WO2014070386A1 - Broad molecular weight distribution polypropylene resins - Google Patents
Broad molecular weight distribution polypropylene resins Download PDFInfo
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- WO2014070386A1 WO2014070386A1 PCT/US2013/063765 US2013063765W WO2014070386A1 WO 2014070386 A1 WO2014070386 A1 WO 2014070386A1 US 2013063765 W US2013063765 W US 2013063765W WO 2014070386 A1 WO2014070386 A1 WO 2014070386A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
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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
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
Definitions
- the resins with molecular weight distribution in the range of 3 to 4.5 are not suitable in converting processes such as blown film applications either in mono-layer or multi-layer applications due to poor melt strength. Similar behavior is observed in sheeting, deep-drawn thermoforming, and foaming applications.
- Other converting applications requiring good melt strength for which such polymers are not suitable include profile extrusion, base stock for thermoplastic vulcanizates (TPV), bi-axially oriented polypropylene (BOPP) film, blow molding applications, and the like.
- polypropylene resins having one or more properties, such as improved melt strength, improved stiffness, and the like.
- polypropylene resins suitable for use in blown film, in multi-layer applications as replacement for HDPE, sheeting, thermoforming in shallow drawn and deep drawn applications, and/or foaming applications are also a need for such polypropylene resins suitable for use in blown film, in multi-layer applications as replacement for HDPE, sheeting, thermoforming in shallow drawn and deep drawn applications, and/or foaming applications.
- a polypropylene resin comprises at least 50 mol% propylene, a MWD (Mw/Mn) of greater than 5, a branching index (g') of at least 0.95, and a melt strength of at least 20 cN determined using an extensional rheometer at 190°C.
- a catalyst system comprises a Ziegler-Natta catalyst comprising a non-aromatic internal electron donor and first and second external electron donors comprising different organosilicon compounds.
- a method to produce a polypropylene resin comprises contacting propylene monomers at propylene polymerization conditions with a catalyst system comprising a Ziegler-Natta catalyst comprising a non-aromatic internal electron donor and first and second external electron donors comprising different organosilicon compounds.
- Figure 1 is a graph plotting the intrinsic viscosity vs. molecular weight of a propylene resin produced according to the instant disclosure.
- Figure 2 shows a plot of the complex viscosity vs. the angular frequency of a propylene resin produced according to the instant disclosure.
- a polypropylene resin may comprise: at least 50 mol% propylene, a melt strength of at least 20 cN or at least 50 cN determined using an extensional rheometer at 190°C, a branching index (g') of at least 0.95, and an MWD (Mw/Mn) of greater than 5.
- a Ziegler-Natta catalyst system may comprise a Ziegler-Natta catalyst comprising a non-aromatic internal electron donor, and first and second external electron donors comprising different organosilicon compounds.
- a method for making a polypropylene resin may comprise contacting propylene monomers at a temperature and a pressure or other appropriate propylene polymerization conditions in the presence of the catalyst system to produce a polypropylene resin comprising at least 50 mol% propylene and a melt strength of at least 20 cN determined using an extensional rheometer at 190°C.
- the catalyst system may comprise a Ziegler-Natta catalyst comprising a non-aromatic internal electron donor and a first external electron donor having the formula R ⁇ SifOR 2 ⁇ , wherein each R 1 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms in which the carbon adjacent to the Si is a secondary or a tertiary carbon atom, and wherein each R 2 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms.
- the catalyst system further may comprise a second external electron donor having the formula R 3 n Si(OR 4 )4- n , wherein each R 3 and R 4 are independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms, n is 1, 2, or 3, and the second external electron donor is different than the first external electron donor.
- hydrocarbyl radical is defined to be Ci to C2 0 radicals, or Ci to C1 0 radicals, or Ce to C2 0 radicals, or C7 to C2 0 radicals that may be linear, branched, or cyclic where appropriate (aromatic or non-aromatic); and includes hydrocarbyl radicals substituted with other hydrocarbyl radicals and/or one or more functional groups comprising elements from Groups 13 - 17 of the periodic table of the elements.
- two or more such hydrocarbyl radicals may together form a fused ring system, including partially or fully hydrogenated fused ring systems, which may include heterocyclic radicals.
- substituted means that a hydrogen atom and/or a carbon atom in the base structure has been replaced with a hydrocarbyl radical, and/or a functional group, and/or a heteroatom or a heteroatom containing group.
- hydrocarbyl radical includes heteroatom containing groups.
- a heteroatom is defined as any atom other than carbon and hydrogen.
- methyl cyclopentadiene is a Cp group, which is the base structure, substituted with a methyl radical, which may also be referred to as a methyl functional group
- ethyl alcohol is an ethyl group, which is the base structure, substituted with an -OH functional group
- pyridine is a phenyl group having a carbon in the base structure of the benzene ring substituted with a nitrogen atom.
- a hydrocarbyl radical may be independently selected from substituted or unsubstituted methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, hexenyl, hexenyl,
- hydrocarbyl radicals may also include isomers of saturated, partially unsaturated and aromatic cyclic structures wherein the radical may additionally be subjected to the types of substitutions described above.
- aryl refers to aromatic cyclic structures, which may be substituted with hydrocarbyl radicals and/or functional groups as defined herein.
- aryl radicals include: acenaphthenyl, acenaphthylenyl, acridinyl, anthracenyl, benzanthracenyls, benzimidazolyl, benzisoxazolyl, benzofluoranthenyls, benzofuranyl, benzoperylenyls, benzopyrenyls, benzothiazolyl, benzothiophenyls, benzoxazolyl, benzyl, carbazolyl, carbolinyl, chrysenyl, cinnolinyl, coronenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, dibenzoanthracenyls, fluoranthenyl, fluorenyl, furanyl, imidazolyl, indazolyl, indenopyrenyls, indolyl, indolinyl, is
- non-aromatic refers to compounds, radicals, and/or functional groups without aromatic character attributed to cyclic conjugated sp 2 carbons having protons with a chemical shift relative to TMS consistent with aromatic protons, or greater than 6, as readily understood by one of minimal skill in the art.
- radical when a radical is listed, it indicates that the base structure of the radical (the radical type) and all other radicals formed when that radical is subjected to the substitutions defined above.
- Alkyl, alkenyl, and alkynyl radicals listed include all isomers including where appropriate cyclic isomers, for example, butyl includes w-butyl, 2-methylpropyl, 1 -methylpropyl, tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls); pentyl includes n-pentyl, cyclopentyl, 1 -methylbutyl, 2- methylbutyl, 3-methylbutyl, 1-ethylpropyl, and nevopentyl (and analogous substituted cyclobutyls and cyclopropyls); butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3- butenyl, 1 -methyl- 1-propenyl, l-methyl-2-propenyl, 2-methyl-l-propenyl, and 2-methyl-2- propenyl (and cyclobutenyls and cyclopropen
- Cyclic compounds having substitutions include all isomer forms, for example, methylphenyl would include ortho-methylphenyl, meta-methylphenyl and para- methylphenyl; dimethylphenyl would include 2,3- dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4- dimethylphenyl, and 3,5-dimethylphenyl.
