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WO2021080803A1 - Compositions de copolymère choc - Google Patents

Compositions de copolymère choc Download PDF

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Publication number
WO2021080803A1
WO2021080803A1 PCT/US2020/055204 US2020055204W WO2021080803A1 WO 2021080803 A1 WO2021080803 A1 WO 2021080803A1 US 2020055204 W US2020055204 W US 2020055204W WO 2021080803 A1 WO2021080803 A1 WO 2021080803A1
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WIPO (PCT)
Prior art keywords
copolymer composition
impact copolymer
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impact
mol
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PCT/US2020/055204
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English (en)
Inventor
Zerong Lin
Antonios K. Doufas
Ranadip GANGULY
George J. Pehlert
Krishnan ANANTHA NARAYANA IYER
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Exxonmobil Chemical Patents Inc.
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Publication of WO2021080803A1 publication Critical patent/WO2021080803A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst

Definitions

  • the present disclosure relates to impact copolymer compositions and processes for production and use of impact copolymer compositions.
  • a variety of polymerization processes can be used to prepare the crystalline polypropylene and the secondary polymer, such as gas phase, slurry, liquid, and/or solution polymerization. It is also possible to make the constituent polymers in two different polymerization processes, for example, slurry phase for the polymerization of the polypropylene and gas phase for the polymerization of the copolymer, or simply “copolymer”.
  • the composition, composition distribution, amount, molecular weight, and/or molecular weight distribution of the secondary polymer primarily determines the engineering properties of the ICP. Accordingly, control over the secondary polymer is desirable in order to control the properties of the ICP produced via the two stage polymerization process.
  • Such control over the secondary polymer may also be important for injection molding of large parts, such as those used in the automotive industry.
  • the injection molding of large parts may suffer from surface appearance defects called “tiger striping” which is detrimental to product quality. Tiger striping is characterized by alternating dull and glossy bands on the polymer surface of injection molded parts. The tiger striping phenomenon may be caused by an unstable flow front causing slip-stick of the polymer within the mold.
  • One potential strategy to reduce tiger striping defects involves increasing the rubber to matrix viscosity ratio.
  • One method used to increase the viscosity ratio involves increasing the molecular weight and/or increasing the intrinsic viscosity of the rubbery secondary copolymer, such as an ethylene :propylene copolymer in an ICP, which improves the viscosity ratio of the rubber and the matrix.
  • the improvement in viscosity ratio may stem from a broader molecular weight distribution of the ICP.
  • a method typically used to increase molecular weight of the secondary copolymer is removing hydrogen prior to entering the gas phase reactor. Hydrogen reduction for achieving high viscosity ratio is limited because of process limitations concerning hydrogen removal and, therefore, the viscosity ratio cannot be increased beyond a certain point. Furthermore, reduction of hydrogen in production of the secondary polymer becomes more difficult when hydrogen is added to the production of the matrix polymer.
  • vinyl-termination in polymers may be useful for post-polymerization
  • post-oligomerization reactions due to the available vinyl unsaturation at one or more chain ends, or one or more branch ends.
  • post-polymerization reactions include (i) addition reactions, such as those used in grafting other unsaturated moieties, (ii) insertion polymerization where the vinyl-terminated polymers are copolymerized with other monomers such as a-olefins and/or other insertion polymerizable monomers and/or (iii) cross-linking reactions where the vinyl terminations are linked creating rubbery materials.
  • an ICP including vinyl chain unsaturation could provide advantages over prior ICPs by allowing for post reactor reactions with the vinyl terminations ⁇ Additionally, the inclusion of vinyl termination may improve the molecular weight of the rubbery ICP components and, therefore, the rheological properties of the ICP, such as melt flow, viscosity ratio, and reduced tiger striping. Furthermore, the inclusion of vinyl terminations may reduce the costs of ICP production. Therefore, there is also a need to provide ICPs with vinyl terminations.
  • Publications of interest include: US 9663647; US 9416262; US 9388304; US 9102823; US 9416238; US 8901259; US 8829113; US 8653198; US 8618220; US 8580890;
  • the present disclosure provides impact copolymer compositions including a polypropylene and a copolymer including ethylene derived units, propylene derived units, and an a, co-diene derived units.
  • the impact copolymer compositions have a melt flow rate of from about 0.1 g/lOmin to about 600 g/lOmin and a loss tangent (tan d) at 0.1 rad/sec angular frequency of about 5 or less.
  • the present disclosure also provides for processes for producing impact copolymer compositions including introducing a catalyst and propylene to a first reactor forming a first polymer, and introducing the first polymer, ethylene, at least one a, co-diene, and optionally additional propylene, to a second reactor.
  • the Figure is a graph depicting tan d versus angular frequency of impact copolymers, according to one or more embodiments.
  • the loss tangent (tan d) in this disclosure is defined as the ratio of the loss modulus (G”) over the storage modulus (G’) at an angular frequency of 0.1 rad/s and a temperature of 190 C. It was determined via isothermal Small angle oscillatory shear (SAOS) frequency sweep experiments at 190°C using a 25 mm cone (1°) and plate configuration on an MCR301 controlled strain/stress rheometer (Anton Paar GmbH). Sample test disks (25 mm diameter, 1 mm thickness) were prepared via compression molding of pellet samples at 190°C using a Schwabenthan laboratory press (200T). Typical cycle for sample preparation is 1 minute without pressure followed by 1.5 minute under pressure (50 bars) and then cooling during 5 minutes between water cooled plates.
  • SAOS Small angle oscillatory shear
  • the sample was first equilibrated at 190°C for 13 min to erase any prior thermal and crystallization history.
  • An angular frequency sweep was next performed from 500 rad/s to 0.1 rad/s using 6 points/decade and a strain lying in the linear viscoelastic region (typically in the range of 5-15%) determined from strain sweep isothemal experiments. All SAOS experiments were performed in a nitrogen atmosphere to minimize any degradation of the sample during rheological testing.
  • the rheological parameter tan d relates to melt elasticity (higher melt elasticity corresponding to lower value of tan d) and can be controlled or changed by controlling the molecular characteristics of the ICP including but not limited to the copolymer content (R%), the comonomer content of the copolymer (C2%), the intrinsic viscosity (IV) of the copolymer, and/or the matrix polypropylene IV or melt flow rate (MFR).
  • the loss tangent (tan d) at a low angular frequency e.g.
  • tiger marking or “tiger stripes”, an undesirable phenomenon that often occurs when extruding a polymer to form an article, leaving a pattern on the solid article that is unappealing
  • tiger stripes an undesirable phenomenon that often occurs when extruding a polymer to form an article, leaving a pattern on the solid article that is unappealing
  • a neat ICP composition or a TPO compound comprising the ICP composition for example, see Maeda, S., K. Fukunaga, and E. Kamei, in “Flow mark in the injection molding of polypropylene/rubber/talc blends,” 35 NIHON REOROJI GAKKAISHI 293-299 (2007); and US 2016/0194488 Al.
  • polymer includes, but is not limited to, homopolymers, copolymers, terpolymers, etc., and alloys and blends thereof.
  • polymer also includes impact, block, graft, random, and alternating to copolymers.
  • polymer shall further include all possible geometrical configurations unless otherwise specifically stated. Such configurations may include isotactic, syndiotactic and random symmetries.
  • copolymer is meant to include polymers having two or more monomers (monomer derived units), optionally, with other monomers, and may refer to interpolymers, terpolymers, etc.
  • blend refers to a mixture of two or more polymers.
  • the term “monomer”, can refer to the monomer used to form a polymer, including the unreacted chemical compound in the form prior to polymerization, and the monomer after it has been incorporated into the polymer. Different monomers are discussed herein, including propylene monomers, ethylene monomers, and diene monomers.
  • the term “comonomer” can refer to a second monomer used to form a polymer, including the unreacted chemical compound in the form prior to polymerization, and the comonomer after it has been incorporated into the polymer.
  • Different comonomers are discussed herein, including ethylene monomers, and diene monomers, such as a, co-dienes.
  • reactor blend means a highly dispersed and mechanically inseparable blend of two or more polymers produced in situ.
  • a reactor blend polymer may be the result of a sequential (or series) polymerization process where a first polymer component is produced in a first reactor and a second polymer component is produced in a second reactor in the presence of the first polymer component.
  • a reactor blend polymer may be the result of a parallel polymerization process where the polymerization effluent containing the polymer components made in separate parallel reactors are solution blended to form the final polymer product.
  • Reactor blends may be produced in a single reactor, a series of reactors, or parallel reactors and are reactor grade blends.
  • IV intrinsic viscosity
  • a solution of polymer in a given solvent at a given temperature when the impact copolymer composition is at infinite dilution and is calculated according to the ASTM D1601 standard.
  • ASTM D1601 the IV measurement utilizes a standard capillary viscosity measuring device, in which the viscosity of a series of concentrations of the polymer in the solvent at a given temperature are determined.
  • decalin is a suitable solvent and a typical temperature is 135 °C. From the values of the viscosity of solutions of varying concentrations, the viscosity at infinite dilution is determined by extrapolation.
  • catalyst system means the combination of one or more catalysts with one or more activators and, optionally, one or more support compositions.
  • An “activator” is a compound or component, or combination of compounds or components, capable of enhancing the ability of one or more catalysts to polymerize monomers to polymers.
  • impact copolymer or “impact copolymer composition” (“ICP”) means those blends including at least two components, the blend being substantially thermoplastic and having a high impact resistance, for example a flexural modulus measurable by ISO 178 method of about 250 MPa or greater, such as about 500 MPa or greater.
  • ISO 178 method a flexural modulus measurable by ISO 178 method of about 250 MPa or greater, such as about 500 MPa or greater.
  • An ICP is a blend of at least two components at least one polypropylene and at least one elastomeric/rubber-like component or copolymer (“the copolymer”).
  • An ICP may include from about 40 wt% to about 95 wt% polypropylene and from about 5 wt% to about 60 wt% the copolymer, or from about 50 wt% to about 90 wt% polypropylene and from about 10 wt% to about 50 wt% the copolymer, or from about 60 wt% to about 90 wt% polypropylene and from about 10 wt% to about 40 wt% the copolymer, or from about 70 wt% to about 85 wt% polypropylene and from about 15 wt% to about 30 wt% the copolymer.
  • the ICP may consist essentially of components A and B.
  • the overall comonomer (e.g., ethylene and a, co-diene) content of the ICP may be from about 3 wt% to about 40 wt%, or from about 5 wt% to about 25 wt%, or from about 6 wt% to about 20 wt%, or from about 7 wt% to about 15 wt%.
