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WO2018034760A1 - Copolymères de propylène-alpha-oléfine et leurs procédés de fabrication - Google Patents

Copolymères de propylène-alpha-oléfine et leurs procédés de fabrication Download PDF

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WO2018034760A1
WO2018034760A1 PCT/US2017/042366 US2017042366W WO2018034760A1 WO 2018034760 A1 WO2018034760 A1 WO 2018034760A1 US 2017042366 W US2017042366 W US 2017042366W WO 2018034760 A1 WO2018034760 A1 WO 2018034760A1
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reactor
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composition
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PCT/US2017/042366
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Andy H. Tsou
Alexander I. NORMAN
John R. Hagadorn
Gabor Kiss
Peijun Jiang
Sarah J. MATTLER
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Exxonmobil Chemical Patents Inc.
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Priority to ES17743455T priority Critical patent/ES2876423T3/es
Priority to CN201780044093.XA priority patent/CN109548404B/zh
Priority to EP17743455.2A priority patent/EP3497139B1/fr
Publication of WO2018034760A1 publication Critical patent/WO2018034760A1/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
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Definitions

  • This invention is related to a process to make a propylene- alpha olefin copolymers having a blend of a co-continuous low reactivity ratio product/alternating sequenced propylene-alpha olefin component and a high reactivity ratio product/blocky sequenced propylene-alpha olefin component to produce a copolymer useful for soft, elastic applications.
  • Polyolefin polymers and polymer blends are known for their utility in a wide variety of applications.
  • many polyolefin polymers including copolymers of propylene with other alpha-olefins such as ethylene, are well suited for use in applications requiring good stretchability, elasticity, and strength.
  • Such polymers often comprise a blend of two or more propylene copolymers, and may be manufactured by physically blending two or more copolymers, or by reactor blending of the copolymers, or by reactor synthesizing two or more copolymers with a single catalyst having multiple reactive sits or with multiple catalysts.
  • the inventors have discovered that incorporating a low reactivity ratio product/alternating sequenced pyridyl diamido-based catalyzed copolymer with high reactivity ratio product/blocky sequenced metallocene catalyzed copolymer can produce a balance of a pellet stable bimodal propylene- alpha olefin copolymer having suitable elastic recovery properties.
  • the olefin copolymers of the invention have a broad split in molecular weight of each component but a narrow split in alpha-olefin content of each component.
  • composition comprising from about 60 wt% to about 95 wt% of a first propylene alpha-olefin copolymer component having a reactivity ratio product of less than 0.75 and a weight average molecular weight of greater than about 450,000 g/mol; and from about 5 wt% to about 40 wt% of a second propylene alpha-olefin copolymer component having a reactivity ratio product of greater than 1.5 and a weight average molecular weight of less than about 215,000 g/mol.
  • copolymer is meant to include polymers having two or more monomers, optionally, with other monomers, and may refer to interpolymers, terpolymers, etc.
  • polymer as used herein includes, but is not limited to, homopolymers, copolymers, terpolymers, etc., and alloys and blends thereof.
  • polymer as used herein also includes impact, block, graft, random, and alternating copolymers.
  • polymer shall further include all possible geometrical configurations unless otherwise specifically stated. Such configurations may include isotactic, syndiotactic and atactic symmetries.
  • blend refers to a mixture of two or more polymers.
  • elastomer shall mean any polymer exhibiting some degree of elasticity, where elasticity is the ability of a material that has been deformed by a force (such as by stretching) to return at least partially to its original dimensions once the force has been removed.
  • the term "monomer” or “comonomer,” as used herein, can refer to the monomer used to form the polymer, i.e., the unreacted chemical compound in the form prior to polymerization, and can also refer to the monomer after it has been incorporated into the polymer, also referred to herein as a "[monomerj-derived unit". Different monomers are discussed herein, including propylene monomers, ethylene monomers, and diene monomers.
  • reactor grade means a polymer that has not been chemically or mechanically treated or blended after polymerization in an effort to alter the polymer's average molecular weight, molecular weight distribution, or viscosity. Particularly excluded from those polymers described as reactor grade are those that have been visbroken or otherwise treated or coated with peroxide or other prodegradants. For the purposes of this disclosure, however, reactor grade polymers include those polymers that are reactor blends.
  • Reactor blend means a highly dispersed and mechanically inseparable blend of two or more polymers produced in situ as the result of sequential or parallel polymerization of one or more monomers with the formation of one polymer in the presence of another, or by solution blending polymers made separately in parallel reactors.
  • Reactor blends may be produced in a single reactor, a series of reactors, or parallel reactors and are reactor grade blends.
  • Reactor blends may be produced by any polymerization method, including batch, semi-continuous, or continuous systems.
  • reactor blend polymers are blends of two or more polymers in which the polymers are blended ex situ, such as by physically or mechanically blending in a mixer, extruder, or other similar device.
  • Propylene Alpha-Olefin Copolymers are particularly excluded from “reactor blend” polymers.
  • the propylene alpha-olefin copolymer of the invention comprises a blend of a first propylene alpha-olefin component and a second propylene alpha-olefin component.
  • the first component is present in the amount of about 60 to about 95 wt% of the copolymer and the second component is present in the amount of about 5 to about 40 wt% of the copolymer.
  • the alpha-olefin comonomer units for each component may be derived from ethylene, butene, pentene, hexene, 4-methyl-l-pentene, octene, or decene. In preferred embodiments the comonomer for each component is ethylene.
  • each of the components consists essentially of propylene and ethylene derived units, or consists only of propylene and ethylene derived units.
  • the copolymer may include at least about 5 wt%, at least about 7 wt%, at least about 9 wt%, at least about 10 wt%, at least about 12 wt%, at least about 13 wt%, at least about 14 wt%, at least about 15 wt% ⁇ -olefin-derived units, based upon the total weight of the copolymer.
  • the copolymer may include up to about 30 wt%, up to about 25 wt%, up to about 22 wt%, up to about 20 wt%, up to about 19 wt%, up to about 18 wt% a-olefin-derived units, based upon the total weight of the copolymer.
  • the copolymer may comprise from about 5 to about 30 wt%, from about 6 to about 25 wt%, from about 7 wt% to about 20 wt%, from about 10 to about 19 wt%, from about 12 wt% to about 19 wt%, or from about 15 wt% to about 18 wt% ⁇ -olefin-derived units, based upon the total weight of the copolymer.
  • the copolymer may include at least about 70 wt%, at least about 75 wt%, at least about 78 wt%, at least about 80 wt%, at least about 81 wt%, at least about 82 wt% propylene- derived units, based upon the total weight of the copolymer.
  • the copolymer may include up to about 95 wt%, up to about 93 wt%, up to about 91 wt%, up to about 90 wt%, up to about 88 wt%, or up to about 87 wt%, or up to about 86 wt%, or up to about 85 wt% propylene- derived units, based upon the total weight of the copolymer.