- a functional group includes both organic and inorganic radicals or moieties comprising elements from Groups 13, 14, 15, 16, and 17 of the periodic table of elements.
- Suitable functional groups may include hydrocarbyl radicals, e.g., alkyl radicals, alkene radicals, aryl radicals, and/or halogen (CI, Br, I, F), O, S, Se, Te, NR * X , OR*, SeR*, TeR*, PR* X , AsR* x , SbR* x , SR*, BR* X , SiR* x , GeR* x , SnR* x , PbR* x , and/or the like, wherein R is a Ci to C 20 hydrocarbyl as defined above, and wherein x is the appropriate integer to provide an electron neutral moiety.
- hydrocarbyl radicals e.g., alkyl radicals, alkene radicals, aryl radicals, and/or halogen (CI, Br, I, F)
- O S, Se, Te, NR * X , OR*, SeR*, TeR*
- Suitable functional groups include those typically referred to as amines, imides, amides, ethers, alcohols (hydroxides), sulfides, sulfates, phosphides, halides, phosphonates, alkoxides, esters, carboxylates, aldehydes, and the like.
- Polypropylene microstructure is determined by 13 C-NMR spectroscopy, including the concentration of isotactic and syndiotactic diads ([m] and [r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]).
- the designation "m” or “r” describes the stereochemistry of pairs of contiguous propylene groups, "m” referring to meso, and “r” to racemic. Samples are dissolved in d2-l, l,2,2-tetrachloroethane, and spectra recorded at 125°C using a 100 MHz (or higher) NMR spectrometer.
- an "olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound comprising carbon and hydrogen having at least one double bond.
- alkene is a linear, branched, or cyclic compound comprising carbon and hydrogen having at least one double bond.
- the olefin present in such polymer or copolymer is the polymerized form of the olefin.
- ethylene content of 35 wt% to 55 wt%
- the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
- An oligomer is typically a polymer having a low molecular weight, such an Mn of less than 25,000 g/mol, or in an embodiment less than 2,500 g/mol, or a low number of mer units, such as 75 mer units or less.
- An "ethylene polymer” or “ethylene copolymer” is a polymer or copolymer comprising at least 50 mol% ethylene derived units
- a "propylene polymer” or “propylene copolymer” is a polymer or copolymer comprising at least 50 mol% propylene derived units, and so on.
- a-olefin includes C2 to C22 olefins.
- Non-limiting examples of a-olefins include ethylene, propylene, 1-butene, 1-pentene, 1- hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene 1-dodecene, 1-tridecene, 1- tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1- eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1- hexacosene, 1-heptacosene, 1-octacosene, 1-nonacos
- Non-limiting examples of cyclic olefins and diolefins include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene, 2-methylcyclopentene, 4- methylcyclopentene, vinylcyclohexane, norbornadiene, dicyclopentadiene, 5-ethylidene-2- norbornene, vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane, 1,2- divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,5-divinylcyclooctane, 1 -allyl-4-vinylcyclohexane, 1,4-dially
- catalystst and “catalyst compound” are defined to mean a compound capable of initiating polymerization catalysis under the appropriate conditions.
- the catalyst may be described as a catalyst precursor, a pre-catalyst compound, or a transition metal compound, and these terms are used interchangeably.
- a catalyst compound may be used by itself to initiate catalysis or may be used in combination with an activator, an internal electron donor, one or more external electron donors, and/or a co-catalyst to initiate catalysis.
- the catalyst compound is often referred to as a pre-catalyst or catalyst precursor.
- a "catalyst system” is a combination of at least one catalyst compound, at least one internal electron donor, one or more external electron donors, a co-catalyst, and/or a support where the system can polymerize monomers to produce a polymer under polymerization conditions of suitable temperature and pressure.
- catalyst systems are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art that the ionic form of the component is the form that reacts with the monomers to produce polymers.
- catalyst productivity is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising (W) grams of catalyst (cat), over a period of time of (T) hours; and may be expressed by the following formula: P/(T x W) and expressed in units of gPgcat ⁇ hr "1 .
- Conversion is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor.
- Catalyst activity is a measure of how active the catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kg P/mol cat).
- a "scavenger” is a compound that is typically added to facilitate oligomerization or polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form a catalyst system. In an embodiment, a co- activator can be pre-mixed with the catalyst compound to form an alkylated catalyst compound.
- Me is methyl
- Ph is phenyl
- Et is ethyl
- Pr is propyl
- iPr is isopropyl
- n-Pr is normal propyl
- Bu is butyl
- iso-butyl is isobutyl
- sec -butyl refers to secondary butyl
- tert-butyl refers to tertiary butyl
- n-butyl is normal butyl
- pMe is para-methyl
- Bz is benzyl
- THF is tetrahydrofuran
- Mes is mesityl, also known as 1,3,5-trimethylbenzene
- Tol is toluene
- TMS is trimethylsilyl
- MAO is methylalumoxane.
- RT room temperature, which is defined as 25 °C unless otherwise specified. All percentages are in weight percent (wt%) unless otherwise specified.
- Mw, Mz number of carbon atoms, g value and g' v i s may be determined by using a High Temperature Size Exclusion Chromatograph (either 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. Experimental details, including detector calibration, are described in: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, 6812-6820, (2001), and references therein. Three Polymer Laboratories PLgel 10mm Mixed-B LS columns are used.
- 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 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 145°C.
- the injection concentration is from 0.75 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
- Prior to running each sample the DRI detector and the injector are purged. Flow rate in the apparatus is then increased to 0.5 ml/minute, and the DRI is allowed to stabilize for 8 to 9 hours before injecting the first sample.
- the LS laser is turned on 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 DR1 , using the following equation:
- K D RiI D Ri /(dn/dc) K D RiI D Ri /(dn/dc)
- K D RI is a constant determined by calibrating the DRI
- (dn/dc) is the refractive index increment for the system.
- (dn/dc) 0.104 for propylene polymers, 0.098 for butene polymers and 0.1 otherwise. Units on parameters throughout this description of the SEC method are such that concentration is expressed in g/cm 3 , molecular weight is expressed in g/mol, and intrinsic viscosity is expressed in dL/g.
- the LS detector is a Wyatt Technology High Temperature mini-DAW .
- 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
- (dn/dc) 0.104 for propylene polymers, 0.098 for butene polymers, and 0.1 otherwise
- ⁇ ( ⁇ ) is the form factor for a monodisperse random coil
- K 0 is the optical constant for the system: where A is Avogadro's number, and (dn/dc) is the refractive index increment for the system.
- 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, n 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:
- the branching index (g' v i s ) is calculated using the output of the SEC-DRI-LS-VIS method as follows.