  • the ICPs may, in any embodiments, be reactor blends, meaning that components A and B are not physically or mechanically blended together after polymerization but are interpolymerized in at least one reactor, often in two or more reactors in series.
  • the ICP as obtained from the reactor or reactors may be blended with various other components including other polymers or additives.
  • an ICP may be formed by producing components A and B in separate reactors and physically blending the components once they have exited their respective reactors.
  • an ICP may be described as “heterophasic.” The term “heterophasic” means that the polymers have two or more phases.
  • heterophasic ICPs include a matrix component in one phase and an elastomeric component phase, for example rubber phase, dispersed within the matrix.
  • the ICPs include a matrix phase including a propylene homopolymer and a dispersed phase including a propylene-ethylene- a, co-diene copolymer (the copolymer).
  • the copolymer component (the copolymer) has rubbery characteristics and provides impact resistance, while the polypropylene component provides overall stiffness.
  • a catalyst system is introduced at the beginning of the polymerization of propylene and may be transferred with the resulting polypropylene to the copolymerization reactor where it may also serve to catalyze the gas phase copolymerization of the copolymer to produce an ICP. Additional catalyst composition may be added in stage 1 and/or stage 2 at any suitable point in the reactor(s).
  • the resultant powder may be passed through a degassing stage before passing to one or more gas phase reactors (stage 2), where propylene is copolymerized with ethylene or an alpha-olefin co-monomer including, C4, C6, or C8 alpha olefins or combinations thereof, and at least one a, co-diene in the presence of the polypropylene produced in stage 1 and the catalyst transferred therewith to produce the copolymer.
  • gas phase reactors include, but are not limited to, a fluidized (horizontal or vertical) or stirred bed reactor or combinations thereof.
  • the impact polymer can have an the copolymer content of about 5 wt% to about 80 wt%, about 5 wt% to about 60 wt%, about 5 wt% to about 50 wt%, about 5 wt% to about 40 wt%, about 6 wt% to about 35 wt%, about 7 wt% to about 30 wt%, or about 8 wt% to about 30 wt%, based on the total weight of the polymers in the ICP.
  • Both the polypropylene and copolymer components of the ICP may include propylene derived units.
  • the impact copolymer can have a total propylene content of about 75 wt% or more, about 80 wt% or more, about 85 wt% or more, about 90 wt% or more, or about 95 wt% or more, based on the combined weight of propylene monomers in polypropylene and the copolymer.
  • the impact copolymer can have a total comonomer (in this instance referring to non-propylene monomers) content from about 1 wt%, about 5 wt%, about 9 wt%, or about 12 wt% to about 18 wt%, about 23 wt%, about 28 wt%, or about 35 wt%, based on the total weight of the impact copolymer.
  • a total comonomer in this instance referring to non-propylene monomers
  • the ICP may have a R % (wt% rubber as determined by low field solid state NMR) of about 5 wt% to about 40 wt%, such as about 8 wt% to about 30 wt% or about 15 wt% to about 25 wt%, based on the weight of the ICP.
  • R % wt% rubber as determined by low field solid state NMR
  • the ICP may have a C2% (wt% ethylene content in the copolymer, determined by total wt% of ethylene measured by IR divided wt% or rubber (R%)) of about 30 wt% to about 70 wt%, such as about 35 wt% to about 65 wt%, or about 40 wt% to about 60 wt%, based on the weight of the copolymer.
  • Melt Flow Rate (“MFR”) of the ICP may be from about 1 g/lOmin to about 1000 g/10 min, such as from about 1 g/lOmin to about 500 g/10 min, from about 1 g/lOmin to about 50 g/10 min, from about 1 g/lOmin to about 25 g/10 min, from about 1 g/lOmin to about 20 g/10 min, or from about 1 g/lOmin to 10 g/10 min.
  • the MFR may be determined by ASTM- 1238 measured at load of 2.16 kg and 230 °C.
  • the ICP can have a weight average molecular weight (Mw) from about 20 kg/mol, about 50 kg/mol, about 75 kg/mol, about 150 kg/mol, about 200 kg/mol, about 250 kg/mol, or about 300 kg/mol to about 600 kg/mol, about 900 kg/mol, about 1,300 kg/mol, or about 2,000 kg/mol.
  • Mw weight average molecular weight
  • the ICP can have a Mw of about 50 kg/mol to about 3,000 kg/mol, about 100 kg/mol to about 2,000 kg/mol, or about 250 kg/mol to about 1,000 kg/mol.
  • the ICP can have a number average molecular weight (Mn) from about 1 kg/mol, about 5 kg/mol, about 10 kg/mol, about 15 kg/mol, or about 20 kg/mol to about 100 kg/mol, about 120 kg/mol, about 130 kg/mol, about 140 kg/mol, or about 150 kg/mol.
  • Mn number average molecular weight
  • the ICP can have a Mn of about 1 kg/mol to about 150 kg/mol, about 5 kg/mol to about 100 kg/mol, or about 15 kg/mol to about 50 kg/mol.
  • the ICP can have a Z average molecular weight (Mz) from about 100 kg/mol, 200 kg/mol, about 400 kg/mol, about 600 kg/mol, about 800 kg/mol, or about 1,000 kg/mol to about 4,000 kg/mol, about 5,000 kg/mol, about 6,000 kg/mol, or about 8,000 kg/mol.
  • Mz Z average molecular weight
  • the ICP can have a Mz of about 100 kg/mol to about 8,000 kg/mol, about 200 kg/mol to about 5,000 kg/mol, or about 400 kg/mol to about 4,000 kg/mol.
  • the ICP can have a polydispersity index (Mw/Mn) from about 1, about 2, about 3, about 4, or about 5 to about 20, about 17, about 15, or about 12.
  • Mw/Mn polydispersity index
  • the impact copolymer composition can have a melting point (Tm, peak second melt) of about 100 °C or more, about 110 °C or more, about 120 °C or more, about 130 °C or more, about 140 °C or more, about 150 °C or more, about 160 °C or more, or about 165 °C or more.
  • the impact copolymer composition can have a melting point from about 100 °C to about 175 °C, such as from about 105 °C to about 165 °C, about 105 °C to about 145 °C, or about 100 °C to about 155 °C
  • the impact copolymer composition can have a heat of fusion (Hf, DSC second heat) from about 20 J/g, about 30 J/g, about 40 J/g, or about 50 J/g to about 60 J/g, about 75 J/g, about 85 J/g, about 95 J/g, about 100 J/g or more.
  • the impact copolymer composition can have a heat of fusion of 60 J/g or more, 70 J/g or more, 80 J/g or more, 90 J/g or more, about 95 J/g or more, or about 100 J/g or more.
  • the impact copolymer composition can have glass transition temperature (Tg) of the copolymer component of -20 °C or less, -30 °C or less, -40 °C or less, or -50 °C or less.
  • Tg glass transition temperature
  • the impact copolymer composition can have a 1 % secant flexural modulus from about 300 MPa, about 600 MPa, about 800 MPa, about 1,100 MPa, or about 1,200 MPa to about 1,500 MPa, about 1,800 MPa, about 2,100 MPa, about 2,600 MPa, or about 3,000 MPa, as measured according to ASTM D 790 (A, 1.3 mm/min).
  • the impact copolymer composition can have a flexural modulus from about 300 MPa to about 3,000 MPa, about 500 MPa to about 2,500 MPa, about 700 MPa to about 2,000 MPa, or about 900 MPa to about 1,500 MPa, as measured according to ASTM D 790 (A, 1.3 mm/min).
  • the impact copolymer composition can have a notched Izod impact strength at 23 °C of about 2.5 KJ/m 2 or more, about 5 KJ/m 2 or more, about 7.5 KJ/m 2 or more, about 10 KJ/m 2 or more, about 15 KJ/m 2 or more, about 20 KJ/m 2 or more, about 25 KJ/m 2 or more, or about 50 KJ/m 2 or more, as measured according to ASTM D 256 (Method A).
  • the impact copolymer composition can have a notched Izod impact strength at 23 °C from about 3 KJ/m 2 , about 6 KJ/m 2 , about 12 KJ/m 2 or about 18 KJ/m 2 to about 30 KJ/m 2 , about 35 KJ/m 2 , about 45 KJ/m 2 , about 55 KJ/m 2 , or about 65 KJ/m 2 , as measured according to ASTM D 256 (Method A).
  • the impact copolymer composition can have a Gardner impact strength at -30 °C from about 2 KJ/m 2 , about 3 KJ/m 2 , about 6 KJ/m 2 , about 12 KJ/m 2 , or about 20 KJ/m 2 to about 55 KJ/m 2 , about 65 KJ/m 2 , about 75 KJ/m 2 , about 85 KJ/m 2 , about 95 KJ/m 2 , or about 105 KJ/m 2 , as measured according to ASTM D 5420 (GC).
  • GC ASTM D 5420
  • the impact copolymer composition can have a Gardner impact strength at -30 °C of about 2 KJ/m 2 to about 100 KJ/m 2 , about 3 KJ/m 2 to about 80 KJ/m 2 , or about 4 KJ/m 2 to about 60 KJ/m 2 , as measured according to ASTM D 5420 (GC).
  • a Gardner impact strength at -30 °C about 2 KJ/m 2 to about 100 KJ/m 2 , about 3 KJ/m 2 to about 80 KJ/m 2 , or about 4 KJ/m 2 to about 60 KJ/m 2 , as measured according to ASTM D 5420 (GC).
  • the impact copolymer composition can have a heat deflection temperature (HDT) from about 75 °C, about 83 °C, about 87 °C, or about 92 °C to about 95 °C, about 100 °C, about 105 °C, or about 120 °C, as measured according to ASTM D 648 (0.45 MPa).
  • HDT heat deflection temperature
  • the impact copolymer composition can have a heat deflection temperature of about 80 °C or more, about 85 °C or more, about 90 °C or more, or about 95 °C or more, as measured according to ASTM D 648 (0.45 MPa).
  • the impact copolymer composition can have the copolymer concentration of at least about 10 wt % to about 35 wt%, based on the combined weight of polymers, a notched Izod impact strength at 23 °C of at least 5 KJ/m 2 to about 75 KJ/m 2 , and a flexural modulus less than 1 ,200 MPa to about 1 ,900 MPa.
  • the impact copolymer composition can have an copolymer concentration of at least about 15 wt% to about 25 wt%, based on the combined weight of the polymers, a notched Izod impact strength at 23 °C of at least 15 KJ/m 2 to about 65 KJ/m 2 , and a flexural modulus less than 1,300 MPa to about 1,800 MPa.