  • the copolymers can be characterized by a melting point (Tm), which can be determined by differential scanning calorimetry (DSC).
  • Tm melting point
  • DSC differential scanning calorimetry
  • a “peak” in this context is defined as a change in the general slope of the DSC curve (heat flow versus temperature) from positive to negative, forming a maximum without a shift in the baseline where the DSC curve is plotted so that an endothermic reaction would be shown with a positive peak.
  • the "glass transition temperature” is measured using dynamic mechanical analysis. This 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 6.3 rad/sec.
  • DMA instrument e.g., TA Instruments DMA 2980 or Rheometrics RSA
  • the copolymer can have a triad tacticity of three propylene units (mm tacticity), as measured by 13C NMR, of 65% or greater, 70% or greater, 75% or greater, 80% or greater.
  • the triad tacticity may range from about 65% to about 99%, from about 70% to about 99%, from about 75% to about 99%, from about 80% to about 99%.
  • Triad tacticity is determined by the methods described in U.S. Patent No. 7,232,871.
  • Propylene crystallinity is probed using X-ray scattering methods. Since polypropylene is a semi-crystalline polymer, the crystal structure can be resolved using X-ray diffraction (XRD) or Wide-Angle X-ray Scattering (WAXS).
  • the unit cells of the crystalline polymer are the building blocks of the crystalline lamellae: planar sheets of crystalline material. Since not all polymer chains can crystallize, amorphous chains also exist and these typically are found in between stacks of crystalline lamellae. WAXS can probe the extent to which these polymer chains crystallize since the data will contain information regarding crystalline and amorphous morphology. WAXS also can determine crystalline orientation and crystallite size.
  • the crystallinity of the film samples is obtained from WAXS: unit cell type and overall extent of crystallinity. WAXS and SAXS patterns were collapsed to an I(q) vs q plot.
  • the overall degree of crystallinity of the film samples was determined by taking the ratio of the peak areas of the (110), (040), (130), (111) and (131) (which were fit to a Gaussian function) to the total area underneath the ID WAXS profile[l].
  • the amorphous region was also fit to a Gaussian curve. See Ryan, A.J., et al., A synchrotron X-ray study of melting and recrystallization in isotactic polypropylene. Polymer, 1997, 38(4): p. 759-768.
  • the comonomer content and sequence distribution of the polymers can be measured using 13 C nuclear magnetic resonance (NMR) by methods well known to those skilled in the art.
  • Comonomer content of discrete molecular weight ranges can be measured using methods well known to those skilled in the art, including Fourier Transform Infrared Spectroscopy (FTIR) in conjunction with samples by GPC, as described in Wheeler and Willis, Applied Spectroscopy, 1993, Vol. 47, pp. 1128-1130.
  • FTIR Fourier Transform Infrared Spectroscopy
  • the comonomer (ethylene) content can be measured using the procedure described in Wheeler and Willis. Reference is made to U.S. Patent No. 6,525,157 which contains more details on GPC measurements, the determination of ethylene content by NMR and the DSC measurements.
  • Mw, Mn and Mw/Mn are determined by using a High Temperature Gel Permeation Chromatography (Agilent PL-220), equipped with three in-line detectors, a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer. Experimental details, including detector calibration, are described in: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, pp. 6812-6820, (2001) and references therein. Three Agilent PLgel ⁇ Mixed-B LS columns are used. The nominal flow rate is 0.5 niL/min, and the nominal injection volume is 300 ⁇ .
  • the various transfer lines, columns, viscometer and differential refractometer (the DRI detector) are contained in an oven maintained at 145°C.
  • Solvent for the experiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.1 ⁇ Teflon filter. The TCB is then degassed with an online degasser before entering the GPC-3D.
  • 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 shaking 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 1.284 g/ml at 145°C.
  • the injection concentration is from 0.5 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
  • the DRI detector and the viscometer Prior to running each sample the DRI detector and the viscometer are purged. Flow rate in the apparatus is then increased to 0.5 ml/minute, and the DRI is allowed to stabilize for 8 hours before injecting the first sample.
  • the LS laser is turned on at least 1 to 1.5 hours before running the samples.
  • the concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, I DRI , using the following equation:
  • K DRI is a constant determined by calibrating the DRI
  • (dn dc) is the refractive index increment for the system.
  • Units on parameters throughout this description of the GPC-3D method are such that concentration is expressed in g/cm 3 , molecular weight is expressed in g/mole, and intrinsic viscosity is expressed in dL/g.
  • the LS detector is a Wyatt Technology High Temperature DAWN HELEOS.
  • M molecular weight
  • the molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M.B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971):
  • AR(9) is the measured excess Rayleigh scattering intensity at scattering angle ⁇
  • c is the polymer concentration determined from the DRI analysis
  • a 2 is the second virial coefficient.
  • ⁇ ( ⁇ ) is the form factor for a monodisperse random coil
  • K 0 is the optical constant for the system:
  • N A is Avogadro 's number
  • (dn/dc) is the refractive index increment for the system, which take the same value as the one obtained from DRI method.
  • a high temperature 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, r ⁇ s for the solution flowing through the viscometer is calculated from their outputs.
  • the intrinsic viscosity, [ ⁇ ] at each point in the chromatogram is calculated from the following equation:
  • n s c[n] + 0.3(c[n])2
  • the branching index (g' v i s ) is calculated using the output of the GPC-DRI-LS-VIS method as follows.
  • ] av g > of the sample is calculated by:
  • the branching index g' vis is defined as:
  • M v is the viscosity-average molecular weight based on molecular weights determined by LS analysis.
  • Mw weight average molecular weight measured using a low angle laser light scattering (LALLS) technique in combination with Gel Permeation Chromatography (GPC)
  • LALLS low angle laser light scattering
  • MwDRI weight average molecular weight
  • MvDRI viscosity average molecular weight
  • DRI differential refractive index
  • IV intrinsic viscosity
  • the weight average molecular weight of the first polymer component is greater than that of the second polymer component.
  • the weight average molecular weight of the first polymer component is greater than about 400,000 g/mol, or about 450,000 g/mol, or about 500,000 g/mol.
  • the weight average molecular weight of the second polymer component is less than about 300,000 g/mol, or about 250,000 g/mol, or about 215,000 g/mol.
  • the copolymer may have a melt flow rate (MFR), as measured according to ASTM D-1238 (2.16 kg weight @ 230°C), greater than about 0.5 g/10 min, greater than about 1.0 g/10 min, greater than about 1.5 g/10 min, greater than about 2.0 g/10 min, or greater than about 2.5 g/10 min.
  • MFR melt flow rate
  • the copolymer may have an MFR less than about 25 g/10 min, less than about 15 g/10 min, less than about 10 g/10 min, less than about 7 g/10 min, or less than about 5 g/10 min.