- the average intrinsic viscosity, [n] avg , of the sample is calculated by:
- M v is the viscosity- average molecular weight based on molecular weights determined by LS analysis.
- a s is the size coefficient for the polymacromer
- ⁇ is the power law coefficient for the polymacromer.
- a functionalized polymer comprises greater than 0.1 wt% of a functional group and/or a g' ⁇ 0.95, and/or is the product of a post reactor functionalization or grafting process.
- the catalyst system may be a solid titanium catalyst component comprising magnesium, titanium, halogen, a non-aromatic internal electron donor, and two or more external electron donors.
- the solid titanium catalyst component also referred to as a Ziegler-Natta catalyst, can be prepared by contacting a magnesium compound, a titanium compound, and at least the internal electron donor.
- Examples of the titanium compound used in the preparation of the solid titanium catalyst component include tetravalent titanium compounds having the formula:
- R is a hydrocarbyl radical
- X is a halogen atom
- n is from 0 to 4.
- suitable titanium compounds for use herein include: titanium tetra-halides such as TiCl 4 , TiBr 4 , and/or Til 4 ; alkoxy titanium trihalides including Ti(OCH 3 )Cl 3 , Ti(OC 2 H 5 )Cl 3 , Ti(0 n-C 4 H 9 )Cl 3 , Ti(OC 2 H 5 )Br 3 , and/or Ti(0 iso-C 4 H 9 )Br 3 ; dialkoxytitanium dihalides including Ti(OCH 3 ) 2 Cl2, Ti(OC 2 Hs) 2 Cl 2 , Ti(0 n-C 4 H 9 ) 2 Cl2 and/or Ti(OC 2 H 5 ) 2 Br 2 ; trialkoxytitanium monohalides including Ti(OCH 3 ) 3 Cl, Ti(OC 2 H 5 ) 3 Cl, Ti(0 n-C 4 H9) 3 Cl and/or Ti(OC 2 H5) 3 Br; and/or t
- the halogen-containing titanium compound may be a titanium tetrahalide, or titanium tetrachloride.
- the titanium compounds may be used singly or in combination with each other.
- the titanium compound may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.
- the magnesium compound to be used in the preparation of the solid titanium catalyst component may include a magnesium compound having reducibility and/or a magnesium compound having no reducibility.
- Suitable magnesium compounds having reducibility may, for example, be magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond.
- Suitable examples of such reducible magnesium compounds include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, magnesium ethyl chloride, magnesium propyl chloride, magnesium butyl chloride, magnesium hexyl chloride, magnesium amyl chloride, butyl ethoxy magnesium, ethyl butyl magnesium, and/or butyl magnesium halides. These magnesium compounds may be used singly or they may form complexes with the organoaluminum co-catalyst as described herein. These magnesium compounds may be a liquid or a solid.
- Suitable examples of the magnesium compounds having no reducibility include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; alkoxy magnesium halides, such as magnesium methoxy chloride, magnesium ethoxy chloride, magnesium isopropoxy chloride, magnesium phenoxy chloride, and magnesium methylphenoxy chloride; alkoxy magnesiums, such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, and 2-ethylhexoxy magnesium; aryloxy magnesiums such as phenoxy magnesium and dimethylphenoxy magnesium; and/or magnesium carboxylates, such as magnesium laurate and magnesium stearate.
- magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride
- alkoxy magnesium halides such as magnesium methoxy chloride, magnesium ethoxy chloride, magnesium isopropoxy chloride, magnesium phenoxy chloride, and magnesium methylphenoxy chloride
- non-reducible magnesium compounds may be compounds derived from the magnesium compounds having reducibility, or may be compounds derived at the time of preparing the catalyst component.
- the magnesium compounds having no reducibility may be derived from the compounds having reducibility by, for example, contacting the magnesium compounds having reducibility with polysiloxane compounds, halogen-containing silane compounds, halogen-containing aluminum compounds, esters, alcohols, and the like.
- the magnesium compounds having reducibility and/or the magnesium compounds having no reducibility may be complexes of the above magnesium compounds with other metals, or mixtures thereof with other metal compounds. They may also be mixtures of two or more types of the above compounds.
- halogen-containing magnesium compounds including magnesium chloride, alkoxy magnesium chlorides and aryloxy magnesium chlorides may be used.
- a suitable solid catalyst component comprising a non- aromatic internal electron donor may be a catalyst solid sold by Lyondell-Basell Inc. under the trade name of AvantTM ZN-168.
- a catalyst is used to exemplify the invention, other titanium supported catalyst systems are contemplated.
- Other catalyst use mechanisms are contemplated. Including, but not limited to, batch prepolymerization, in situ prepolymerization and other such mechanisms.
- supported Ziegler-Natta catalysts may be used in combination with a co-catalyst, also referred to herein as a Ziegler-Natta co-catalyst.
- a co-catalyst also referred to herein as a Ziegler-Natta co-catalyst.
- compounds containing at least one aluminum-carbon bond in the molecule may be utilized as the co-catalysts, also referred to herein as an organoaluminum co-catalyst.
- Suitable organoaluminum compounds include organoaluminum compounds of the general formula:
- R 1 and R 2 are identical or different, and each represents a hydrocarbyl radical containing from 1 to 15 carbon atoms, or 1 to 4 carbon atoms;
- organoaluminum compounds include complex alkylated compounds of metals of Group I and aluminum represented by the general formula:
- M 1 is Li, Na, or K and R 1 is as defined above.
- Suitable organoaluminum compounds include compounds represented by the following general formulae:
- R x and R 2 are as defined above, and m is preferably 1.5 ⁇ m ⁇ 3; wherein R 1 is as defined above, X is halogen, and m is 0 ⁇ m ⁇ 3, or 2 ⁇ m ⁇ 3; and/or
- Suitable examples of the organoaluminum compounds include trialkyl aluminums such as trimethyl aluminum, triethyl aluminum and tributyl aluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkyl aluminum alkoxides such as diethyl aluminum ethoxide and dibutyl aluminum ethoxide; alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesqui-butoxide; partially alkoxylated alkyl aluminums having an average composition represented by the general formula R 1 2.5Al(OR 2 )o.5; partially halogenated alkyl aluminums, for example, alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; partially hydrogenated alkyl aluminums, for example, alkyl aluminum dihydrides such as ethyl aluminum dihydride and propyl aluminum dihydride; and partially alkyl aluminum
- the organoaluminum compound may comprise two or more aluminum atoms bonded through an oxygen or nitrogen atom.
- examples include (C 2 H5)2A10A1(C 2 H5)2, (C 4 H9)2A10A1(C 4 H9)2, and/or methylaluminoxane (MAO).
- Other suitable examples include LiAl(C2Hs) 4 and LiAl(C7Hi5) 4 .
- the trialkyl aluminums and alkyl-aluminums resulting from bonding of at least two aluminum compounds may be used.