  • the impact copolymer composition can comprise a copolymer having a weight average molecular weight of at least 30 kg/mol to about 200 kg/mol, a notched Izod impact strength at 23 °C of at least 5 KJ/m 2 to about 75 KJ/m 2 , and an MFR at 230 °C of from 10 to 75.
  • the impact copolymer composition can comprise a copolymer having a weight average molecular weight of at least 10 kg/mol to about 35 kg/mol, a notched Izod impact strength at 23 °C of at least 5 KJ/m 2 to about 75 KJ/m 2 , and an MFR at 230 °C of from 10 to 75.
  • the impact copolymer composition can comprise a copolymer having a weight average molecular weight of at least 45 kg/mol to about 150 kg/mol, a notched Izod impact strength at 23 °C of at least 15 KJ/m 2 to about 65 KJ/m 2 , and an MFR at 230 °C from about 10 g/lOmin to about 75 g/lOmin.
  • the impact copolymer composition can comprise a copolymer having a weight average molecular weight of at least 35 kg/mol to about 250 kg/mol, a notched Izod impact strength at 23 °C of at least 15 KJ/m 2 to about 65 KJ/m 2 , and an MFR at 230 °C from about 10 g/lOmin to about 75 g/10min.
  • the ICP may be prepared using a Ziegler-Natta catalyst system with a blend of electron donors as described in US 6,087,459 or US 2010/0105848, incorporated by reference.
  • the ICP may be prepared using a succinate Ziegler-Natta type catalyst system.
  • the ICP compositions can be prepared using a Ziegler-Natta type catalyst, a co catalyst such as triethylaluminum (“TEA”), and optionally an electron donor including the non- limiting examples of dicyclopentyldimethoxysilane (“DCPMS”), cyclohexylmethyldimethoxysilane (“CMDMS”), diisopropyldimethoxysilane (“DIPDMS”), di-t-butyldimethoxysilane, cyclohexylisopropyldimethoxysilane, n- butylmethyldimethoxysilane, tetraethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane, mono and di-alkylaminotrialkoxysilanes or other electron donors or combination(s) thereof
  • DCPMS dicyclopentyldimethoxysilane
  • CMDMS cyclohexylmethyldime
  • the catalyst can be or include one or more Ziegler-Natta and/or one or more single-site, e.g., metallocene, polymerization catalysts.
  • the catalyst(s) can be supported, e.g., for use in heterogeneous catalysis processes, or unsupported, e.g., for use in homogeneous catalysis processes.
  • the polypropylene and copolymer components of the ICP can be made with a common supported Ziegler-Natta or single-site catalyst.
  • the catalyst system may have a mileage of about 30,000 glCP/gCatalyst or greater, such as about 35,000 glCP/gCatalyst or greater, or about 40,000 glCP/gCatalyst or greater.
  • Polypropylenes include those solid, typically high-molecular weight plastic resins that primarily include units deriving from the polymerization of propylene. In any embodiments, at least 75%, in other embodiments at least 90%, in other embodiments at least 95%, and in other embodiments at least 97% of the units of the propylene-based polymer are derived from the polymerization of propylene.
  • Polypropylene may be a propylene homopolymer with little or substantially no comonomer content, such as about 5 wt% or less, about 4 wt% or less, about 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, or 0.05 wt% or less (substantially no comonomer).
  • polypropylene is a propylene homopolymer, such as an isotactic propylene homopolymer.
  • Polypropylene homopolymer can include linear chains and/or chains with long chain branching.
  • the polymer component of polypropylene consists essentially of propylene-derived units and does not contain comonomer except that which may be present due to impurities in the propylene feed stream.
  • polypropylene consists essentially of propylene-derived units.
  • small amounts (less than 10 wt%) of a comonomer may be used in polypropylene to obtain desired polymer properties.
  • Such copolymers contain less than 10 wt%, or less than 6 wt%, or less than 4 wt%, or less than 2 wt%, or less than 1 wt% of comonomer.
  • the propylene-based polymers may also include units deriving from the polymerization of ethylene and/or a-olefins such as 1 -butene, 1 -hexene, 1-octene, 2-methyl- 1-propene, 3-methyl- 1-pentene, 4-methyl- 1-pentene, 5-methyl- 1 -hexene, and mixtures thereof.
  • a-olefins such as 1 -butene, 1 -hexene, 1-octene, 2-methyl- 1-propene, 3-methyl- 1-pentene, 4-methyl- 1-pentene, 5-methyl- 1 -hexene, and mixtures thereof.
  • a-olefins such as 1 -butene, 1 -hexene, 1-octene, 2-methyl- 1-propene, 3-methyl- 1-pentene, 4-methyl- 1-pentene, 5-methyl- 1 -hexene, and mixtures thereof.
  • the polypropylene includes a homopolymer, random copolymer, or impact copolymer composition polypropylene or combination thereof.
  • the polypropylene is a high melt strength (HMS) long chain branched (LCB) homopolymer polypropylene.
  • the propylene-based polymers may be synthesized by using an appropriate polymerization techniques such as Ziegler-Natta type polymerizations, and catalysis employing single-site organometallic catalysts including metallocene catalysts.
  • Propylene based polymer crystallinity and isotacticity and, therefore, the crystallinity and tacticity of polypropylene can be controlled by the ratio of co-catalyst to electron donor, and the type of co-catalyst/donor system and is also affected by the polymerization temperature. The appropriate ratio of co-catalyst to electron donor is dependent upon the catalyst/donor system selected.
  • Examples of polypropylene useful for ICP blends may include ExxonMobilTM PP5341 (available from ExxonMobil); AchieveTM PP6282NE1 (available from ExxonMobil) and/or polypropylene resins with broad molecular weight distribution as described in US 9,453,093 and US 9,464,178; and other polypropylene resins described in US20180016414 and US20180051160; Waymax MFX6 (available from Japan Polypropylene Corp.); Borealis DaployTM WB140 (available from Borealis AG); and Braskem Ampleo 1025MA and Braskem Ampleo 1020GA (available from Braskem Ampleo).
  • propylene-based matrix examples include, but are not limited to, homopolymer polypropylene and random ethylene-propylene or random propylene-alpha olefin copolymer, where the comonomer includes, but is not limited to, C4, C6 or C8 alpha olefins or combinations thereof.
  • the polymerization of propylene and, if present, other monomer(s) to produce polypropylene can form particles having a weight average particle size along the longest cross- sectional length thereof from about 0.01 mm, about 0.05 mm, about 0.1 mm, about 0.3 mm, or about 0.5 mm to about 2 mm, about 3 mm, about 4 mm, about 5 mm, or about 6 mm.
  • the particles can have a weight average particle size along the longest cross-sectional length thereof of from about 0.05 mm to about 5 mm, about 0.1 mm to about 4 mm, about 1 mm to about 4.5 mm, about 1.5 mm to about 3 mm, about 2 mm to about 4 mm, or about 0.2 mm to about 3.5 mm.
  • the particles can also have one or more pores formed within and/or through.
  • the polypropylene particles can have a pore volume of less than 80%, less than 75%, less than 70%, less than 60%, less than 50%, or less than 40%.
  • the particles can have a pore volume from about 5%, about 10%, about 15%, or about 20% to about 55%, about 65%, about 75%, about 80%, about 85%, or about 90%.
  • the particles have a pore volume of less than 80%.
  • the pores formed in and/or through the particles may have an average volume from about 10 -9 mm 3 , about 10 -8 mm 3 , about 10 -7 mm 3 , or about 10 -5 mm 3 , to about 10 -3 mm 3 , about 10 -2 mm3, about 10 -1 mm 3 , about 1 mm 3 , or about 10 mm 3 .
  • the polypropylene particles can have pores having an average volume of about 10 -9 mm 3 to about 10 mm 3 , about 10 -7 mm 3 to about 10 -2 mm 3 , or about 10 -5 mm 3 to about 10 -4 mm 3 .
  • the pores formed in and/or through the particles may have a cross-sectional length or in the case of spherical pores a diameter from about 10 -6 mm, about 10 -5 mm, about 10 -4 mm, or about 10 -3 mm to about 10 -3 mm, about 10 -2 mm, about 10 -1 mm, about 1 mm, or about 10 mm.
  • the polypropylene component of the inventive ICP includes one or more of the following characteristics:
  • Mw Polypropylene weight average molecular weight from about 50,000 g/mol to about 2,000,000 g/mol, such as from about 100,000 g/mol to about 1,000,000 g/mol, from about 100,000 g/mol to about 600,000 g/mol, or from about 400,000 g/mol to about 800,000 g/mol, as measured by gel permeation chromatography (GPC) with polystyrene standards.
  • GPC gel permeation chromatography
  • Polypropylene may have a number average molecular weight (Mn) from about 25,000 g/mol to about 1,000,000 g/mol, such as from about 50,000 g/mol to about 300,000 g/mol as measured by GPC with polystyrene standards.
  • Mn number average molecular weight
  • Polypropylene may have a Z average molecular weight (Mz) from about 75,000 g/mol to about 3,000,000 g/mol, such as from about 100,000 g/mol to about 2,000,000 g/mol as measured by GPC with polystyrene standards.
  • Mz Z average molecular weight
  • Polypropylene may have a broad polydispersity index, Mw/Mn, of about 4.5 or greater, about 5 or greater, about 5.5 or greater, or about 6 or greater.
  • polypropylene has a Mw/Mn of about 15 or less, about 14 or less, about 13 or less, about 12 or less, about 11 or less, about 10 or less, about 9.5 or less, or about 9 or less.
  • polypropylene has a Mw/Mn from about 4.5 to about 15, such as from about 4.5 to about 12, from about 5 to about 10, or from about 6 to about 9.
  • these polydispersity indices are obtained in the absence of visbreaking using peroxide or other post reactor treatment designed to reduce molecular weight.
  • Polypropylene may have an Mz/Mw ratio of about 2.5 or greater, about 2.6 or greater, about 2.7 or greater, about 2.8 or greater, about 2.9 or greater, about 3 or greater, about 3.1 or greater, or about 3.2 or greater. Polypropylene may have an Mz/Mw ratio of about 7 or less, about 6.5 or less, about 6 or less, about 5.5 or less, or about 5 or less.6) Polypropylene may have a melting point (T m ) that is from about 110 °C to about 170 °C, such as from about 140 °C to about 168 °C, or from about 160 °C to about 165 °C, as determined by ISO 11357-1,2,3.