  • the copolymer may have an MFR from about 0.5 to about 10 g/10 min, from about 1.0 to about 7 g/10 min, or from about 1.5 to about 5 g/10 min, where desirable ranges may include ranges from any lower limit to any upper limit.
  • the copolymer is a reactor grade or reactor blended polymer, as defined above. That is, in preferred embodiments, the copolymer is a reactor blend of a first polymer component and a second polymer component.
  • the comonomer content of the copolymer can be adjusted by adjusting the comonomer content of the first polymer component, adjusting the comonomer content of second polymer component, and/or adjusting the ratio of the first polymer component to the second polymer component present in the copolymer.
  • the a-olefin content of the first polymer component (“Ri") may be greater than 5 wt%, greater than 7 wt%, greater than 10 wt%, greater than 12 wt%, greater than 15 wt% based upon the total weight of the first polymer component.
  • the a-olefin content of the first polymer component may be less than 30 wt%, less than 27 wt%, less than 25 wt%, less than 22 wt%, less than 20 wt%, or less than 19 wt%, based upon the total weight of the first polymer component.
  • the ⁇ -olefin content of the first polymer component may range from 5 wt% to 30 wt%, from 7 wt% to 27 wt%, from 10 wt% to 25 wt%, from 12 wt% to 22 wt%, from 15 wt% to 20 wt%, or from 15 wt% to 19 wt%.
  • the first polymer component comprises propylene and ethylene derived units, or consists essentially of propylene and ethylene derived units.
  • the a-olefin content of the second polymer component may be greater than 5 wt%, greater than 7 wt%, greater than 10 wt%, greater than 12 wt%, greater than 15 wt%, a-olefin, based upon the total weight of the second polymer component.
  • the ⁇ -olefin content of the second polymer component may be less than 30 wt%, less than 27 wt%, less than 25 wt%, less than 22 wt%, less than 20 wt%, or less than 19 wt%, based upon the total weight of the second polymer component.
  • the ⁇ -olefin content of the second polymer component may range from 5 wt% to 30 wt%, or from 7 wt% to 27 wt%, or from 10 wt% to 25 wt%, or from 12 wt% to 22 wt%, or from 15wt% to 20 wt%, or from 15 wt% to 19 wt%.
  • the second polymer component comprises propylene and ethylene derived units, or consists essentially of propylene and ethylene derived units.
  • the difference between the ⁇ -olefin of the first polymer component and that of the second polymer component is less than about 15 wt%, preferably less than about 10 wt%, and most preferably less than about 5 wt%.
  • the copolymer may comprise from 3 wt% to 45 wt% of the second polymer component, from 5 wt% to 40 wt% of the second polymer component, from 7.5 wt% to 35 wt% of the second polymer component, based on the weight of the copolymer, where desirable ranges may include ranges from any lower limit to any upper limit.
  • the copolymer may comprise from 55 wt% to 97 wt% of the first polymer component, from 60 wt% to 95 wt% of the first polymer component, from 65 wt% to 92.5 wt% of the first polymer component, based on the weight of the copolymer, where desirable ranges may include ranges from any lower limit to any upper limit.
  • Copolymerization of monomer Ml and monomer M2 leads to two types of polymer chains - one with monomer Ml at the propagating chain end (Ml * ) and other with monomer M2 (M2 * ). Four propagation reactions are then possible.
  • Monomer Ml and monomer M2 can each add either to a propagating chain ending in monomer Ml or to one ending in monomer M2, i.e.,
  • n and r 2 are defined as
  • ri and r 2 as defined above is the ratio of the rate constant for a reactive propagating species adding its own type of monomer to the rate constant for its addition of the other monomer.
  • the tendency of two monomers to copolymerize is noted by values of n and r 2 .
  • An n value greater than unity means that Ml* preferentially inserts Ml instead of M2, while an n value less than unity means that Ml* preferentially inserts M2.
  • An n value of zero would mean that Ml is incapable of undergoing homopolymerization.
  • a block copolymer In a block copolymer, one type of monomer is grouped together in a chain segment, and another one is grouped together in another chain segments.
  • a block copolymer can be thought of as a polymers with multiple chain segments with each segment consisting of the same type of monomer:
  • the copolymer is "statistically random.” For the case, where the two monomer reactivity ratios are different, for example, n >1 and ⁇ 2 ⁇ 1 or n ⁇ 1 and ⁇ 2 >1, one of the monomers is more reactive than the other toward both propagating chains.
  • the copolymer will contain a larger proportion of the more reactive monomer in random placement.
  • n and r 2 are greater than unity (and therefore, also nr 2 > 1), there is a tendency to form a block copolymer in which there are blocks of both monomers in the chain.
  • n » r 2 i.e. n » 1 and ⁇ 2 « 1
  • both types of propagating chains preferentially add to monomer Ml.
  • monomer Ml there is a tendency toward "consecutive homopolymerization" of the two monomers to form block copolymer.
  • a copolymer having reactivity product, nr 2 , greater than 1.5 contains relatively long homopolymer sequences and is said to be "blocky.”
  • This type of copolymerization is referred to as alternating copolymerization.
  • Each of the two types of propagating chains preferentially adds to the other monomer, that is, Ml adds only to M2 * and M2 adds only to Ml * .
  • the copolymer has the alternating structure irrespective of the co- monomer feed composition.
  • nr 2 4 (EE)(PP)/(EP) 2 .
  • the copolymers are preferably prepared using homogeneous conditions, such as a continuous solution polymerization process.
  • the copolymer are prepared in parallel solution polymerization reactors, such that the first reactor component is prepared in a first reactor and the second reactor component is prepared in a second reactor, and the reactor effluent from the first and second reactors are combined and blended to form a single reactor effluent from which the final copolymer is separated.
  • Exemplary methods for the preparation of copolymers may be found in U.S. Patent Nos.
  • the first reactor component of the copolymer is polymerized using a non-metallocene catalyst and the second reactor component of the copolymer is polymerized using a metallocene catalyst.
  • non-metallocene catalyst also known as “post- metallocene catalyst” describe transition metal complexes that do not feature any pi- coordinated cyclopentadienyl anion donors (or the like) and are useful the polymerization of olefins when combined with common activators. See Baier, M. C; Zuideveld, M. A.; Mecking, S. Angew. Chem. Int. Ed. 2014, 53, 2-25; Gibson, V. C, Spitzmesser, S. K.
  • the first reactor component of the copolymer is a pyridyl diamide catalyzed and the second reactor component of the copolymer is metallocene catalyzed.