- the co-catalyst may be an organoaluminum compound that is halogen free.
- Suitable halogen free organoaluminum compounds are, in particular, branched unsubstituted alkylaluminum compounds of the formula AIR3, where R denotes an alkyl radical having 1 to 10 carbon atoms, such as for example, trimethylaluminum, triethylaluminum, triisobutylaluminum and tridiisobutylaluminum.
- Additional compounds that are suitable for use as a co-catalyst are readily available and amply disclosed in the prior art including U.S. Patent No. 4,990,477.
- the organoaluminum Ziegler- Natta co-catalyst may be trimethyl aluminum, triethylaluminum (TEAL), or a combination thereof.
- Electron donors suitable for use herein generally may be used in two ways in the formation of Ziegler-Natta catalysts and catalyst systems.
- an internal electron donor may be used in the formation reaction of the catalyst as the transition metal halide is reacted with the metal hydride or metal alkyl.
- suitable internal electron donors include amines, amides, ethers, esters, esters, ketones, nitriles, phosphines, stilbenes, arsines, phosphoramides, thioethers, thioesters, aldehydes, alcoholates, and salts of organic acids.
- the internal donor may be non-aromatic.
- the non-aromatic internal electron donor may comprise an aliphatic amine, amide, ester, ether, ketone, nitrile, phosphine, phosphoramide, thioethers, thioester, aldehyde, alcoholate, carboxylic acid, or a combination thereof.
- the solid titanium catalyst component may be prepared using a non-aromatic internal electron donor.
- suitable non-aromatic internal electron donors include oxygen-containing electron donors such as alcohols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic oxides, ethers, acid amides and acid anhydrides; nitrogen-containing electron donors such as ammonia, amines, nitriles, and/or isocyanates.
- Suitable examples include alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol, and the like; ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, and the like; organic acid esters having 2 to 30 carbon atoms including the esters desired to be included in the titanium catalyst component, such as methyl formate, ethyl formate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl
- the non-aromatic internal electron donor may comprise a Ci to C2 0 diester of a substituted or unsubstituted C2 to C 10 dicarboxylic acid.
- the non-aromatic internal electron donor may be a succinate according to formula (I):
- R 1 and R 2 are independently Ci to C2 0 linear or branched alkyl, alkenyl, or cycloalkyl hydrocarbyl radicals;
- R 3 to R 6 are independently, hydrogen, halogen, or Ci to C2 0 linear or branched alkyl, alkenyl, or cycloalkyl hydrocarbyl radicals, wherein the R 3 to R 6 radicals are not joined together, wherein at least two of the R 3 to R 6 radicals are joined to form a cyclic divalent radical, or a combination thereof.
- R 3 to R 5 of formula I may be hydrogen and R 6 may be a radical selected from the group consistent of a primary branched, secondary or tertiary alkyl, or cycloalkyl radical having from 3 to 20 carbon atoms.
- the internal donor may be a monosubstituted non-aromatic succinate compound.
- suitable examples include diethyl secbutylsuccinate, diethylhexylsuccinate, diethyl cyclopropylsuccinate, diethyl trimethylsilylsuccinate, diethyl methoxysuccinate, diethyl cyclohexylsuccinate, diethyl (cyclohexylmethyl) succinate, diethyl t-butylsuccinate, diethyl isobutylsuccinate, diethyl isopropylsuccinate, diethyl neopentylsuccinate, diethyl isopentylsuccinate, diethyl (l, l, ltrifluoro-2-propyl) succinate, diisobutyl sec -butylsuccinate, diisobutylhexylsuccinate, diisobutyl
- the internal electron donor having a structure consistent with formula (I) may comprise at least two radicals from R 3 to R 6 , which are different from hydrogen and are selected from Ci to C2 0 linear or branched alkyl, alkenyl, and/or cycloalkyl hydrocarbyl groups, which may contain heteroatoms.
- two radicals different from hydrogen may be linked to the same carbon atom.
- Suitable examples include 2,2-disubstituted succinates including diethyl 2,2-dimethylsuccinate, diethyl 2-ethyl-2- methylsuccinate, diethyl 2- (cyclohexylmethyl)-2-isobutylsuccinate, diethyl 2-cyclopentyl-2- n-propylsuccinate, diethyl 2,2-diisobutylsuccinate, diethyl 2-cyclohexyl-2-ethylsuccinate, diethyl 2-isopropyl-2-methylsuccinate, diethyl 2,2-diisopropyl diethyl 2isobutyl-2- ethylsuccinate, diethyl 2- (1, 1, l-trifluoro-2-propyl)-2-methylsuccinate, diethyl 2 isopentyl-2- isobutylsuccinate, diisobutyl 2,2dimethylsuccinate, diisobutyl 2-
- Suitable non-aromatic succinate compounds include: diethyl 2,3-bis (trimethylsilyl) succinate, diethyl 2,2-secbutyl-3 -methylsuccinate, diethyl 2- (3,3,3-trifluoropropyl)-3- methylsuccinate, diethyl 2,3bis (2-ethylbutyl) succinate, diethyl 2,3-diethyl-2- isopropylsuccinate, diethyl 2,3-diisopropyl-2methylsuccinate, diethyl 2,3-dicyclohexyl-2- methylsuccinate, diethyl 2,3-diisopropylsuccinate, diethyl 2,3-bis (cyclohexylmethyl) succinate, diethyl 2,3-di-t
- the compounds according to formula (I) may include two or four of the radicals R 3 to R 6 joined to the same carbon atom which are linked together to form a cyclic multivalent radical.
- suitable compounds include l-(ethoxycarbonyl)- 1 - (ethoxyacetyl)-2,6-dimethylcyclohexane, l-(ethoxycarbonyl)- 1 -(ethoxyacetyl)-2,5-dimethyl- cyclopentane, l-(ethoxycarbonyl)-l-(ethoxyacetylmethyl)-2-methylcyclohexane, and/or 1- (ethoxycarbonyl)-l-(ethoxy (cyclohexyl) acetyl) cyclohexane.
- the internal electron donor compound may be selected from the group consisting of diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, diethyl 2,3-dicyclohexyl-2-methylsuccinate, diisobutyl 2,3-dicyclohexyl-2-methylsuccinate, diisobutyl 2,2-dimethylsuccinate, diethyl 2,2- dimethylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl 2-(cyclohexylmethyl)-3-ethyl-3-methylsuccinate, diisobutyl 2-(cyclohexylmethyl)-3- ethyl-3-methylsuccinate, diisobutyl 2-(cyclohexylmethyl)-3-e
- two or more external electron donors may also use in combination with a catalyst.
- External electron donors include, but are not limited to, organic silicon compounds, e.g., tetraethoxysilane (TEOS), methylcyclohexyldimethoxysilane (MCMS), propyltriethoxysilane (PTES) and dicyclopentydimethoxysilane (DCPMS).