  • T m melting point
  • Polypropylene may have a glass transition temperature (T g ) that is from about -50 °C to about 10 °C, such as from about -30 °C to about 5 °C, or from about -20 °C to about 2 °C, as determined by ISO 11357-1,2,3. 8) Polypropylene may have a crystallization temperature (T c ) that is about 75 °C or more, such as about 95 °C or more, about 100 °C or more, about 105 °C or more, or from about 105 °C to about 130 °C), as determined by ISO 11357-1,2,3
  • Polypropylene may have a melt flow rate (MFR) from about 0.1 g/10min to about 500 g/10 min, such as from about 0.2 g/lOmin to about 200 g/10 min, from about 0.5 g/lOmin to about 175 g/10 min, from about 1 g/lOmin to about 160 g/10 min, from about 1.5 g/lOmin to about 150 g/10 min, or from about 3 to about 100 g/10 min.
  • MFR melt flow rate
  • the MFR may be determined by ASTM-1238 measured at load of 2.16 kg and 230 °C.
  • Polypropylene may have a heat of fusion (Hf) that is about 52.3 J/g or more, such as about 100 J/g or more, about 125 J/g or more, or about 140 J/g or more.
  • Hf heat of fusion
  • Polypropylene may have a g' vis that is about 1 or less, such as about 0.9 or less, about 0.8 or less, about 0.6 or less, or about 0.5 or less).
  • the polypropylene component of the ICP includes a homopolymer of a high-crystallinity isotactic or syndiotactic polypropylene.
  • the polypropylene component can have a density of from about 0.89 g/cc 3 to about 0.91 g/cc 3 , with the largely isotactic polypropylene having a density of from about 0.90 g/cc 3 to about 0.91 g/cc 3 .
  • high and ultra-high molecular weight polypropylene that has a fractional melt flow rate can be employed.
  • polypropylene resins may be characterized by a MFR (ASTM D-1238; 2.16 kg @ 230 °C) that is about 10 g/lOmin or less, such as about 1 g/lOmin or less, or about 0.5 g/lOmin or less.
  • MFR ASTM D-1238; 2.16 kg @ 230 °C
  • the copolymer is formed by the polymerization of ethylene, propylene, and at least one a, co-diene.
  • the copolymer includes those solid, typically high-molecular weight resins that include units derived from the polymerization of ethylene, units derived from polymerization of propylene, and units derived from polymerization of at least one a, co-diene.
  • the copolymer component of the ICP may also include units deriving from the polymerization of additional a-olefins such as 1 -butene, 1 -hexene, 1-octene, 2-methyl- 1- propene, 3-methyl- 1-pentene, 4-methyl- 1-pentene, 5 -methyl- 1 -hexene, and mixtures thereof.
  • additional a-olefins such as 1 -butene, 1 -hexene, 1-octene, 2-methyl- 1- propene, 3-methyl- 1-pentene, 4-methyl- 1-pentene, 5 -methyl- 1 -hexene, and mixtures thereof.
  • An a, co-diene is a hydrocarbon with two or more carbon-carbon double-bonds at an end of a chain or branch.
  • co-dienes include unbranched hydrocarbons with an alkene at each terminus of the carbon chain, such as 1,3-butadiene, 1 ,4-pentadiene, 1,5- hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1 ,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, 1,14-pentadecadiene, or 1,15- hexadecadiene.
  • 1,3-butadiene 1,1 ,4-pentadiene, 1,5- hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1 ,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-
  • co-dienes may include substituted or branched versions of hydrocarbons with an alkene at each terminus of a carbon chain discussed above. Additionally, a, co-dienes may include carbon chains that include aromatics, heterocycles, and/or other cyclics, such as divinylbenzene (para, meta, ortho, or combination(s) of isomers), 1,2- divinylcyclohexane, 1,3-divinylcyclopentane, or 1 ,4-divinylfuran. Additionally, a, co-dienes may include chains with two or more vinyl terminations including any suitable combination of linear aliphatic, branched aliphatic, aromatics, heterocycles, and/or cyclic aliphatic.
  • the method of making the copolymer can be slurry, solution, gas-phase, high- pressure, or other suitable processes, through the use of catalyst systems appropriate for the polymerization of polyolefins, such as Ziegler-Natta catalysts, metallocene catalysts, other appropriate catalyst systems, or combinations thereof.
  • catalyst systems appropriate for the polymerization of polyolefins such as Ziegler-Natta catalysts, metallocene catalysts, other appropriate catalyst systems, or combinations thereof.
  • the copolymer may be produced using a metallocene catalyst system, such as a mono- or bis-cyclopentadienyl transition metal catalyst in combination with an activator of alumoxane and/or a non-coordinating anion in solution, slurry, high-pressure, or gas-phase.
  • a metallocene catalyst system such as a mono- or bis-cyclopentadienyl transition metal catalyst in combination with an activator of alumoxane and/or a non-coordinating anion in solution, slurry, high-pressure, or gas-phase.
  • the catalyst and activator may be supported or unsupported and the cyclopentadienyl rings may be substituted or unsubstituted.
  • the copolymer can be synthesized by employing solution, slurry, or gas phase polymerization techniques or combination(s) thereof that employ various catalyst systems including Ziegler-Natta systems including vanadium.
  • Exemplary catalysts include single-site catalysts including constrained geometry catalysts involving Group IV- VI metallocenes.
  • the copolymer can be produced via Zeigler-Natta catalyst using a slurry process, especially those including Vanadium compounds, as disclosed in US 5,783,645, as well as metallocene catalysts, which are also disclosed in US 5,756, 416.
  • Other catalysts systems such as the Brookhart catalyst system may also be employed.
  • the copolymer is a copolymer including propylene, a,w- diene, and other comonomer-derived units.
  • the other comonomer may be an a-olefin, such as ethylene, 1 -butene, 1 -hexene, 1-octene, 2-methyl- 1-propene, 3-methyl- 1-pentene, 4-methyl- 1-pentene, 5 -methyl- 1 -hexene, and mixtures thereof.
  • the copolymer is a terpolymer of propylene, ethylene, and a, co-diene.
  • propylene copolymers or terpolymers may be suitable depending on the product properties desired.
  • propylene/butene, hexene, or octene copolymers may be used.
  • the copolymer may include a propylene content from about 30 wt % to about 80 wt%, from about 35 wt% to about 70 wt%, from about 40 wt% to about 65 wt%, or from about 60 wt% to about 80 wt%.
  • the copolymer may have an ethylene content of about 20 wt% or more, about 25 wt% or more, about 30 wt% or more, about 35 wt% or more, about 40 wt% or more, or about 45 wt% or more.
  • the copolymer may have an ethylene content of about 85 wt% or less, about 80 wt% or less, about 75 wt% or less, about 70 wt% or less, about 65 wt% or less, about 60 wt% or less, or about 55 wt% or less.
  • the copolymer can have an a, co-diene content from about 5 wt%, about 8 wt%, about 10 wt%, or about 15 wt% to about 25 wt%, about 30 wt%, about 38 wt%, or about 42 wt%.
  • the copolymer can have an a, co-diene content from about 5 wt% to about 40 wt%, such as from about 6 wt% to about 35 wt%, from about 7 wt% to about 30 wt%, or from about 8 wt% to about 30 wt%.
  • the gas phase composition of the reactor(s) is maintained such that the ratio of the moles of ethylene in the gas phase to the total moles of propylene, ethylene and a, co-diene is held constant.
  • monomer feeds of propylene, ethylene, and a, co-diene may be adjusted.
  • the gas phase composition of the reactor(s) is maintained such that the ratio of the moles of a, co-diene in the gas phase to the total moles of propylene, ethylene and a, co-diene is held constant.
  • monomer feeds of propylene, ethylene and a, co-diene may be adjusted.
  • the catalyst resides, occupies or at least partially resides or occupies within the pores or along the inner walls of the pores that are at least partially formed in or through the polypropylene particles. Accordingly, it is believed that the polymerization of the ethylene and the at least one comonomer, or at least a majority of the polymerization of the ethylene and the at least one comonomer, occurs within the pores of the polypropylene particles as opposed to outside or external the polypropylene particles.
  • the resulting impact copolymer composition can be in the form of polymer particles having a continuous phase composed of the polypropylene particles with a disperse, discontinuous, or occluded phase made up of the copolymer.
  • the copolymer component can at least partially occupy one or more of the pores that were present in the polypolypropylene particles prior to polymerization of the ethylene and comonomer therein.
  • Hydrogen may be optionally added in the gas phase reactor(s) to control the Mw and, therefore, the intrinsic viscosity of the ICP.
  • the composition of the gas phase is maintained such that the ratio of hydrogen to ethylene (mol/mol) referred to as R, is held constant.
  • the copolymer may be a unimodal copolymer rubber, meaning a copolymer rubber of uniform IV and composition in co-monomers, or a bimodal or multi modal rubber copolymer, such as copolymer rubber with components of different IV or composition in co-monomer or type of co-monomer(s) or combinations thereof.
  • the copolymer component of the ICP may have one or more of the following properties:
  • the copolymer may have a density of about 0.915 g/cm 3 or less, such as about 0.910 g/cm 3 or less, or about 0.905 g/cm 3 or less, or about 0.902 g/cm 3 or less; and about 0.85 g/cm 3 or more, about 0.86 g/cm 3 or more, about 0.87 g/cm 3 or more, about 0.88 g/cm 3 or more, or about 0.885 g/cm 3 or more, such as from about 0.85 g/cm 3 to about 0.915 g/cm 3 , from about 0.86 g/cm 3 to about 0.91 g/cm 3 , from about 0.87 g/cm 3 to about 0.91 g/cm 3 , from about 0.88 g/cm 3 to about 0.905 g/cm 3 , from about 0.88 g/cm 3 to about 0.902 g/cm 3 , or from about 0.885 g/
  • the copolymer may have a heat of fusion (Hf) of about 90 J/g or less, such as about 70 J/g or less, about 50 J/g or less, or about 30 J/g or less, such as from about 10 J/g to about 70 J/g, from about 10 J/g to about 50 J/g, or from about 10 J/g to about 30 J/g);
  • Hf heat of fusion
  • the copolymer may have a crystallinity of about 40% or less, such as about 30% or less, or about 20% or less and about 5% or more.
  • the copolymer may have crystallinity from about 5 to about 30%, or from about 5 to about 20%.
  • the copolymer may have a melting point (T m , peak first melt) of about 100 °C or less, such as about 95 °C or less, about 90 °C or less, about 80 °C or less, about 70 °C or less, about 60 °C or less, or about 50 °C or less.
  • T m peak first melt
  • the copolymer may have a glass transition temperature (T g ), as determined by Differential Scanning Calorimetry (DSC) according to ASTM E 1356, that is about - 20 °C or less (such as about -30 °C or less, or about -50 °C or less). In any embodiments, T g is from about -60 °C to about -20 °C.