  • the pyridyl diamide catalyst has the following structural formula:
  • M is a Group 3-12 metal
  • E is selected from carbon, silicon, or germanium
  • X is an anionic leaving group, such as, but not limited to alkyl, aryl, hydride, alkylsilane, fluoride, chloride, bromide, iodide, triflate, carboxylate, alkylsulfonate, amide, alkoxide, and hydroxide
  • L is a neutral Lewis base, such as, but not limited to ether, amine, thioether
  • R 1 and R 13 are independently selected from the group consisting of hydrocarbyls, substituted hydrocarbyls, and silyl groups
  • R 2 through R 12 are independently selected from the group consisting of hydrogen, hydrocarbyls, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyls, halogen, and phosphino
  • n is 1 or 2 or 3
  • m is 0, 1, or 2
  • two X groups may be joined together to form
  • M is a Group 4 metal, such as zirconium or hafnium.
  • n is 2 and m is 0;
  • E is carbon.
  • Preferred X groups include chloride, fluoride, methyl, ethyl, propyl, butyl, isobutyl, benzyl, hydrido, dialkylamido, dimethylamido, diethylamide, trimethylsilylmethyl, and neopentyl.
  • Rl groups include aryls, substituted aryls, 2,6- disubstituted aryls, 2,4,6-trisubstituted aryls, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methyl-phenyl, xylyl, mesityl, and 2-ethyl-6-isopropylphenyl.
  • Preferred R13 groups include aryls, substituted aryls, 2-substituted aryls, cycloalkyl, cyclohexyl, cyclopentyl, 2,5-disubstituted aryl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl, phenyl, and 4-methylphenyl.
  • Preferred R2/R3 pairs include H/H, H/aryl, H/2-substituted aryl, H/alkyl, H/phenyl, H/2-methylphenyl, and H/2-isopropylphenyl.
  • both R 7 and R 8 are hydrogen.
  • R 7 and R 8 are joined together to form a six-membered aromatic ring.
  • R 10 and R 11 are joined together to form a five or six- membered ring.
  • R 11 and R 12 are both hydrogen.
  • R 1 and R 13 may be independently selected from phenyl groups that are variously substituted with between zero to five substituents that include F, CI, Br, I, CF 3 , N0 2 , alkoxy, dialkylamino, aryl, and alkyl groups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof.
  • R 3 -E-R 2 groups and preferred R 12 -E-R u groups include CH 2 , CMe 2 , SiMe 2 , SiEt 2 , SiPr 2 , SiBu 2 , SiPh 2 , Si(aryl) 2 , Si(alkyl) 2 , CH(aryl), CH(Ph), CH(alkyl), and CH(2-isopropylphenyl), where alkyl is a Q to C 40 alkyl group (preferably Q to C 20 alkyl, preferably one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof), aryl is a C 5 to C 40 aryl group (preferably a C 6 to C 20 aryl group, preferably phenyl or substituted phenyl,
  • Useful metallocene compounds include compounds represented by the formula: TyCpmMGnXq wherein Cp is a cyclopentadienyl group (such as cyclopentadiene, indene or fluorene), which may be substituted or unsubstituted, M is a Group 4 to Group 6 transition metal, for example, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten, G is a heteroatom group represented by the formula JR* Z , where J is a group 15 or 16 element, preferably N, P, O, or S, and R* is a Ci to C20 hydrocarbyl group and z is 1 or 2, T is an optional bridging group that joins a cyclopentadienyl group to either another cyclopentadienyl group or a G group, and y is 0 or 1, each X is, independently, a leaving group,
  • M is a Group 4 transition metal (preferably Hf, Ti, and/or Zr).
  • M is Ti
  • m is 1.
  • M is Zr or Hf
  • m is 2 or 3.
  • M is Ti
  • m is 1 and when M is Zr or Hf, then m is 2.
  • y is 1, T is dialkylsilyl, and q is 2.
  • each Cp is a cyclopentadiene, indene or fluorene, which may be substituted or unsubstituted
  • each M is titanium, zirconium, or hafnium
  • each X is, independently, a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group.
  • M is Zr or Hf, n is 0, q is 2, m is 2, and y is 1.
  • M is Zr or Hf, n is 0, q is 2, m is 2, y is 1, and each Cp is a substituted indene.
  • M is Zr or Hf, n is 0, q is 2, m is 2, y is 1, and each Cp is a 2,4-disubstituted indene with the substituents being Ci to C30 hydrocarbyls.
  • each G is, independently, a heteroatom group represented by the formula JR* Z , where J is a group 15 or 16 element, preferably N, P, O, or S (preferably N or O, preferably N), and R* is a Ci to C20 hydrocarbyl group.
  • a linear branched or cyclic hydrocarbyl group having from one to twenty carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof, including t-butyl, cyclododecyl, cyclooctyl, and the like) and z is 1 or 2.
  • n is preferably 1 and G is a heteroatom group represented by the formula JR* Z , where J is a group 15 or 16 element, preferably N, P, O, or S (preferably N or O, preferably N), and R* is a linear branched or cyclic hydrocarbyl group having from one to twenty carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof, including t-butyl, cyclodecyl, cyclooctyl, and the like) and z is 1 or 2, preferably JR*z is cyclododecyl amido, t- butyl amido, and or 1-adamantyl amido.
  • JR*z is cyclododecyl amido, t- butyl
  • n 0.
  • each X may be, independently, a halide, a hydride, an alkyl group, an alkenyl group, or an arylalkyl group.
  • each X is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, aryls, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X's may form a part of a fused ring or a ring system), preferably each X is independently selected from halides, aryls and C 1 to C 5 alkyl groups, preferably each X is a phenyl, methyl, ethyl, propyl, butyl, pentyl, or chloro group.
  • each Cp group is, independently, a substituted or unsubstituted cyclopentadiene, a substituted or unsubstituted indene, or a substituted or unsubstituted fluorene.
  • each Cp group may be substituted with a combination of substituent groups R.
  • substituent groups R include one or more from the group selected from hydrogen, or linear, branched alkyl radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbamoyl radicals, alkyl- or dialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or combinations thereof.
  • substituent groups R have up to 50 non- hydrogen atoms, preferably from 1 to 30 carbon, that can also be substituted with halogens or heteroatoms or the like.
  • alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, or phenyl groups, and the like, including all their isomers, for example, tertiary butyl, isopropyl, and the like.
  • hydrocarbyl radicals include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl chlorobenzyl, and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl- substituted organometalloid radicals including tris(trifluoromethyl)-silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals including dimethylboron, for example; and disubstituted pnictogen radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide, and ethylsulfide.
  • Non-hydrogen substituents R include the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium, and the like, including olefins such as, but not limited to, olefinically unsaturated substituents including vinyl-terminated ligands, for example, but-3- enyl, prop-2-enyl, hex-5-enyl, and the like. Also, at least two R groups, preferably two adjacent R groups, may be joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, or a combination thereof.