- TEOS tetraethoxysilane
- MCMS methylcyclohexyldimethoxysilane
- PTES propyltriethoxysilane
- DCPMS dicyclopentydimethoxysilane
- Internal and external-type electron donors are described, for example, in US 4,535,068.
- the use of organic silicon compounds as external electron donors is described, for example, in US 4,218,339; US 4,395,360; US 4,328, 122; and US 4,473,660.
- the external electron donors act to control stereoregularity, which affects the amount of isotactic versus atactic polymers produced in a given system.
- the more stereoregular isotactic polymer is more crystalline, which leads to a material with a higher flexural modulus.
- Highly crystalline, isotactic polymers also display lower MFRs, as a consequence of a reduced hydrogen response during polymerization.
- the stereoregulating capability and hydrogen response of a given external electron donor are directly and inversely related.
- the DCPMS donor has a substantially lower hydrogen response than the PTES donor, but produces a significantly higher level of stereoregularity than PTES.
- the two external electron donors A and B also referred to herein as the first external electron donor and the second external electron donor, may be selected such that the melt flow rate MFR (A) of homopolypropylene obtained by homopolymerizing propylene by using the first external electron donor (A) in combination with the solid titanium catalyst component and the organoaluminum compound catalyst component and the MFR (B) of homopolypropylene obtained by homopolymerizing propylene by using the second external electron donor (B) under the same conditions as in the case of using the external electron donor (A) have the following relation:
- the external electron donors to be used in the preparation of the electron donor catalyst component may be those electron donors which are used in preparing the solid titanium catalyst component.
- each of the external electron donors (A) and (B) may comprise organic silicon compounds.
- one or more of the external electron donors may comprise an organic silicon compound of formula:
- R 3 and R 4 independently represent a hydrocarbyl radical and 0 ⁇ n ⁇ 4.
- Examples of the suitable organic silicon compounds include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diiso-propyldiethoxysilane, t-butylmethyl- n-diethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o- tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p- tolyldimethoxysilane, bisethylphenyldimethoxy-silane, dicyclohexyldiethoxysilane, cyclohexylmethyl-
- one of the two or more organic silicon compounds may comprise the formula:
- R 1 represents a hydrocarbyl radical in which the carbon adjacent to Si is secondary or tertiary. Suitable examples include substituted and unsubstituted alkyl groups such as isopropyl, sec -butyl, t-butyl and t-amyl groups, cyclo-alkyl groups such as cyclopentyl and cyclohexyl groups, cycloalkenyl groups such as a cyclopentenyl group, and aryl groups such as phenyl and tolyl groups.
- R 2 may represent a hydrocarbyl radical, or a hydrocarbyl radical having 1 to 5 carbon atoms, or a hydrocarbyl radical having 1 or 2 carbon atoms.
- suitable organic silicon compound examples include diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-sec-butyldimethoxysilane, di-t- butyldimethoxysilane, di-t-amyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxy-silane, diphenyldimethoxysilane, bis-o-tolyldimethoxy-silane, bis-m- tolyldimethoxysilane, bis-p-tolyldi-methoxysilane, and/or bis-ethylphenyldimethoxysilane.
- organic silicon compound may be represented by the following general formula:
- R 1 each represents a hydrocarbyl radical and at least one of the two hydrocarbyl radicals is a hydrocarbon group in which the carbon adjacent to Si is a primary carbon.
- suitable hydrocarbon groups include alkyl groups such as ethyl, n- propyl and n— butyl groups, aralkyl groups such as cumyl and benzyl groups, and alkenyl groups such as a vinyl group, and the like.
- R 2 may represent a hydrocarbyl radical preferably having 1 to 5 carbon atoms, or from 1 to 2 carbon atoms.
- Suitable examples of the organic silicon compounds in which n is 2 include diethyldimethoxysilane, dipropyldimethoxysilane, di-n- butyldimethoxysilane, dibenzyldimethoxysilane, and/or divinyldimethoxysilane.
- the external electron donors include methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, decyl-trimethoxysilane, decyltriethoxysilane, propyltri-ethoxysilane, butyltriethoxysilane, phenyltriethoxy-silane, vinyltrimethoxysilane, vinyltributoxysilane and/or cyclohexyltrimethoxysilane.
- the above disclosed organic silicon compounds may be used such that a compound capable of being changed into such an organic silicon compound is added at the time of polymerizing or preliminarily polymerizing an olefin, and the organic silicon compound may be formed in situ during the polymerization or the preliminary polymerization of the olefin.
- a first external electron donor may have the formula R 1 2Si(OR 2 )2, wherein each R 1 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms in which the carbon adjacent to the Si is a secondary or a tertiary carbon atom, and wherein each R 2 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms; and
- n 1, 2, or 3; and the second external electron donor is different than the first external electron donor.
- the first external electron donor and the second external electron donor may be selected from the group consisting of tetraethoxysilane, methylcyclohexyldimethoxysilane, propyltriethoxysilane, dicyclopentydimethoxysilane, and combinations thereof.
- the Ziegler-Natta catalyst system may comprise 2.5 mol% to less than 50 mol% of the first external electron donor and greater than 50 mol% of a second external electron donor based on total mol% of external electron donors.
- the first electron donor may comprise, consist of, or consist essentially of dicyclopentyldimethoxysilane (DCPMS) and the second external electron donor may comprise, consist of, or consist essentially of propyltriethoxysilane (PTES).
- DCPMS dicyclopentyldimethoxysilane
- PTES propyltriethoxysilane
- a relationship between the first external electron donor and the second external electron donor may be defined by the equation:
- MFR(A) is a first melt flow rate of a homopolymer formed by polymerizing propylene monomers in the presence of the Ziegler-Natta catalyst and the first external electron donor
- MFR(B) is a second melt flow rate of a homopolymer formed by polymerizing propylene monomers in the presence of the Ziegler-Natta catalyst and the second external electron donor, and wherein the MFR(A) is lower than the MFR(B).
- a method to make a polypropylene resin may comprise contacting propylene monomers at propylene polymerization conditions with a catalyst system to produce a polypropylene resin comprising at least 50 mol% propylene, an MWD greater than 5 and a melt strength of at least 20 cN determined using an extensional rheometer at 190°C, the catalyst system comprising: a Ziegler-Natta catalyst comprising a non-aromatic internal electron donor; and first and second external electron donors comprising different organosilicon compounds.
- the first external electron donor may have the formula R 1 2Si(OR 2 )2, wherein each R 1 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms in which the carbon adjacent to the Si is a secondary or a tertiary carbon atom, and wherein each R 2 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms; and the second external electron donor has the formula R 3 n Si(OR 4 )4_ n , wherein each R 3 and R 4 are independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms, n is 1, 2, or 3, and the second external electron donor is different than the first external electron donor.