  • DSC Differential Scanning Calorimetry
  • the copolymer may have an Mw of about 30 to about 2,000 kg/mol, such as about 50 kg/mol to about 1,000 kg/mol, or about 90 to about 500 kg/mol.
  • the copolymer may have a melt index (Mh .i e) at 190 °C of about 0.1 g/lOmin to about 100 g/10 min, such as about 0.3 g/lOmin to about 60 g/10 min, or about 0.5 g/lOmin to about 40 g/10 min, or about 0.7 g/lOmin to about 20 g/10 min).
  • a melt index Mh .i e
  • the copolymer may have a gVi s that is about 0.8 or more, such as about 0.85 or more, about 0.9 or more, about 0.95 or more.
  • the copolymer may have a g’ ViS that is about 0.96, about 0.97, about 0.98, about 0.99, or about 1.
  • the copolymer may have a long-chain branching index at 125 °C, that is about 5 or less, such as about 4 or less, about 3 or less, about 2.5 or less, about 2 or less, about 1.5 or less.
  • a long-chain branching index is defined based on large amplitude oscillatory shear measurements using a strain of 1000 %, and frequency of 0.6 rad/s.
  • the copolymer may have an intrinsic viscosity greater than about 1 dl/g, or greater than about 1.5 dl/g, or greater than about 1.75 dl/g.
  • the copolymer may have an intrinsic viscosity of less than 5 dl/g, or less than 4 dl/g, or less than 3.5 dl/g.
  • the copolymer may have a vinyl content, which is vinyl groups per 1000 Carbon atoms as measured by H'-NMR from about 0.01 to about 5, such as from about 0.01 to about 2.5, from about 0.05 to about 1, or from about 0.1 to about 0.75.
  • additives may be incorporated into the ICP for various purposes.
  • such additives may include, stabilizers, antioxidants, fillers, colorants, nucleating agents, and mold release agents.
  • Primary and secondary antioxidants may include, for example, hindered phenols, hindered amines, and phosphates.
  • Nucleating agents may include, for example, sodium benzoate, and talc.
  • Dispersing agents such as Acrowax C may also be included.
  • Slip agents may include, for example, oleamide, and eruc amide.
  • Catalyst deactivators may also be used, for example, calcium stearate, hydrotalcite, and calcium oxide.
  • additional external donor may be added in the gas phase copolymerization process (second stage) as described in US 2006/0217502.
  • the external donor added in the second stage may be the same or different from the external donor added to the first stage. In any embodiments, external donor is added only on the first stage.
  • a suitable organic compound/agent such as antistatic inhibitor or combination of organic compounds/agents are also added in stage 2, e.g., as described in US 2006/0217502, US 2005/0203259 and US 2008/0161510 A1 and US 5,410,002.
  • antistatic inhibitors or organic compounds include, but are not limited to, chemical derivatives of hydroxylethyl alkylamine available under the trade names AtmerTM 163 and ArmostatTM 410 LM, a major antistatic agent including at least one polyoxyethylalkylamine in combination with one minor antistatic agent including at least one fatty acid sarcosinate or similar compounds or combination(s) thereof.
  • Additives such as antioxidants and stabilizers (including UV stabilizers and other UV absorbers, such as chain-breaking antioxidants), fillers (such as mineral aggregates, fibers, clays, and the like), nucleating agents, slip agents, block, anti-block, pigments, dyes, color masterbatches, waxes, processing aids (including pine or coal tars or resins and asphalts), neutralizers (such as hydro talcite), adjuvants, oils, lubricants, low molecular weight resins, surfactants, acid scavengers, anticorrosion agents, cavitating agents, blowing agents, quenchers, antistatic agents, cure or cross linking agents or systems (such as elemental sulfur, organo-sulfur compounds, and organic peroxides), fire retardants, coupling agents (such as silane), and combinations thereof may also be present in the impact copolymer compositions.
  • additives such as antioxidants and stabilizers (including UV stabilizers and other UV absorbers, such as chain-breaking antioxidants), fill
  • additives used in polypropylene and polypropylene blends are described in POLYPROPYLENE HANDBOOK 2 nd ED., (N. Pasquini, ed., Hanser Publishers, 2005).
  • Additives may be present in amounts from about 0.001 wt% to about 50 wt%, such as from about 0.01 wt% to about 20 wt%, about 0.1 wt% to about 10 wt%, or about 0.1 wt% to about 1 wt%, based upon the weight of the ICP.
  • Pigments, dyes, and other colorants may be present from about 0.01 wt% to about 10 wt%, such as about 0.1 wt% to about 6 wt%.
  • additives includes, for example, stabilizers, surfactants, antioxidants, anti-ozonants (e.g., thioureas), fillers, colorants, nucleating agents, anti-block agents, UV- blockers/absorbers, coagents (cross-linkers and cross-link enhancers), hydrocarbon resins (e.g., OpperaTM resins), and slip additives and combinations thereof.
  • Primary and secondary antioxidants include, for example, hindered phenols, hindered amines, and phosphates.
  • Slip agents include, for example, oleamide and erucamide.
  • fillers include carbon black, clay, talc, calcium carbonate, mica, silica, silicate, and combinations thereof.
  • additives include dispersing agents and catalyst deactivators such as calcium stearate, hydrotalcite, and calcium oxide, and/or other acid neutralizers known in the art.
  • catalyst deactivators such as calcium stearate, hydrotalcite, and calcium oxide, and/or other acid neutralizers known in the art.
  • cross linkers and cross-link enhancers are absent from the propylene impact copolymers.
  • the impact copolymer composition can be blended with one or more additional polymeric additives in amounts of about 25 wt% or less, such as about 20 wt% or less, about 15 wt% or less, about 10 wt% or less, or about 5 wt% or less.
  • the impact copolymer composition can be blended with one or more additional polymeric additives in amounts of about 0.5 wt% to about 25 wt%, such as about 0.75 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1.5 wt% to about 10 wt%, or about 2 wt% to about 5 wt%, based upon the weight of the ICP.
  • Suitable polymers useful as polymeric additives can include, but are not limited to, polyethylenes, including copolymers of ethylene and one or more polar monomers, such as vinyl acetate, methyl acrylate, n-butyl acrylate, acrylic acid, and vinyl alcohol (e.g., EVA, EMA, EnBA, EAA, and EVOH); ethylene homopolymers and copolymers synthesized using a high-pressure free radical process, including LDPE; copolymers of ethylene and C3 to C40 olefins, such as propylene and/or butene, with a density of about 0.91 g/cm 3 to about 0.94 g/cm 3 , including LLDPE; and high density PE, about 0.94 g/cm 3 to about 0.98 g/cm 3 .
  • polyethylenes including copolymers of ethylene and one or more polar monomers, such as vinyl acetate, methyl acrylate, n-butyl acrylate
  • Suitable polymers can also include polybutene-1 and copolymers of polybutene- 1 with ethylene and/or propylene. Suitable polymers can also include non-EP Rubber Elastomers.
  • Non-EP Rubber Elastomers can include Polyisobutylene, butyl rubber, halobutyl rubber, copolymers of isobutylene and para-alkylstyrene, halogenated copolymers of isobutylene and para-alkylstyrene, natural rubber, polyisoprene, copolymers of butadiene with acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber, acrylonitrile chlorinated isoprene rubber, and polybutadiene rubber (both cis and trans).
  • suitable polymers can include low-crystallinity propylene/olefin copolymers, such as random copolymers.
  • the low-crystallinity or random copolymer can have about 70 wt% or more propylene and about 5 wt% to about 30 wt% comonomer, such as about 5 wt% to about 20 wt% of comonomer selected from ethylene and C4 to C12 olefins.
  • the polymers can be made via a metallocene-type catalyst; and may have one or more of the following properties: a) a Mw of about 20 kg/mol to about 5,000 kg/mol, such as about 30 kg/mol to about 2,000 kg/mol, about 40 kg/mol to about 1,000 kg/mol, about 50 kg/mol to about 500 kg/mol, or about 60 kg/mol to about 400 kg/mol; b) a polydispersity index (Mw/Mn) of about 1.5 to about 10, such as about 1.7 to about 5, or about 1.8 to about 3; c) a branching index (g') of about 0.9 or greater, such as about 0.95 or greater, or about 0.99 or greater; d) a density of about 0.85 g/cm 3 to about 0.90 g/cm 3 , such as about 0.855 g/cm 3 to about 0.89 g/cm 3 , or about 0.86 g/cm 3 to about 0.88 g/cm 3 ; e) a melt
  • Useful low-crystallinity propylene/olefin copolymers that may be used as additives are available from ExxonMobil Chemical; suitable examples include VistamaxxTM 6100, VistamaxxTM 6200 and VistamaxxTM 3000. Other useful low-crystallinity propylene/olefin copolymers are described in WO 03/040095, WO 03/040201, WO 03/040233, and WO 03/040442, which disclose propylene-ethylene copolymers made with non-metallocene catalyst compounds. Still other useful low-crystallinity propylene/olefin copolymers are described in US 5 ,504, 172. Low-crystallinity propylene/olefin copolymers are described in US
  • suitable polymers can include propylene oligomers suitable for adhesive applications, such as those described in WO 2004/046214, including those described in pages 8 to 23. Still other suitable polymers can include Olefin block copolymers, including those described in WO 2005/090425, WO 2005/090426, and WO 2005/090427. Other suitable polymers can include polyolefins that have been post-reactor functionalized with maleic anhydride (so-called maleated polyolefins), including maleated ethylene polymers, maleated EP Rubbers, and maleated polypropylenes.
  • maleated polyolefins polyolefins that have been post-reactor functionalized with maleic anhydride
  • the amount of free acid groups present in the maleated polyolefin is less than about 1,000 ppm, such as less than about 500 ppm, or less than about 100 ppm, and the amount of phosphite present in the maleated polyolefin is less than 100 ppm.
  • SBCs Styrenic Block Copolymers
  • polystyrene resins such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET/PEI copolymer, polyacrylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxalkylene diimide diacid/polybutyrate
  • polyamide resins such as nylon 6 (N6), nylon 66 (N66), nylon 46 (N46), nylon 11 (Nil), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), nylon 6/66 copolymer (N6/66), nylon 6/66/610 (N6/66/610), nylon MXD6 (MXD6), nylon 6T (N6T), nylon 6/6T copolymer, nylon 66/PP copolymer, and nylon 66/PPS copolymer; polyester resins, such as polybutylene terephthalate (PBT), polyethylene terephthalate (
  • an impact copolymer composition can include no added polymeric additives, or if present the polymeric additives can be present at about 0.5 wt % or less.
