylene copolymers, their preparation and use
US8192813B2 (en) 2003-08-12 2012-06-05 Exxonmobil Chemical Patents, Inc. Crosslinked polyethylene articles and processes to produce same
US8703030B2 (en) 2003-08-12 2014-04-22 Exxonmobil Chemical Patents Inc. Crosslinked polyethylene process
US7745526B2 (en) 2004-11-05 2010-06-29 Exxonmobil Chemical Patents Inc. Transparent polyolefin compositions
US8709560B2 (en) 2004-12-16 2014-04-29 Exxonmobil Chemical Patents Inc. Polymeric compositions including their uses and methods of production
US7319077B2 (en) 2004-12-17 2008-01-15 Exxonmobil Chemical Patents Inc. Polymer blends and nonwoven articles therefrom
US7476710B2 (en) 2004-12-17 2009-01-13 Exxonmobil Chemical Patents Inc. Heterogeneous polymer blends and molded articles therefrom
US7619038B2 (en) 2004-12-17 2009-11-17 Exxonmobil Chemical Patents Inc. Homogeneous polymer blend and articles therefrom
US7683129B2 (en) 2004-12-17 2010-03-23 Exxonmobil Chemical Patents Inc. Films from polymer blends
WO2006065649A1 (fr) 2004-12-17 2006-06-22 Exxonmobil Chemical Patents Inc. Melanges de polymeres heterogenes et articles moules realises avec ces melanges
US7655730B2 (en) 2005-04-14 2010-02-02 Exxonmobil Chemical Patents Inc. Transparent polyolefin compositions
US8227547B2 (en) 2008-12-15 2012-07-24 Exxonmobil Chemical Patents Inc. Foamable thermoplastic reactor blends and foam article therefrom
US8093335B2 (en) 2008-12-15 2012-01-10 Exxonmobil Chemical Patents Inc. Thermoplastic polyolefin in-reactor blends and molded articles therefrom
US8106127B2 (en) 2008-12-15 2012-01-31 Exxonmobil Chemical Patents Inc. Heterogeneous in-reactor polymer blends
US8410217B2 (en) 2008-12-15 2013-04-02 Exxonmobil Chemical Patents Inc. Thermoplastic polyolefin blends
US8497325B2 (en) 2008-12-15 2013-07-30 Exxonmobil Chemical Patents Inc. Thermoplastic polyolefin blends and films therefrom
WO2010077881A3 (fr) * 2008-12-15 2010-09-10 Exxonmobil Chemical Patents Inc. Mélanges en réacteur de polyoléfines thermoplastiques et articles moulés à base de ceux-ci
WO2010077881A2 (fr) * 2008-12-15 2010-07-08 Exxonmobil Chemical Patents Inc. Mélanges en réacteur de polyoléfines thermoplastiques et articles moulés à base de ceux-ci
EP2390279A1 (fr) * 2009-12-17 2011-11-30 ExxonMobil Chemical Patents Inc. Composition en polypropylène avec plastifiant pour films stérilisables
WO2011084468A1 (fr) * 2009-12-17 2011-07-14 Exxonmobil Chemical Patents, Inc. Composition de polypropylène incluant un plastifiant adaptée à des pellicules stérilisables
WO2011156262A1 (fr) * 2010-06-10 2011-12-15 Dow Global Technologies Llc Copolymères chocs de propylène à rigidité et résistance aux chocs élevées
US8178623B2 (en) 2010-06-10 2012-05-15 Dow Global Technologies Llc High stiffness high impact propylene impact copolymers field of the invention
US9085684B2 (en) 2010-06-10 2015-07-21 W.R. Grace & Co.-Conn. High stiffness high impact propylene impact copolymers

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