- the non-aromatic internal electron donor may comprise an aliphatic amine, amide, ester, ether, ketone, nitrile, phosphine, phosphoramide, thioether, thioester, aldehyde, alcoholate, carboxylic acid, or a combination thereof, or a Ci to C2 0 diester of a substituted or unsubstituted C2 to C 10 dicarboxylic acid, or a succinate according to the formula:
- R 1 and R 2 are, independently, Ci to C20 linear or branched alkyl, alkenyl, or cycloalkyl hydrocarbyl radicals;
- R 3 to R 6 are, independently, hydrogen, halogen, or Ci to C2 0 linear or branched alkyl, alkenyl, or cycloalkyl hydrocarbyl radicals, wherein the R 3 to R 6 radicals are not joined together, or wherein at least two of the R 3 to R 6 radicals are joined to form a cyclic divalent radical, or a combination thereof.
- the polymerization process according to the instant disclosure may include contacting propylene with any embodiment herein described of the catalyst system under polymerization conditions.
- the polymerization process may include a preliminary polymerization step.
- the preliminary polymerization may include utilizing the Ziegler-Natta catalyst system comprising the non- aromatic internal electron donor in combination with at least a portion of the organoaluminum co-catalyst wherein at least a portion of the external electron donors are present wherein the catalyst system is utilized in a higher concentration than utilized in the subsequent "main" polymerization process.
- the concentration of the catalyst system in the preliminary polymerization, based on the moles of titanium present may be 0.01 to 200 millimoles, or 0.05 to 100 millimoles, calculated as a titanium atom, per liter of an inert hydrocarbon medium.
- the organoaluminum co-catalyst may be present in an amount sufficient to produce 0.1 to 500 g, or 0.3 to 300 g, of a polymer per gram of the titanium catalyst present, and may be present at 0.1 to 100 moles, or 0.5 to 50 moles, per mole of the titanium atom present in the catalyst component.
- the preliminary polymerization may be carried out under mild conditions in an inert hydrocarbon medium in which an olefin and the catalyst components are present.
- the inert hydrocarbon medium used include aliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons, such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons, such as benzene, toluene and xylene; halogenated hydrocarbons, such as ethylene chloride and chlorobenzene; and mixtures thereof.
- the olefin used in the preliminary polymerization may be the same as an olefin to be used in the main polymerization.
- the reaction temperature for the preliminary polymerization may be a point at which the resulting preliminary polymerization does not dissolve substantially in the inert hydrocarbon medium, which may be -20 to +100°C, or -20 to +80°C, or from 0 to 40°C.
- a molecular weight controlling agent such as hydrogen may be used during the preliminary polymerization.
- the molecular weight controlling agent may desirably be used in such an amount that the polymer obtained by preliminary polymerization has properties consistent with the intended product.
- the preliminary polymerization may be carried out so that 0.1 to 1000 g, or 0.3 to 300 g, of a polymer forms per gram of the titanium catalyst.
- a method for making a polypropylene resin may comprise contacting propylene monomers at a temperature and a pressure in the presence of catalyst system to produce a propylene resin comprising at least 50 mol% propylene, wherein the catalyst system comprises:
- a Ziegler-Natta catalyst comprising a non-aromatic internal electron donor
- each R 1 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms in which the carbon adjacent to the Si is a secondary or a tertiary carbon atom, and wherein each R 2 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms;
- each R 3 and R 4 are independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms,
- n 1, 2, or 3;
- the second external electron donor is different than the first external electron donor.
- the propylene polymer resin may have a melt strength of at least 20 cN determined using an extensional rheometer at 190°C.
- polymerization may be carried out by slurry polymerization wherein the inert hydrocarbon may be used as a reaction solvent, or an olefin liquid under the reaction conditions may be used as the solvent.
- the titanium catalyst may be present in the reactor at 0.005 to 0.5 millimole, preferably 0.01 to 0.5 millimole, based on Ti moles per liter of the reaction zone.
- the organoaluminum co-catalyst may be present in an amount sufficient to produce 1 to 2,000 moles, or 5 to 500 moles of aluminum per mole of the titanium atom in the catalyst system.
- the internal electron donor may be present at 0.2 to 5.0, or 0.5 to 2.0 per mole of Ti.
- the total amount of the external electron donors may be 0.001 to 50 moles, or 0.01 to 20 moles, or 0.05 to 10 mole Si per mole of Ti present.
- the first external electron donor may be present in the catalyst system at from 2.5 to 50 mol%, or 2.5 to 10 mol% of the total amount of external electron donor present.
- the polymerization process may include contacting the titanium catalyst component, the internal electron donor, the organoaluminum co-catalyst, and the two external electron donors with each other at the time of the main polymerization, before the main polymerization, for example, at the time of the preliminary polymerization, or a combination thereof. In contacting them before the main polymerization, any two or more of these components may be freely selected and contacted. In any embodiment, two or more of the components may be contacted individually or partly and then contacted with each other in total to produce the catalyst system.
- the catalyst system components may be contacted with each other before the polymerization in an inert gaseous atmosphere, the individual catalyst components may be contacted with each other in an olefin atmosphere, or any combination thereof.
- hydrogen may be used during the polymerization to control the molecular weight and other properties of the resulting polymer.
- polymerization conditions may include a polymerization temperature of 20 to 200°C, or 50 to 180°C, and a pressure from atmospheric pressure to 100 kg/cm 2 , or from 2 to 50 kg/cm 2 .
- the polymerization process according to the instant disclosure may be carried out batchwise, semicontinuously, or continuously.
- the polymerization may be carried out in two or more stages, using two or more reactors under different reaction conditions, utilizing different internal electron donors, different external electron donors, and/or different catalyst systems.
- the polypropylene resin according to the instant disclosure may be produced in a bulk continuous reactor.
- a catalyst system comprising a magnesium chloride supported titanium catalyst according to one or more embodiments of the instant disclosure is utilized.
- Catalyst preparation may be carried out continuously in situ by contacting the catalyst solids, triethylaluminum, and the external electron donor system under conditions known in the art to yield active, stereospecific catalyst for polymerization of propylene.
- the activated catalyst may then be continuously fed into a prepolymerization reactor where it was continuously polymerized in propylene to a productivity of approximately 100 to 400 g-polymer/g-cat.
- the prepolymerized catalyst may then be continuously fed into a bulk slurry reactor, and polymerization continued at 70°C to 80°C, for a residence time of 90 minutes.
- the reaction slurry (homopolymer granules in bulk propylene) may then be removed from the reactor and the polymer granules continuously separated from the liquid propylene.
- the polymer granules may then be separated from the unreacted monomer to produce a granular product for compounding and/or mechanical properties.
- hydrogen may be used in the reactor to control the melt flow rate of the polypropylene resin.
- the granules from the bulk reactor after removing the monomer, may be fed directly into a gas phase reactor (GPR) where polymerization is continued under conditions known in the art to produce ethylene- propylene bipolymer within the pores of the polymer granules.
- GPR gas phase reactor
- the final product, referred to in the art as an "impact copolymer” may be continuously withdrawn from the gas phase reactor and separated from unreacted monomer to produce a granular product for compounding and further processing.