  • the impact copolymer composition can include less than 10 wt % LLDPE having a density of 0.912 g/cm 3 to 0.935 g/cm 3 , such as about 5 wt% or less, about 1 wt% or less, or about 0.1 wt% or less, based upon the total weight of the ICP and PE.
  • the ICP can be formed by any suitable means into articles of manufacture such as automotive components, pallets, crates, cartons, appliance components, sports equipment and other articles that would benefit from high impact resistance.
  • the impact copolymers can include from about 200 ppm to about 1,500 ppm of a nucleating agent.
  • the presence of nucleating agents can benefit the impact copolymers by reducing the crystallization rate and hence improve the cycle time (injection, packing, cooling and part ejection) in the injection molding process.
  • the propylene impact copolymers include a nucleating agent and have a crystallization half-time at 135 °C of about 15 minutes or less, such as about 12 minutes or less, about 10 minutes or less, about 5 minutes or less, about 2 minutes or less, about 60 seconds or less, or about 40 seconds or less.
  • compositions also referred to as “blends” of the present disclosure may be produced by mixing the polypropylene polymer, the copolymer polymer, and optional additives together, by one or more of connecting reactors together in series to make reactor blends or by using more than one catalyst, for example, a dual metallocene catalyst, in the same reactor to produce multiple species of polymer. Additionally or alternatively, the polymers can be mixed together prior to being put into an extruder or may be mixed in an extruder.
  • compositions may be formed by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the polymers together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder.
  • a mixer such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder.
  • the polymers and components of the present disclosure can be blended by any suitable means, and are typically blended to yield an intimately mixed composition which may be a homogeneous, single phase mixture.
  • they may be blended in a static mixer, batch mixer, extruder, or a combination thereof, that is sufficient to achieve an adequate dispersion of the components of the composition.
  • Mixing may involve first dry blending using, for example, a tumble blender, where the polymers (and optional additive) are brought into contact first, without intimate mixing, which may then be followed by melt blending in an extruder.
  • Another method of blending the components is to melt blend the first polymer as a pellet and the second polymer as a pellet directly in an extruder or batch mixer. It can also involve a “master batch” approach, where the final modifier concentration is achieved by combining a neat polymer with an appropriate amount of modified polymer that had been previously prepared at a higher additive concentration.
  • the mixing may take place as part of a processing method used to fabricate articles, such as in the extruder on an injection molding machine or blown-film line or fiber line.
  • polypropylene polypropylene
  • copolymer copolymer
  • optional additional polymers may be “melt blended” in an apparatus such as an extruder (single or twin screw) or batch mixer or may be “dry blended” with one another using a tumbler, double-cone blender, ribbon blender, or other suitable blender.
  • the polymers and the optional additional additive(s) are blended by a combination of approaches, for example a tumbler followed by an extruder.
  • a suitable method of blending is to include the final stage of blending as part of an article fabrication step, such as in the extruder used to melt and convey the composition for a molding step like injection molding or blow molding.
  • This can include direct injection of one or more polymer and/or elastomer into the extruder, either before or after a different one or more polymer and/or elastomer is fully melted.
  • Extrusion technology for polymers is described in more detail in, for example, PLASTIC EXTRUSION TECHNOLOGY 26-37 (Friedhelm Hensen, ed. Hanser Publishers 1988).
  • the polymers and the optional additional additive(s) may be blended in solution by any suitable means by using a solvent that dissolves the components of the composition to a suitable extent.
  • the blending may occur at any temperature or pressure where the components remain in solution. Suitable conditions include blending at high temperatures, such as 10 °C or more, such as 20 °C or more over the melting point of one or more polymer and/or elastomer.
  • Such solution blending would be particularly useful in processes where one or more polymer and/or elastomer is made by solution process and a modifier is added directly to the finishing train, rather than added to the dry polymer, polymer and/or elastomer in another blending step altogether.
  • Such solution blending would also be particularly useful in processes where one or more polymer and/or elastomer is made in a bulk or high pressure process where one or more polymer and/or elastomer and the modifier are in soluble in the monomer (as solvent).
  • one or more polymer and/or elastomer can be added directly to the finishing train rather than added to the dry one or more polymer and/or elastomer in another blending step altogether.
  • any suitable means of combining the one or more components of the composition to achieve the desired composition serve equally well as fully formulated pre blended pellets, since the forming process can include a re-melting and mixing of the raw material; example combinations include simple blends of neat polymer and/or elastomer pellets (and optional additive(s)), neat polymer and/or elastomer granules, and neat polymer and/or elastomer pellets and pre-blended pellets.
  • little mixing of the melt components occurs in the process of compression molding, and pre-blended pellets would be preferred over simple blends of the constituent pellets.
  • a composition of the present disclosure is combined with one or more additional polymers prior to being formed into a film, molded part or other article.
  • Other useful polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and/or butene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene- 1 , isotactic polybutene, ABS resins, ethylene- propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polyethylene-propylene
  • the blends may be produced by mixing the polymers and/or elastomers of the present disclosure with one or more polymers (e.g., as described above), by connecting reactors together in series to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer.
  • the polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.
  • the heterogeneous polymer/elastomer blends described herein may be formed into desirable end use products by any suitable means. They are particularly useful for making articles by blow molding, extrusion, injection molding, thermoforming, gas foaming, elasto- welding and compression molding techniques.
  • Blow molding forming includes injection blow molding, multi-layer blow molding, extrusion blow molding, and stretch blow molding, and is especially suitable for substantially closed or hollow objects, such as, for example, gas tanks and other fluid containers.
  • Blow molding is described in more detail in, for example, CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 90-92 (Jacqueline I. Kroschwitz, ed., John Wiley & Sons 1990).
  • profile co extrusion can be used.
  • the profile co-extrusion process parameters are as above for the blow molding process, except the die temperatures (dual zone top and bottom) can be from 150 °C to 235 °C, the feed blocks are from 90 °C to 250 °C, and the water cooling tank temperatures are from 10 °C to 40 °C.
  • One embodiment of an injection molding process is described as follows. The shaped laminate is placed into the injection molding tool. The mold is closed and the substrate material is injected into the mold. The substrate material has a melt temperature between 200 °C and 300 °C, such as between 215 °C and 250 °C and is injected into the mold at an injection speed of between 2 and 10 seconds.
  • molded articles may be fabricated by injecting molten polymer into a mold that shapes and solidifies the molten polymer into a desirable geometry and thickness of molded articles.
  • Sheet may be made either by extruding a substantially flat profile from a die, onto a chill roll, or alternatively by calendaring. Sheet will generally be considered to have a thickness of from 10 mils to 100 mils (254 mhi to 2540 mpi), although sheet may be substantially thicker.
  • Tubing or pipe may be obtained by profile extrusion for uses in medical, potable water, land drainage applications or the like. The profile extrusion process involves the extrusion of molten polymer through a die. The extruded tubing or pipe is then solidified by chill water or cooling air into a continuous extruded article.
  • Sheet made from a composition of the present disclosure may be used to form a container. Such containers may be formed by thermoforming, solid phase pressure forming, stamping and other shaping techniques. Sheets may also be formed to cover floors or walls or other surfaces.
  • the oven temperature is between 160 °C and 195 °C, the time in the oven between 10 and 20 seconds, and the die temperature, typically a male die, between 10 °C and 71 °C.
  • the melt temperature of the substrate material is between 225 °C and 255 °C in one embodiment, and between 230 °C and 250 °C in another embodiment
  • the fill time is from 2 to 10 seconds in one embodiment, from 2 to 8 seconds in another embodiment
  • a tool temperature of from 25 °C to 65 °C in one embodiment, and from 27 °C and 60 °C in another embodiment.
  • the substrate material is at a temperature that is hot enough to melt any tie-layer material or backing layer to achieve adhesion between the layers.
  • the compositions are secured to a substrate material using a blow molding operation.
  • Blow molding is particularly useful in such applications as for making closed articles such as fuel tanks and other fluid containers, playground equipment, outdoor furniture and small enclosed structures.
  • a composition of the present disclosure is extruded through a multi-layer head, followed by placement of the uncooled laminate into a parison in the mold. The mold, with either male or female patterns inside, is then closed and air is blown into the mold to form the part.
  • the steps outlined above may be varied, depending upon the desired result.
  • an extruded sheet formed from a composition of the present disclosure may be directly thermoformed or blow molded without cooling, thus skipping a cooling step.
  • Other parameters may be varied as well in order to achieve a finished composite article having desirable features.
  • a composition of the present disclosure is formed into an article such as a weather seal, a hose, a belt, a gasket, a molding, boots, an elastic fiber and like articles. Foamed end-use articles are also envisioned.
  • the blends of the present disclosure can be formed as part of a vehicle part, such as a weather seal, a brake part including, but not limited to cups, coupling disks, diaphragm cups, boots such as constant velocity joints and rack and pinion joints, tubing, sealing gaskets, parts of hydraulically or pneumatically operated apparatus, o-rings, pistons, valves, valve seats, valve guides, and other elastomeric polymer based parts or elastomeric polymers combined with other materials such as metal, plastic combination materials which will be known to those of ordinary skill in the art.
  • a vehicle part such as a weather seal
  • a brake part including, but not limited to cups, coupling disks, diaphragm cups, boots such as constant velocity joints and rack and pinion joints, tubing, sealing gaskets, parts of hydraulically or pneumatically operated apparatus, o-rings, pistons, valves, valve seats, valve guides, and other elastomeric polymer based parts or elastomeric polymers combined with other
  • transmission belts including V-belts, toothed belts with truncated ribs containing fabric faced V's, ground short fiber reinforced Vs or molded gum with short fiber flocked V's.
  • the cross section of such belts and their number of ribs may vary with the final use of the belt, the type of market and the power to transmit. They also can be flat made of textile fabric reinforcement with frictioned outside faces. Vehicles contemplated where these parts will find application include, but are not limited to passenger autos, motorcycles, trucks, boats and other vehicular conveyances.
  • Stretch films can be used in a variety of bundling and packaging applications.
  • the term “stretch film” indicates films capable of stretching and applying a bundling force, and includes films stretched at the time of application as well as "pre-stretched” films, i.e., films which are provided in a pre-stretched form for use without additional stretching.
  • Stretch films can be monolayer films or multilayer films, and can include conventional additives, such as cling- enhancing additives such as tackifiers, and non-cling or slip additives, to tailor the slip/cling properties of the film.
  • compositions of the present disclosure may be utilized to prepare shrink films.
  • Shrink films also referred to as heat-shrinkable films, are widely used in both industrial and retail bundling and packaging applications. Such films are capable of shrinking upon application of heat to release stress imparted to the film during or subsequent to extrusion. The shrinkage can occur in one direction or in both longitudinal and transverse directions. Conventional shrink films are described, for example, in WO 2004/022646.