  • the substituent(s) R are, independently, hydrocarbyl groups, heteroatoms, or heteroatom-containing groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof, N, O, S, P, or a Ci to C20 hydrocarbyl substituted with an N, O, S, and/or P heteroatom or heteroatom-containing group (typically having up to 12 atoms, including the N, O, S, and P heteroatoms).
  • hydrocarbyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof, N, O, S, P, or a Ci to
  • Non-limiting examples of Cp groups include cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraenyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands, phosphinimine ligands (WO 99/40125), pyrrolyl ligands, pyrazolyl ligands, carbazolyl ligands, borabenzene ligands, and the like, including hydrogenated versions thereof, for example tetrahydroindenyl ligands.
  • each Cp may, independently comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, sulfur, and phosphorus, in combination with carbon atoms to form an open, acyclic, or preferably a fused, ring or ring system, for example, a heterocyclopentadienyl ancillary ligand.
  • heteroatoms for example, nitrogen, silicon, boron, germanium, sulfur, and phosphorus
  • T is present and is a bridging group containing at least one Group 13, 14, 15, or 16 element, in particular boron or a Group 14, 15, or 16 element.
  • Preferred examples for the bridging group T include CH 2 , CH 2 CH 2 , SiMe 2 , SiPh 2 , SiMePh, Si(CH 2 ) 3 , Si(CH 2 ) 4 , O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me 2 SiOSiMe 2 , and PBu.
  • T is represented by the formula R a 2 J or (R a 2 J) 2 , where J is C, Si, or Ge, and each R a is, independently, hydrogen, halogen, Ci to C 2 o hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a Ci to C 2 o substituted hydrocarbyl, and two R a can form a cyclic structure including aromatic, partially saturated, or saturated cyclic, or fused ring system.
  • T is a bridging group comprising carbon or silica, such as dialkylsilyl, preferably T is selected from CH2, CH 2 CH 2 ,
  • useful metallocene compounds include those compounds represented by the formula (A):
  • M is a group 4 metal (preferably Hf, Ti, Zr, preferably Hf or Zr);
  • T is a bridging group
  • X is an anionic leaving group
  • each R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 , R 12 , and R 13 is independently, halogen atom, hydrogen, a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, substituted germylcarbyl substituents or a
  • R' is one of a halogen atom, a C 1 to C 10 alkyl group, or a C 6 to C 10 aryl group, provided that R 2 and R 8 may not be hydrogen; and R ⁇ and R 10 are, independently, a substituted or unsubstituted aryl group.
  • M may be Hf or Zr
  • T may be represented by the formula, (R*2G)g, where each G is C, Si, or Ge, g is 1 or 2, and each R* is, independently, hydrogen, halogen, Ci to C20 hydrocarbyl or a Ci to C20 substituted hydrocarbyl, and two or more R* can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system;
  • X may be an anionic leaving group; each R 3 , R 5 , R 6 , R 7 , R 9 , R 11 , R 12 , and R 13 independently may be hydrogen, a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, provided that R 2 and R 8 are independently a Ci to C20 hydrocarbyl group; and
  • M may be Zr or Hf .
  • each X independently may be selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and a combination thereof, (two X' s may form a part of a fused ring or a ring system), preferably each X is independently selected from halides and Ci to C5 alkyl groups, preferably each X is a methyl group.
  • each R 3 , R 5 , R 6 , R 7 , R 9 , R 11 , R 12 , or R 13 independently may be hydrogen or a substituted hydrocarbyl group or unsubstituted hydrocarbyl group, or a heteroatom, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.
  • each R 3 , R 4 , R 5 , R 6 , R 7 , R 9 , R 10 , R 11 , R 12 , or R 13 independently may be selected from hydrogen, methyl, ethyl, phenyl, benzyl, cyclobutyl, cyclopentyl, cyclohexyl, naphthyl, anthracenyl, carbazolyl, indolyl, pyrrolyl, cyclopenta[b]thiophenyl, fluoro, chloro, bromo, iodo and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl,
  • T may be a bridging group and comprises Si, Ge, or C, preferably T is dialkyl silicon or dialkyl germanium, preferably T is dimethyl silicon.
  • T is CH 2 , CH 2 CH 2 , C(CH 3 ) 2 , SiMe 2 , SiPh 2 , SiMePh, silylcyclobutyl (Si(CH 2 ) 3 ), (Ph) 2 C, (p-(Et) 3 SiPh) 2 C, cyclopentasilylene (Si(CH 2 ) 4 ), or Si(CH 2 ) 5 .
  • each R 2 and R 8 independently may be a Ci to C20 hydrocarbyl, or a Ci to C20 substituted hydrocarbyl, Ci to C20 halocarbyl, Ci to C20 substituted halocarbyl, Ci to C20 silylcarbyl, Ci to C20 substituted silylcarbyl, Ci to C20 germylcarbyl, or Ci to C20 substituted germylcarbyl substituents.
  • each R 2 and R 8 is independently, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docedyl, or an isomer thereof, preferably cyclopropyl, cyclohexyl, (1-cyclohexyl methyl) methyl, isopropyl, and the like.
  • R 4 and R 10 independently may be a substituted or unsubstituted aryl group.
  • Preferred substituted aryl groups include aryl groups where a hydrogen has been replaced by a hydrocarbyl, or a substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, a heteroatom or heteroatom-containing group.
  • aryl and substituted aryl groups include phenyl, naphthyl, anthracenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4- dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5- dimethylphenyl, 2,4,5-trimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2-ethylphenyl, 3- ethylphenyl, 4-ethylphenyl, 2,3-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,6- diethylphenyl, 3,4-diethylphenyl, 3,5-diethylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 3,5-di-isopropylphenyl,
  • R 2 and R 8 may be Ci to C20 hydrocarbyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docedyl or an isomer thereof, preferably cyclopropyl, cyclohexyl, (1- cyclohexyl methyl) methyl, or isopropyl; and R 4 and R 10 independently may be selected from phenyl, naphthyl, anthraceneyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3- dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4- dimethylphenyl, 3,5-dimethylphenyl, 2,4,5-trimethylphenyl, 2,3,
  • racemic metallocenes such as rac-dimethylsiladiyl(2- isopropyl,4-phenylindenyl)2 zirconium dichloride; rac-dimethylsiladiyl(2- isopropyl,4-[l- naphthyl]indenyl)2 zirconium dichloride; rac-dimethylsiladiyl(2- isopropyl,4-[3,5- dimethylphenyl]indenyl)2 zirconium dichloride; rac-dimethylsiladiyl(2-isopropyl,4-[ortho- methyl-phenyl]indenyl)2 zirconium dichloride; rac-dimethylsilyl bis-(2-methyl, 4- phenylindenyl)zirconium dichloride, rac dimethylsiladlyl bis-(2-methyl, 4-napthylindeny
  • Alkylated variants of these metallocenes are also useful, particularly when combined with a non-coordinating anion type activator.