- the molecular weight of the ethylene-propylene rubber or more appropriately, Intrinsic Viscosity (IV) of the rubber phase may be controlled by the concentration of hydrogen in the GPR.
- the granules from the reactor may be stabilized with at least 0.01 wt% of an additive, e.g., 0.15 wt% IrganoxTM 1010, 0.05 wt% UltranoxTM 626A, and/or with 0.075 wt% sodium benzoate (fine form) and then pelletized, e.g., on a 30 mm Werner & Pfleiderer twin screw extruder. The pellets may then be injection molded, and/or subjected to further processing.
- an additive e.g., 0.15 wt% IrganoxTM 1010, 0.05 wt% UltranoxTM 626A, and/or with 0.075 wt% sodium benzoate (fine form)
- pelletized e.g., on a 30 mm Werner & Pfleiderer twin screw extruder.
- the pellets may then be injection molded, and/or subjected to further processing.
- a polypropylene resin may comprise at least 50 mol% propylene and has a melt strength of at least 20 cN determined using an extensional rheometer at 190°C.
- the melt strength of a polymer at a particular temperature e.g., 190°C, is determined with a Gottfert Rheotens Melt Strength Apparatus (e.g., Gottfert Rheotens 71.97).
- the measurement is accomplished by grasping the extrudate from a capillary rheometer (e.g., a Gottfert Rheograph 2002 capillary rheometer), or from an extruder equipped with a capillary die, after the extrudate has been extruded 100 mm using variable speed gears and increasing the gear speed at a constant acceleration (12 mm/s 2 , starting from an initial, zero-force calibration velocity of 10 mm/s) until the molten polymer strand breaks.
- the force in the strand is measured with a balance beam in conjunction with a linear variable displacement transducer.
- the force required to extend and then break the extrudate is defined as the melt strength.
- the force is measured in centinewtons (cN).
- a typical plot of force vs. wheel velocity is known in the art to include a resonate immediately before the strand breaks. In such cases, the plateau force is approximated by the midline between the oscillations.
- melt strength is a key property of products used in blown film, thermoforming, blow molding processes, and the like.
- high melt strength is required to maintain a stable bubble when running at high temperatures and/or at high production rates, especially on large lines. If the melt strength is unacceptably low, holes form in a molten web, which causes the bubble to collapse and occasionally tear off. This, in turn, results in loss of production, and can lead to subsequent quality problems if the material in the extruder begins to degrade during the down-time.
- Low melt strength in linear polyethylenes precludes the film manufacturer from taking advantage of the excellent draw-down characteristics inherent with most linear polyethylenes unless a melt strength enhancer, such as LDPE, is added.
- a polypropylene resin according to any of the embodiments disclosed herein may comprise at least 50 mol% propylene and have a melt strength of at least 35 cN, or at least 40 cN, or at least 45 cN, or at least 50 cN, or at least 55 cN, or at least 60 cN, or at least 65 cN, or at least 70 cN, or at least 75 cN, or at least 80 cN, or from 50 cN to 200 cN, or from 60 cN to 150 cN, or from 70 cN to 200 cN, or any combination thereof, determined using an extensional rheometer at 190°C as described herein.
- a polypropylene resin according to any of the embodiments disclosed herein may comprise at least 50 mol% propylene and has an MWD (Mw/Mn) of greater than 5, or greater than or equal to 6, or from 6 to 20, or from 6 to 15, or any combination thereof.
- a polypropylene resin according to any of the embodiments disclosed herein further may comprise at least 75 mol%, or at least 80 mol%, or at least 90 mol%, or at least 95 mol%, or at least 99 mol% propylene.
- a polypropylene resin according to any of the embodiments disclosed herein may be a propylene homopolymer.
- a polypropylene resin according to any of the embodiments disclosed herein may comprise from 0.1 to 10 mol% of a comonomer.
- the comonomer may be an alpha olefin.
- the comonomer may be selected from the group consisting of ethylene and C 4 to C20 olefins.
- a polypropylene resin according to any of the embodiments disclosed herein may have a branching index (g') of at least 0.95, or at least 0.99.
- a polypropylene resin according to any of the embodiments disclosed herein may have a stiffness of greater than 2000 MPa, or greater than 2100 MPa, or 290 kpsi (2000 MPa) to 360 kpsi (2500 MPa) determined according to ASTM D790A on nucleated samples with 0.1% sodium benzoate.
- a polypropylene resin according to any of the embodiments disclosed herein may have a viscosity ratio of greater than or equal to 35, or 40, or 45, or from 35 to 80 determined at an angular frequency ratio of 0.01 and at an angular frequency ratio of 100 rad/s (at an angular frequency ratio of 0.01 to 100 rad/s) at a fixed strain of 10% at 190°C.
- a polypropylene resin according to any of the embodiments disclosed herein may have a MFR range from 0.1 to 100, or from 0.3 to 10, when determined according to ASTM D1238 Condition L.
- a polypropylene resin according to any of the embodiments disclosed herein may be an impact copolymer.
- an impact copolymer refers to a resin comprising a homopolymer made in a bulk polymerization reactor followed by transferring the granules to the gas phase reactor and making ethylene-propylene rubber within the granules.
- the polypropylene resin may be a non-functionalized polymer or resin.
- a non-functionalized resin does not comprise grafted or otherwise post-reactor processed olefin polymers.
- functionalized or grafted it is meant that various functional groups are incorporated, grafted, bonded to, and/or physically or chemically attached to the polymer backbone of the polymer being functionalized after formation of the base polymer.
- functionalized polymers include polymers in which functional groups are grafted onto the polymer backbone or pendent groups utilizing radical copolymerization of a functional group, referred to in the art as graft copolymerization.
- Examples of functional groups utilized to produce functionalized polymers include unsaturated carboxylic acids, esters of the unsaturated carboxylic acids, acid anhydrides, di-esters, salts, amides, imides, aromatic vinyl compounds, hydrolyzable unsaturated silane compounds, and unsaturated halogenated hydrocarbons.
- unsaturated carboxylic acids and acid derivatives include, but are not limited to, maleic anhydride, citraconic anhydride, 2-methyl maleic anhydride, 2-chloromaleic anhydride, 2,3-dimethylmaleic anhydride, bicyclo[2,2, l]-5-heptene-2,3-dicarboxylic anhydride and 4-methyl-4-cyclohexene-l,2-dicarboxylic anhydride, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, crotonic acid, bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5, &g, lo- octahydronaphthalene-2,3-dicarboxylic acid anhydride, 2-oxa-l,3-diketospiro(4.4)non-7-ene, bicyclo(2.2.1)h
- esters of the unsaturated carboxylic acids include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
- Hydrolyzable unsaturated silane compounds useful as functional groups present in functionalized polymers include a radical polymerizable unsaturated group having an alkoxysilyl group or a silyl group in its molecule.