  • Industrial shrink films can be used for bundling articles on pallets. Typical industrial shrink films are formed in a single bubble blown extrusion process to a thickness of about 80 to 200 pm, and provide shrinkage in two directions, typically at a machine direction (MD) to transverse direction (TD) ratio of about 60:40.
  • MD machine direction
  • TD transverse direction
  • Retail films can be used for packaging and/or bundling articles for consumer use, such as, for example, in supermarket goods. Such films are typically formed in a single bubble blown extrusion process to a thickness of about 35 pm to 80 pm, with a typical MD:TD shrink ratio of about 80:20.
  • Films may be used in “shrink-on-shrink” applications.
  • “Shrink-on-shrink,” as used herein, refers to the process of applying an outer shrink wrap layer around one or more items that have already been individually shrink wrapped (herein, the “inner layer” of wrapping). In these processes, it is desired that the films used for wrapping the individual items have a higher melting (or shrinking) point than the film used for the outside layer. When such a configuration is used, it is possible to achieve the desired level of shrinking in the outer layer, while preventing the inner layer from melting, further shrinking, or otherwise distorting during shrinking of the outer layer.
  • Some films described herein have been observed to have a sharp shrinking point when subjected to heat from a heat gun at a high heat setting, which indicates that they may be especially suited for use as the inner layer in a variety of shrink-on-shrink applications.
  • Greenhouse Films Compositions of the present disclosure may be utilized to prepare stretch to prepare greenhouse films.
  • Greenhouse films are generally heat retention films that, depending on climate requirements, retain different amounts of heat. Less demanding heat retention films are used in warmer regions or for spring time applications. More demanding heat retention films are used in the winter months and in colder regions. Bags
  • compositions of the present disclosure may be utilized to prepare bags.
  • Bags include those bag structures and bag applications known to those skilled in the art.
  • Exemplary bags include shipping sacks, trash bags and liners, industrial liners, produce bags, and heavy duty bags.
  • compositions of the present disclosure may be utilized to prepare packaging.
  • Packaging includes those packaging structures and packaging applications known to those skilled in the art.
  • Exemplary packaging includes flexible packaging, food packaging, e.g., fresh cut produce packaging, frozen food packaging, bundling, packaging and unitizing a variety of products.
  • Applications for such packaging include various foodstuffs, rolls of carpet, liquid containers, and various like goods normally containerized and/or palletized for shipping, storage, and/or display.
  • compositions of the present disclosure may be used in suitable blow molding processes and applications. Such processes involve a process of inflating a hot, hollow thermoplastic preform (or parison) inside a closed mold. In this manner, the shape of the parison conforms to that of the mold cavity, enabling the production of a wide variety of hollow parts and containers.
  • Blow molding processes may include extrusion and/or injection blow molding, as described above.
  • Extrusion blow molding is typically suited for the formation of items having a comparatively heavy weight, such as greater than about 12 ounces, including but not limited to food, laundry, or waste containers.
  • Injection blow molding is typically used to achieve accurate and uniform wall thickness, high quality neck finish, and to process polymers that cannot be extruded.
  • Typical injection blow molding applications include, but are not limited to, pharmaceutical, cosmetic, and single serving containers, typically weighing less than 12 ounces.
  • compositions of the present disclosure may also be used in injection molded applications.
  • Injection molding is a process commonly known in the art, and is a process that usually occurs in a cyclical fashion. Cycle times generally range from 10 to 100 seconds and are controlled by the cooling time of the polymer or polymer blend used.
  • Polymer pellets or powder are fed from a hopper and melted in a reciprocating screw type injection molding machine. The screw in the machine rotates forward, filling a mold with melt and holding the melt under high pressure. As the melt cools in the mold and contracts, the machine adds more melt to the mold to compensate. Once the mold is filled, it is isolated from the injection unit and the melt cools and solidifies. The solidified part is ejected from the mold and the mold is then closed to prepare for the next injection of melt from the injection unit.
  • Injection molding processes offer high production rates, good repeatability, minimum scrap losses, and little to no need for finishing of parts. Injection molding is suitable for a wide variety of applications, including containers, household goods, automobile components, electronic parts, and many other solid articles.
  • compositions of the present disclosure may be used in extrusion coating processes and applications.
  • Extrusion coating is a plastic fabrication process in which molten polymer is extruded and applied onto a non-plastic support or substrate, such as paper or aluminum in order to obtain a multi-material complex structure.
  • This complex structure typically combines toughness, sealing and resistance properties of the polymer formulation with barrier, stiffness or aesthetic attributes of the non-polymer substrate.
  • the substrate is typically fed from a roll into a molten polymer as the polymer is extruded from a slot die, which is similar to a cast film process.
  • the resultant structure is cooled, typically with a chill roll or rolls, and formed into finished rolls.
  • Extrusion coating materials can be used in, for example, food and non-food packaging, pharmaceutical packaging, and manufacturing of goods for the construction (insulation elements) and photographic industries (paper). Foamed Articles
  • compositions of the present disclosure may be used in foamed applications.
  • a blowing agent such as, for example, carbon dioxide, nitrogen, or a compound that decomposes to form carbon dioxide or nitrogen
  • a blowing agent is injected into a polymer melt by means of a metering unit.
  • the blowing agent is then dissolved in the polymer in an extruder, and pressure is maintained throughout the extruder.
  • a rapid pressure drop rate upon exiting the extruder creates a foamed polymer having a homogenous cell structure.
  • the resulting foamed product is typically light, strong, and suitable for use in a wide range of applications in industries such as packaging, automotive, aerospace, transportation, electric and electronics, and manufacturing. Wire and Cable Applications
  • Such devices include, for example, electronic cables, computer and computer-related equipment, marine cables, power cables, telecommunications cables or data transmission cables, and combined power/telecommunications cables.
  • Rotomolded products including one or more layers formed of or comprising composition(s) of the present disclosure.
  • Rotomolding or rotational molding involves adding an amount of material to a mold, heating and slowly rotating the mold so that the softened material coats the walls of the mold. The mold continues to rotate at all times during the heating phase, thus maintaining even thickness throughout the part and preventing any deformation during the cooling phase.
  • Examples of rotomolded products include but are not limited to furniture, toys, tanks, road signs tornado shelters, containers including United Nations-approved containers for the transportation of nuclear fissile materials.
  • Clause 8 The impact copolymer composition of clause 7, where the impact copolymer composition has an Mw of from about 250 kg/mol to about 900 kg/mol.
  • Clause 16 The impact copolymer composition of clause 14, where the impact copolymer composition has an intrinsic viscosity ratio of from about 2 to about 10.
  • Clause 18 The impact copolymer composition of clause 14, where the impact copolymer composition has a tan d at 0.1 rad/sec angular frequency of about 5 or less.
  • Clause 27 The impact copolymer composition of clause 1, where the a, co-diene is selected from the group consisting of 1,5-hexadiene, 1 ,6-heptadiene, 1,7-octadiene, 1,8- nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13- tetradecadiene, 1,14-pentadecadiene, 1,15-hexadecadiene, and a combination thereof.
  • the a, co-diene is selected from the group consisting of 1,5-hexadiene, 1 ,6-heptadiene, 1,7-octadiene, 1,8- nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13- tetradecadiene, 1,14-pentadecadiene
  • Clause 28 A process for producing an impact copolymer composition, the process including: introducing a catalyst and propylene to a first reactor forming a first polymer; and introducing the first polymer, ethylene, at least one a, co-diene, and optionally additional propylene to a second reactor.
  • Clause 29 The process of clause 28, where the a, co-diene is selected from the group consisting of 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, 1,14- pentadecadiene, 1,15-hexadecadiene, and a combination thereof.
  • Clause 31 The process of clause 30, where the first polymer has an MFR of about 800 glOmin or less.
  • Clause 32 The process of clause 28, further including introducing hydrogen to the first reactor.
  • Clause 33 The process of clause 32, further including removing hydrogen before introducing the first polymer to the second reactor. Examples
  • the glass transition temperature (Tg) was measured using dynamic mechanical analysis.
  • a dynamic mechanical analysis test provides information about the small-strain mechanical response of a sample as a function of temperature over a temperature range that includes the glass transition region and the visco-elastic region prior to melting.
  • Specimens are tested using a commercially available DMA instrument (e.g., TA Instruments DMA 2980 or Rheometrics RSA) equipped with a dual cantilever test fixture.
  • the specimen is cooled to -130 °C then heated to 60 °C at a heating rate of 2 °C/min while subjecting to an oscillatory deformation at 0.1% strain and a frequency of 1 rad/sec.
  • the output of these DMA experiments is the storage modulus (E') and loss modulus (E").
  • the storage modulus measures the elastic response or the ability of the material to store energy
  • the loss modulus measures the viscous response or the ability of the material to dissipate energy.
  • the ratio of E7E', called Tan-delta gives a measure of the damping ability of the material; peaks in Tan-delta are associated with relaxation modes for the material.
  • Tg is defined to be the peak temperature associated with the b-relaxation mode, which typically occurs from about -80 °C to about 20 °C for polyolefins.
  • a hetero-phase blend separate b-relaxation modes for each blend component can cause more than one Tg to be detected for the blend; assignment of the Tg for each component may be based on the Tg observed when the individual components are similarly analyzed by DMA (although slight temperature shifts are possible).
  • DSC Differential Scanning Calorimetry
  • Crystallization temperature (Tc) and melting temperature (or melting point, Tm) are measured using Differential Scanning Calorimetry (DSC) on a commercially available instrument (e.g., TA Instruments 2920 DSC).
  • DSC Differential Scanning Calorimetry
  • 6 to 10 mg of molded polymer or plasticized polymer are sealed in an aluminum pan and loaded into the instrument at room temperature.
  • Melting data (first heat) is acquired by heating the sample to at least 30 °C above its melting temperature, typically 220 °C for polypropylene, at a heating rate of 10 °C/min. The sample is held for at least 5 minutes at this temperature to destroy its thermal history.
  • Crystallization data are acquired by cooling the sample from the melt to at least 50 °C below the crystallization temperature, typically -50 °C for polypropylene, at a cooling rate of 20 °C/min. The sample is held at this temperature for at least 5 minutes, and finally heated at 10 °C/min to acquire additional melting data (second heat).
  • the endothermic melting transition (first and second heat) and exothermic crystallization transition are analyzed according to standard procedures. The melting temperatures reported are the peak melting temperatures from the second heat unless otherwise specified.