  • These and other metallocene compositions are described in detail in U.S. Patent Nos. 6,376,407, 6,376,408, 6,376,409, 6,376,410, 6,376,411, 6,376,412, 6,376,413, 6,376,627, 6,380,120, 6,380,121, 6,380,122, 6,380,123, 6,380,124, 6,380,330, 6,380,331, 6,380,334, 6,399,723 and 6,825,372.
  • the activators for these metallocene catalysts can methylaluminoxane (MAO), or a non-coordinating anion activator selected from the group consisting of dimethylanilinium- or trityl-fluoroarylborates, wherein the fluoroaryl group is pentafluorophenyl, perfluoronaphthyl, or quadrafluoro-trihydronaphthyl.
  • MAO methylaluminoxane
  • a non-coordinating anion activator selected from the group consisting of dimethylanilinium- or trityl-fluoroarylborates, wherein the fluoroaryl group is pentafluorophenyl, perfluoronaphthyl, or quadrafluoro-trihydronaphthyl.
  • room temperature is used to refer to the temperature range of about 20°C to about 23.5°C.
  • the propylene-alpha olefin copolymer can be made using general polymerization techniques known in the art. Any solution, suspension, slurry and bulk and gas phase polymerization process known in the art can be used. Such processes can be run in batch, semi-batch or continuous mode. Homogeneous solution processes are preferred.
  • reactor temperatures can range from about 60°C to about 250°C, while pressures are generally higher than 300 psig.
  • the polymerization temperature is preferably at least 50, or 60, or 70°C, or within a range from 50, or 60, or 70, or 80, or 90, or 100, or 120 to 130, or 140, or 150, or 160, or 170°C.
  • the monomers are dissolved/dispersed in the solvent either prior to being fed to the first reactor (or for gaseous monomers the monomer may be fed to the reactor so that it will dissolve in the reaction mixture).
  • the solvent and monomers Prior to mixing, the solvent and monomers are generally purified to remove potential catalyst poisons.
  • the feedstock may be heated or cooled prior to feeding to the first reactor. Additional monomers and solvent may be added to the second reactor, and it may be heated or cooled.
  • the catalysts/activators can be fed in the first reactor or split between two reactors. In solution polymerization, polymer produced is molten and remains dissolved in the solvent under reactor conditions, forming a polymer solution (also referred as to effluent).
  • the solution polymerization process of this invention uses stirred reactor system comprising one or more stirred polymerization reactors.
  • the reactors should be operated under conditions to achieve a thorough mixing of the reactants.
  • the first polymerization reactor preferably operates at lower temperature.
  • the residence time in each reactor will depend on the design and the capacity of the reactor.
  • the catalysts/activators can be fed into the first reactor only or split between two reactors. Alternatively, a loop reactor is preferred.
  • the polymer solution is then discharged from the reactor as an effluent stream and the polymerization reaction is quenched, typically with coordinating polar compounds, to prevent further polymerization.
  • the polymer solution On leaving the reactor system the polymer solution is passed through a heat exchanger system on route to a devolatilization system and polymer finishing process. Under certain conditions of temperature and pressure, the polymer solution can phase separate into a polymer lean phase and a polymer rich phase. Phase separation occurs at the lower critical solution temperature (LCST). Increasing the temperature or decreasing the pressure at the LCST point leads to further phase separation.
  • LCST critical solution temperature
  • a polymer can be recovered from the effluent of either reactor or the combined effluent, by separating the polymer from other constituents of the effluent.
  • Conventional separation means may be employed.
  • polymer can be recovered from effluent by coagulation with a non-solvent such as isopropyl alcohol, acetone, or n-butyl alcohol, or the polymer can be recovered by stripping the solvent or other media with heat or steam.
  • a non-solvent such as isopropyl alcohol, acetone, or n-butyl alcohol
  • One or more conventional additives such as antioxidants can be incorporated in the polymer during the recovery procedure.
  • Possible antioxidants include phenyl-beta-naphthylamine; di-tert- butylhydroquinone, triphenyl phosphate, heptylated diphenylamine, 2,2'-methylene-bis(4- methyl-6-tert-butyl)phenol, and 2,2,4-trimethyl-6-phenyl-l,2-dihydroquinoline.
  • Other methods of recovery such as by the use of lower critical solution temperature (LCST) followed by devolatilization are also envisioned.
  • LCST critical solution temperature
  • the propylene-alpha olefin copolymer described herein is produced in either batch or continuous multistage polymerization processes.
  • Each polymerization stage is defined as a single polymerization reactor or a polymerization zone within a single reactor. More specifically, a multistage polymerization may involve either two or more sequential polymerizations (also referred to as a series process) or two or more parallel polymerizations (also referred to herein as a "parallel process").
  • the polymerization is conducted in a parallel process.
  • each component of the propylene-alpha olefin copolymer made in the respective reactors of the continuous, multiple reactor solution process are blended in solution without prior isolation from the solvent.
  • the blends may be a result of series reactor operation, where at least part of the effluent of a first reactor enters a second reactor and where the effluent of the second reactor can be submitted to finishing steps involving devolatilization.
  • the blend may also be the result of parallel reactor operation where the effluents of both reactors are combined and submitted to finishing steps.
  • Either option provides an intimate admixture of the polymers in the de volatilized copolymers.
  • Either case permits a wide variety of poly splits to be prepared whereby the proportion of the amounts of each component produced in the respective reactors can be varied widely.
  • the propylene- alpha olefin copolymer is a reactor blend.
  • the method discussed herein has the advantage of eliminating the need for a melt blending operation and enables intimate blends of the copolymers to be made in the original reaction medium. Such materials have unique properties because they are not subjected to shear degradation in melt processing equipment. The degree of mixing of each component of the blend is more intimate.
  • the process comprises contacting monomers including ethylene and propylene with a catalyst system in a first polymerization zone, thereby forming a mixture that includes the propylene copolymers, said propylene copolymer having a reactivity ratio product of less than 0.75 and a weight average molecular weight of greater than about 450,000 g/mol; polymerizing in a second polymerization zone by contacting a second monomer system and a second catalyst system capable of providing propylene copolymer, said propylene copolymer preferably having a reactivity ratio product of greater than 1.5 and a weight average molecular weight of less than about 215,000 g/mol.
  • the said second catalyst is different from the first catalyst system.
  • two reactors are configured such that monomers, catalyst(s) and solvent are fed independently to each reactor.
  • the first and second polymerizations are preferably taking place simultaneously in a parallel process.
  • the molecular weight characteristics (e.g., Mw, Mn, etc.) of the propylene- alpha olefin copolymer and also of the individual-propylene copolymer components can in certain circumstances be adjusted depending upon the desired properties of the propylene-alpha olefin copolymer. Those molecular weight characteristics are described elsewhere herein.