  • the melting temperature is defined to be the peak melting temperature from the melting trace associated with the largest endothermic calorimetric response (as opposed to the peak occurring at the highest temperature).
  • the crystallization temperature is defined to be the peak crystallization temperature from the crystallization trace associated with the largest exothermic calorimetric response (as opposed to the peak occurring at the highest temperature).
  • H° H°
  • a value of 290 J/g is used for H° (polyethylene)
  • a value of 140 J/g is used for H° (polybutene)
  • a value of 207 J/g is used for H° (polypropylene).
  • Molecular weight (weight-average molecular weight, Mw, number-average molecular weight, Mn, and molecular weight distribution, Mw/Mn) are determined using a commercial High Temperature Size Exclusion Chromatograph (e.g., from Waters Corporation or Polymer Laboratories) equipped with three in-line detectors: a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer.
  • DRI differential refractive index detector
  • LS light scattering
  • the various transfer lines, columns, DRI detector and viscometer are contained in an oven maintained at 135 °C.
  • the TCB solvent is filtered through a 0.7 pm glass pre-filter and subsequently through a 0.1 pm Teflon filter, then degassed with an online degasser before entering the SEC.
  • Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160 °C with continuous agitation for about 2 hours. All quantities are measured gravimetrically.
  • the TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/mL at room temperature and 1.324 g/mL at 135 °C.
  • Injection concentrations may include about 1 mg/mL to about 2 mg/mL, with lower concentrations being used for higher molecular weight samples.
  • the DRI detector and injector Prior to running a set of samples, the DRI detector and injector are purged, the flow rate increased to 0.5 mL/min, and the DRI allowed to stabilize for 8-9 hours; the LS laser is turned on 1 hr before running samples.
  • the concentration, c, at each point in the chromatogram is calculated from the baseline- subtracted DRI signal, IDRI, using the following equation:
  • KDRI is a constant determined by calibrating the DRI
  • (dn/dc) is the same as described below for the light scattering (LS) analysis.
  • Lor purposes of this disclosure (dn/dc) 0.104 for polypropylenes and ethylene polymers, and 0.1 otherwise.
  • the LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII.
  • the LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering ( Light Scattering from Polymer Solutions, Huglin, M. B., Ed.; Academic Press, 1972.):
  • AR(0) is the measured excess Rayleigh scattering intensity at scattering angle Q
  • c is the polymer concentration determined from the IR5 analysis
  • A2 is the second virial coefficient
  • R(q) is the form factor for a monodisperse random coil
  • K 0 is the optical constant for the system: where NA is Avogadro’s number, and (dn/dc) is the refractive index increment for the system.
  • a high temperature Agilent (or Viscotek Corporation) viscometer which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity.
  • One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure.
  • the specific viscosity, h 8 for the solution flowing through the viscometer is calculated from their outputs.
  • the intrinsic viscosity, [h] q s /c, where c is concentration and is determined from the IR5 broadband channel output.
  • the viscosity MW at each point is calculated as M - K ps M a s+1 /[h] , where cc ps is 0.67 and K ps is 0.000175.
  • the branching index (g'vis) is calculated using the output of the GPC-IR5-LS-VIS method as follows.
  • V g, of the sample is calculated by: where the summations are over the chromatographic slices, i, between the integration limits.
  • Ethylene content in copolymers is determined by ASTM D 5017-96, except that the minimum signal-to-noise should be 10,000:1.
  • Propylene content in propylene copolymers is determined by following the approach of Method 1 in Di Martino and Kelchermans, 56 J. APPL. POLYM. SCI. 1781 (1995), and using peak assignments from Zhang, 45 POLYMER 2651 (2004) for higher olefin comonomers.
  • MFR Melt Flow Rate
  • MI Melt Index
  • Density was measured by density-gradient column, such as described in ASTM D1505, on a compression- molded specimen that has been slowly cooled to room temperature.
  • Test specimens for mechanical property testing were injection-molded, unless otherwise specified.
  • the testing temperature was standard laboratory temperature (23 ⁇ 2 °C) as specified in ASTM D618, unless otherwise specified.
  • Instron load frames were used for tensile and flexure testing.
  • Tensile properties were determined according to ASTM D638, including Young's modulus (also called modulus of elasticity), yield stress (also called tensile strength at yield), yield strain (also called elongation at yield), break stress (also called tensile strength at break), and break strain (also called elongation at break).
  • the energy to yield is defined as the area under the stress-strain curve from zero strain to the yield strain.
  • the energy to break is defined as the area under the stress-strain from zero strain to the break strain.
  • Injection-molded tensile bars were of either ASTM D638 Type I or Type IV geometry, tested at a speed of 2 inch/min.
  • Compression- molded tensile bars were of ASTM D412 Type C geometry, tested at a speed of 20 inch/min.
  • the yield stress and yield strain were determined as the 10% offset values as defined in ASTM D638. Break properties were reported only if a majority of test specimens broke before a strain of about 2000%, which is the maximum strain possible on the load frame used for testing.
  • Flexure properties were determined according to ASTM D790A, including the 1% secant modulus and 2% secant modulus. Test specimen geometry was as specified under “Molding Materials (Thermoplastics and Thermosets)”, and the support span was 2 inches. [0190] Heat deflection temperature was determined according to ASTM D648, at 66 psi, on injection-molded specimens.
  • Gardner impact strength was determined according to ASTM D5420, on 0.125 inch thick injection-molded disks, at the specified temperature.
  • Notched Izod impact resistance was determined according to ASTM D256, at the specified temperature. A TMI Izod Impact Tester was used. Specimens were either cut individually from the center portion of injection-molded ASTM D638 Type I tensile bars, or pairs of specimens were made by cutting injection-molded ASTM D790 “Molding Materials (Thermoplastics and Thermosets)” bars in half. The notch was oriented such that the impact occurred on the notched side of the specimen (following Procedure A of ASTM D256) in most cases; where specified, the notch orientation was reversed (following Procedure E of ASTM D256). All specimens were assigned a thickness of 0.122 inch for calculation of the impact resistance. All breaks were complete, unless specified otherwise. Fabric and Film Properties
  • Flexure and tensile properties are determined by ASTM D 882.
  • Elmendorf tear is determined by ASTM D 1922. Puncture and puncture energy are determined by ASTM D 3420. Total energy dart impact is determined by ASTM D 4272 Fluid Properties
  • the number-average molecular weight (Mn) can be determined by Gel Permeation Chromatography (GPC), as described in “Modem Size Exclusion Liquid Chromatographs”, W. W. Yan, J. J. Kirkland, and D. D. Bly, J. Wiley & Sons (1979); or estimated by ASTM D 2502; or estimated by freezing point depression, as described in “Lange's Handbook of Chemistry”, 15th Edition, McGrawHill.
  • Impact copolymers without hydrogen in the second stage were synthesized as follows. During first stage polymerization, to a 2 L ZipperClave reactor was introduced 0.8 mmol TEAL, 0.08 mmol donor and 250 mmol hydrogen. 0.08 mmol TEAL, 0.08 mmol donor and 6 mg commercial Toho THC- 133 Ziegler-Natta catalyst precontacted in a charge tube were flushed into the reactor with 1250 mL propylene.
  • the “A-donor” is a mixture of 5 mol% dicyclopentyldimethoxysilane and 95 mol% n-propyltriethoxysilane, and the B-donor is diethylaminotriethoxysilane.
  • the agitation was started.
  • the reaction mixture was heated up from room temperature to 70 °C and the polymerization reaction was carried out for 1 hr.
  • volatiles were vented off.
  • 40/60 molar ethylene and propylene gases were added to reach 180 psig total pressure and the reaction mixture was allowed to agitate for 0.5 hr at 70°C.
  • the homopolymer polypropylene matrix had a MFR of 138 g/10 min (230 °C, 2.16 kg, ASTM ASTM-1238).
  • the homopolymer PP matrix MFR was about 171 g/10 min (230 °C, 2.16 kg, ASTM ASTM-1238).
  • the homopolymer PP matrix MFR was about 257 g/10 min (230 °C, 2.16 kg, ASTM ASTM-1238).
  • ICPs synthesized according to the above method are included in Tables 1, 2, and
  • ICPs with higher MW of the rubber-like component and advantageous rheological properties including a higher IV ratio, lower melt flow rate, a broader molecular weight distributions. Additionally, the inclusion of a, co-dienes increases the vinyl content of the ICPs providing increased functionality and opportunities for post-production modifications [0198]
  • Impact copolymers with hydrogen in the second stage were synthesized as follows. During first stage polymerization, to a 2 L ZipperClave reactor was introduced 0.8 mmol TEAL, 0.08 mmol donor and 250 mmol hydrogen.
  • Line 101 depicts the measurements of tan d at various angular frequencies for Example 1 , which is a comparative example with high MFR, a low IV ratio, and a tan d greater than 2.5.
  • Line 103 depicts measurements of tan d at various angular frequencies for Example 2.
  • Example 2 has a relatively low MFR, a higher IV ratio, and a tan d near 1.
  • Line 105 depicts measurements of tan d at various angular frequencies for Example 5.
  • Example 5 has a relatively low MFR, an even higher IV ratio, and a tan d less than 2.
  • Line 107 depicts measurements of tan d at various angular frequencies for Example 15, which is a comparative example of an ICP sold by ExxonMobil Chemical as PP7143KNE1.
  • Example 5 has a relatively low MFR, and a tan d greater than 5.
  • the comparative examples have a much higher tan d from 0.01 rad/sec to 1 rad/sec.
  • An ICP with a low tan d (less than 2.5) from 0.01 rad/sec to 1 rad/sec may have superior tiger-striping performance over ICPs with a greater tan d at those angular frequencies.
  • examples according to embodiments of the present disclosure may have a lower MFR, a higher IV ratio, and/or a lower tan d (from about 0.01 rad/sec to about 1 rad/sec) than comparative examples.
  • ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne des compositions de copolymère choc comprenant un polypropylène et un copolymère comportant de l'éthylène, du propylène et un α, ω-diène. Ces compositions de copolymère choc possèdent un indice de fluidité d'environ 5 g/10 min à environ 200 g/10 min et un tan(δ) à une fréquence angulaire de 0,1 rad/sec d'environ 5 ou moins. La présente invention concerne également des procédés de production de compositions de copolymère choc comprenant les étapes consistant à : introduire un catalyseur et du propylène dans un premier réacteur pour former un premier polymère, et introduire ce premier polymère, de l'éthylène, au moins un α, ω-diène, et éventuellement un propylène supplémentaire, dans un second réacteur.
PCT/US2020/055204 2019-10-22 2020-10-12 Compositions de copolymère choc WO2021080803A1 (fr)

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