  • the molecular weight characteristics of each polymer can be set by choosing the reactor temperature, monomer concentration, and by optionally adding chain transfer agents such as hydrogen. Also, molecular weight can generally be lowered by increasing reaction temperatures, and raised by increasing monomer concentrations.
  • the propylene-alpha olefin copolymer may be used to prepare nonwoven elastic articles.
  • the nonwoven products described above may be used in articles such as hygiene products, including, but not limited to, diapers, feminine care products, and adult incontinent products.
  • the nonwoven products may also be used in medical products such as a sterile wrap, isolation gowns, operating room gowns, surgical gowns, surgical drapes, first aid dressings, and other disposable items.
  • the nonwoven products may be useful as facing layers for medical gowns, and allow for extensibility in the elbow area of the gown.
  • the nonwoven products may also be useful in disposable protective clothing, and may add toughness to elbow and knee regions of such clothing.
  • the nonwoven products may also be useful as protective wrapping, packaging, or wound care.
  • the nonwoven products may also be useful in geotextile applications, as the fabric may have improved puncture resistance in that the fabric will deform instead of puncture. See U.S. Patent Publication No. 2011/81529 and U.S. Patent No. 7,319,077.
  • the propylene olefin copolymer may also be suitable for use in an elastic films, as described in U.S. Patent No. 6,500,563; blow films, as described in U.S. Patent Publication No. 2009/94027; and cast-films, as described in U.S. Patent No. 7,655,317.
  • the propylene-alpha olefin copolymer has suitable elastic properties for use in nonwoven articles, including low tension set, top load, and hysteresis.
  • the method of measurement for evaluating these elastic properties is described in the Examples section below.
  • the tension set of the copolymer is less than about 20 %, preferably less than about 15 %, most preferably less than about 12 %.
  • the top load of the copolymer is less than about 15 N, preferably less than about 10 N, most preferably less than about 7 N.
  • the hysteresis of the copolymer is less than about 45 %, preferably less than about 40 %, most preferably less than about 30 %.
  • CE1 is a reactor blended propylene-based elastomer where the major component has 16 wt% ethylene content and 3 MFR (Mw of 240,000 g/mol) and the minor component has 4 wt% ethylene and 8 MFR (Mw of 195,000 g/mol). Both the first and second components of CE1 have an rlr2 of about 0.8 to about 0.9.
  • CE1 is made in a reactor using C2-symmetric metallocene catalyst of dimethylsilyl bis(indenyl) hafnium dimethyl precursor activated by dimethylanilinium tetrakis(heptafluoronaphthyl) borate.
  • CE1 was selected as the comparable example for its good elasticity.
  • Example 1 is a blocky propylene-ethylene elastomer with 16 wt% ethylene content. It is made in a 0.15 liter continuous reactor using C2-symmetric dimethyl ⁇ - dimethylsilyl)bis(2-methyl-4-naphthylindenyl) zirconium precursor activated by dimethylanilinium tetrakis(heptafluoronaphthyl) borate. Polymerization experiments were performed in a continuous stirred tank reactor (CSTR) made by Autoclave Engineers, Erie PA. The reactor was designed to operate at a maximum pressure and temperature of 2000 bar (30 kpsi) and 225 °C, although the current experiments the nominal reactor pressures were lower, from 1600 to 1700 psig.
  • CSTR continuous stirred tank reactor
  • the nominal reactor vessel volume was 150 mL.
  • the reactor was equipped with a magnetically coupled stirrer drive (Magnedrive).
  • a pressure transducer measured the pressure in the reactor.
  • the reactor temperature was measured using a type-K thermocouple.
  • a flush-mounted rupture disk located on the side of the reactor provided protection against catastrophic pressure failure. All product lines were heated to ⁇ 120°C to prevent fouling.
  • the reactor had an electric heating band that was controlled by a programmable logic control device. Except for the heat losses to the environment, the reactor did not have cooling (close to adiabatic operations).
  • the conversion in the reactor was monitored by an on-line gas chromatograph (GC) that sampled both the feed and the effluent.
  • GC on-line gas chromatograph
  • the GC analysis utilized the propane impurity present in the propylene feed as internal standard.
  • the reactor temperature and the temperature difference across the reactor wall was maintained constant by adjusting the reactor heater output (skin temperature) and the catalyst feed rate. At low catalyst concentrations condition, impurity control was the most critical factor in achieving controlled, steady state reactor conditions. Feed purification traps were used to control impurities carried by the monomer feed.
  • the purification traps were placed right before the feed pumps and comprised of two separate beds in series: activated copper (reduced in flowing 3 ⁇ 4 at 225 °C and 1 bar) for O2 removal followed by a molecular sieve (5 A, activated in flowing N2 at 270°C) for water removal.
  • Propylene was fed from a low-pressure cylinder equipped with a dip leg for liquid delivery to the reactor.
  • a heating blanket (Ace) was used to increase the propylene cylinder head pressure to approx. 17 bar (-250 psig). This increased head pressure allowed the monomer to be delivered to the monomer feed pump head at a pressure above its bubble point at the pump.
  • the low-pressure monomer feed was also stabilized against bubble formation by cooling the pump head using 10°C chilled water.
  • the purified monomer feed was fed by a two-barrel continuous ISCO pump (model 500D). The monomer flow rate was adjusted by adjusting the motor speed of the pump and was measured by a Coriolis mass flow meter (Model PROline Promass 80, Endress and Hauser).
  • the catalyst feed solution was prepared inside an argon-filled dry box (Vacuum Atmospheres). The atmosphere in the glove box was purified to maintain ⁇ 1 ppm O2 and ⁇ 1 ppm water. All glassware was oven-dried for a minimum of 4 hours at 110°C and transferred hot to the antechamber of the dry box. Stock solutions of the catalyst precursor and the activator were prepared using purified toluene that was stored in amber bottles inside the dry box. Aliquots were taken to prepare fresh activated catalyst solutions. The activated catalyst solution was charged inside the argon-filled dry box to a heavy-walled glass reservoir (Ace Glass, Inc. Vineland, NJ) and was pressurized to 5 psig with argon. The activated catalyst solution was delivered to the unit by a custom made two-barrel continuous high-pressure syringe pump (PDC Machines).
  • PDC Machines custom made two-barrel continuous high-pressure syringe pump
  • HPLC grade hexane (95% n-hexane, J.T. Baker) was used as solvent. It was purged with nitrogen for a minimum of four hours then passed through a series of copper and mol sieve beds (similar to the ones used for the propylene feed, see above) and finally was filtered once over activated basic alumina.
  • the filtered hexane was stored in a 4-liter glass vessel (Ace Glass, Vineland, NJ) inside an argon-filled dry box. The hexane was further purified by adding 1.5 mL (1.05 g) of trioctylaluminum solution (Aldrich #38,655-3) to the 4- liter reservoir of filtered hexane.
  • 5-10 psig head pressure of argon was applied to the glass vessel to deliver the scavenger-treated solvent to a metal feed vessel from which the hexane was delivered to the reactor by a two-barrel continuous ISCO pump (model 500D).
  • 5-10 psig head pressure of argon was applied to the glass vessel to deliver the scavenger solution to a 500 mL single-barrel ISCO pump, which in turn fed diene to the reactor.
  • Polymerization grade ethylene was compressed by a Fluitron A%-200 compressor and metered by a mass flow meter into the reactor.
  • the reactor was preheated to ⁇ 10-15°C below that of the desired reaction temperature, ranging from 85 to 89°C.
  • the solvent pump was turned on to deliver hexane/trioctylaluminum scavenger solution to the reactor from the 4-liter scavenger solution feed vessel.
  • This stream of scavenger/catalyst solution entered the reactor through a port on the top of the stirrer assembly to keep the polymer from fouling the stirrer drive.
  • the monomer feeds were turned on. The monomers were fed to the reactor through a side port.
  • the catalyst feed rate was adjusted to reach and maintain the target reaction temperature and conversion.
  • the residence time was 12.7 min.
  • the products were collected and weighed after vacuum-drying overnight at 70°C. Aliquots of the product were used for characterization without homogenizing the entire product yield.
  • Example 2 is the high molecular weight alternating propylene-ethylene elastomer with 15.7 wt% ethylene content made using CI symmetric 2,6-diisopropyl-N-((6-(2-((o- tolylamido)methyl)naphthalen- 1 -yl)pyridin-2-yl)methyl)anilidohafnium dimethyl precursor activated by dimethylanilinium tetrakis (pentafluorophenyl) borate. Polymerizations were carried out in a continuous stirred tank reactor system. A 0.5-liter Autoclave reactor was equipped with a stirrer, a pressure controller, and a water cooling/steam heating element with a temperature controller.
  • the reactor was operated in liquid fill condition at a reactor pressure in excess of the bubbling point pressure of the reactant mixture, keeping the reactants in liquid phase. All feeds (solvent and monomers) were pumped into the reactors by Pulsa feed pumps and the flow rates were controlled using Coriolis mass flow controller (Quantim series from Brooks) except for the ethylene, which flowed as a gas under its own pressure through a Brooks flow controller. Similarly, H2 feed was controlled using a Brooks flow controller. Ethylene, H2 and propylene feeds were combined into one stream and then mixed with a pre- chilled isohexane stream that had been cooled to at least 0°C. The mixture was then fed to the reactor through a single line. Scavenger solution was added to the combined solvent and monomer stream just before it entered the reactor to further reduce any catalyst poisons. Similarly, catalyst solution was fed to the reactor using an ISCO syringe pump through a separated line.
  • Isohexane used as solvent
  • monomers e.g., ethylene and propylene
  • Toluene for preparing catalyst solutions was purified by the same technique.
  • An isohexane solution of tri-n-octyl aluminum (TNOA) 25 wt % in hexane, Sigma Aldrich was used as scavenger solution.
  • the polymer produced in the reactor exited through a back pressure control valve that reduced the pressure to atmospheric. This caused the unconverted monomers in the solution to flash into a vapor phase which was vented from the top of a vapor liquid separator.
  • the liquid phase comprising mainly polymer and solvent, was collected for polymer recovery.
  • the collected samples were first air-dried in a hood to evaporate most of the solvent, and then dried in a vacuum oven at a temperature of about 90°C for about 12 hours. The vacuum oven dried samples were weighed to obtain yields.
  • the scavenger feed rate was adjusted to optimize the catalyst efficiency and the feed rate varied from 0 (no scavenger) to 15 ⁇ / ⁇ .
  • the catalyst feed rates may also be adjusted according to the level of impurities in the system to reach the targeted conversions listed. All the reactions were carried out at a pressure of about 2.4 MPa/g unless otherwise mentioned. The reaction was carried out at a temperature of 70°C, propylene feed rate of 14 g/min, an ethylene feed rate of 0.9 g/min, 3 ⁇ 4 feed rate of 3.62 cc/min (H2 was diluted in N2 at a concentration of 24 vol% of 3 ⁇ 4), and isohexane feed rate of 56.7 g/min. The overall conversion was 32.9 wt%.
  • CE1, El, and E2 samples have similar crystallizable sequence lengths, similar crystallinity, and similar molecular weights. However, due to their differences in the rlr2, each requires a different amount of ethylene to achieve the same final crystallinity (E2 has the highest rlr2 and the lowest ethylene content of the inventive propylene-ethylene elastomers, and El has the lowest rlr2 and the highest ethylene content). Tg values reflect the ethylene content - samples with higher ethylene content have lower Tg values.
  • the individual reactor components of CE1 are reported in Table 1. TABLE 1: COMPOSITIONAL CHARACTERIZATION RESULTS
  • a Fontijne melt vacuum press was used to mold a 2mm thick plaque of each sample. The temperature was ramped up to 190°C and held for 5 minutes followed by 5 minutes under compression before cooling to room temperature. ASTM type 3 dog bones are punched out using a clicker press in L210. The sample was aged for a minimum of 7 days after molding before mechanical test. The time is required for the pellet unstable samples to slowly crystallize so to arrive at their final crystallinity. It is critical for the sample to develop its full crystallinity so that consistent and reproducible mechanical testing can be conducted. An Instron tensile tester was used for the mechanical tests. The sample was placed in the grips with a 35-mm grip separation. Slack was manually removed so that the reading on the instrument registers a positive tensile force before starting the test. The sample is stretched to a 100% extension at 100 mm min. The crosshead returns to 0% extension and repeats this cycle once more.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition comportant de 60 % en poids à 95 % en poids d'un premier composant d'un copolymère de propylène-alpha-oléfine présentant un produit des rapports de réactivité inférieur à 0,75 et un poids moléculaire moyen en poids supérieur à environ 450 000 g/mol ; et 5 % en poids à 40 % en poids d'un second composant d'un copolymère de propylène-alpha-oléfine présentant un rapport de réactivité supérieur à 1,5 et un poids moléculaire moyen en poids inférieur à environ 215 000 g/mol.
PCT/US2017/042366 2016-08-15 2017-07-17 Copolymères de propylène-alpha-oléfine et leurs procédés de fabrication WO2018034760A1 (fr)

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ES17743455T ES2876423T3 (es) 2016-08-15 2017-07-17 Copolímeros de propileno/alfa-olefina y métodos para fabricar los mismos
CN201780044093.XA CN109548404B (zh) 2016-08-15 2017-07-17 丙烯-α烯烃共聚物及其制造方法
EP17743455.2A EP3497139B1 (fr) 2016-08-15 2017-07-17 Copolymères de propylène/alpha-oléfine et leurs procédés de fabrication

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