- Examples include a compound having a hydrolyzable silyl group bonded to a vinyl group and/or a hydrolyzable silyl group bonded to the vinyl group via an alkylene group, and/or a compound having a hydrolyzable silyl group bonded to an ester or an amide of acrylic acid, methacrylic acid, or the like.
- Examples thereof include vinyltrichlorosilane, vinyltris(beta-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxy silane, gamma- methacryloxypropyltrimethoxysilane, monovinylsilane, and monoallylsilane.
- Examples of unsaturated halogenated hydrocarbons useful as functional groups include vinyl chloride and vinylidene chloride.
- functionalized polymers further include polymers grafted onto other polymers.
- a functionalized polymer is considered to have indications of long chain branching (i.e., a g' less than 0.95), consistent with the cross-linking and intermolecular bonding associated with functionalized polymers.
- a functionalized polymer comprises greater than 0.1 wt% of a functional group and/or a g' ⁇ 0.95, and/or is the product of a post reactor functionalization or grafting process. Accordingly, in any embodiment, the non-functionalized polymer may comprise less than 0.1 wt% of a functional group and/or is not the product of a post-reactor functionalization process, and/or is not a post-reactor grafted polymer and/or has a g' > 0.95 determined as described herein.
- the resin may be produced by contacting propylene monomers at propylene polymerization conditions with a catalyst system comprising a Ziegler-Natta catalyst comprising a non-aromatic internal electron donor, and first and second external electron donors comprising different organosilicon compounds.
- a catalyst system comprising a Ziegler-Natta catalyst comprising a non-aromatic internal electron donor, and first and second external electron donors comprising different organosilicon compounds.
- the resin may be free of functionalized polypropylene or comprises less than 5 weight percent of functional groups selected from hydroxide, aryls, substituted aryls, halogens, alkoxys, carboxylates, esters, acrylates, and carboxyl, based upon the weight of the polypropylene resin, and wherein the number of carbons of the polypropylene resin involved in olefinic bonds is less than 5% of the total number of carbon atoms in the resin.
- the resin may be free of post-reactor grafted polypropylene or comprises less than 5 percent by weight of post-reactor grafted polypropylene.
- a polypropylene resin according to any of the embodiments disclosed herein may have a heat distortion temperature of greater than or equal to 100°C, determined according to ASTM D648 using a load of 0.45 MPa (66 psi).
- a polypropylene resin according to any of the embodiments disclosed herein may have an isopentad percentage of greater than 90%, or greater than 95%, or greater than 99%.
- a polypropylene resin according to any of the embodiments disclosed herein may comprise a blend of various components.
- the blends may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components 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
- a polypropylene resin according to any of the embodiments disclosed herein further may comprise greater than or equal to 0.01 wt% of one or more fillers; antioxidants; anti-cling agents; tackifiers; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; talc; or a combination thereof.
- a polypropylene resin according to any of the embodiments disclosed herein may comprise at least 50 mol% propylene, has a melt strength of at least 20 cN determined using an extensional rheometer at 190°C, and an MWD (Mw/Mn) of greater than 5, wherein the resin is produced by contacting propylene monomers at a temperature and a pressure according to any method or process disclosed herein utilizing any embodiment or combination of embodiments of the catalyst system as disclosed herein.
- a polypropylene resin according to any of the embodiments disclosed herein may comprise at least 50 mol% propylene, has a melt strength of at least 20 cN determined using an extensional rheometer at 190°C, and an MWD (Mw/Mn) of greater than 5, wherein the resin is produced by contacting propylene monomers at a temperature and a pressure in the presence of catalyst system comprising a Ziegler-Natta catalyst comprising a non-aromatic internal electron donor and two or more external electron donors.
- a polypropylene resin comprising:
- melt strength greater than 20 cN determined using an extensional rheometer at
- E4 The resin of any of the above embodiments, comprising a viscosity ratio of from 35 to 80 determined from the complex viscosity ratio at 0.01 to 100 rad/s angular frequency at a fixed strain of 10% at 190°C.
- E5. The resin of any of the above embodiments, having a heat distortion temperature of greater than or equal to 100°C, determined according to ASTM D648 using a load of 0.45 MPa (66 psi).
- E6 The resin of any of the above embodiments, wherein the resin is an impact copolymer.
- El 1 The resin of any of the above embodiments, comprising a stiffness of from 2000 MPa (290 kpsi) to 2500 MPa (360 kpsi) determined according to ASTM D790A on nucleated samples with 0.1% sodium benzoate.
- E12 The resin of any of the above embodiments, further comprising greater than or equal to 0.01 wt% of one or more fillers; antioxidants; anti-cling agents; tackifiers; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; talc; or a combination thereof.
- El 3 The resin of any of the above embodiments, wherein the resin is produced by contacting propylene monomers at propylene polymerization conditions with a catalyst system comprising a Ziegler-Natta catalyst comprising a non-aromatic internal electron donor, and first and second external electron donors comprising different organosilicon compounds.
- a catalyst system comprising a Ziegler-Natta catalyst comprising a non-aromatic internal electron donor, and first and second external electron donors comprising different organosilicon compounds.
- the first external electron donor has the formula R ⁇ SilOR 2 ⁇ , wherein each R 1 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms in which the carbon adjacent to the Si is a secondary or a tertiary carbon atom, and wherein each R 2 is independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms; and
- the second external electron donor has the formula R 3 n Si(OR 4 )4_ n , wherein each R 3 and R 4 are independently a hydrocarbyl radical comprising from 1 to 10 carbon atoms, n is 1, 2, or 3, and the second external electron donor is different than the first external electron donor.
- non-aromatic internal electron donor comprises an aliphatic amine, amide, ester, ether, ketone, nitrile, phosphine, phosphoramide, thioether, thioester, aldehyde, alcoholate, carboxylic acid, or a combination thereof.
- non-aromatic internal electron donor comprises a Ci to C20 diester of a substituted or unsubstituted C2 to Cio dicarboxylic acid.
- R 1 and R 2 are, independently, Ci to C20 linear or branched alkyl, alkenyl, or cycloalkyl hydrocarbyl radicals;
- R 3 to R 6 are, independently, hydrogen, halogen, or Ci to C2 0 linear or branched alkyl, alkenyl, or cycloalkyl hydrocarbyl radicals, wherein the R 3 to R 6 radicals are not joined together, or wherein at least two of the R 3 to R 6 radicals are joined to form a cyclic divalent radical, or a combination thereof.
- the Ziegler-Natta catalyst system comprises 2.5 mol% to less than 50 mol% of the first electron donor based on total mol% of external electron donors wherein the first electron donor comprises dicyclopentyldimethoxysilane (DCPMS) and greater than 50 mol% of a second electron donor based on total mol% of electron donors wherein the second electron donor comprises propyltriethoxysilane (PTES).
- DCPMS dicyclopentyldimethoxysilane
- PTES propyltriethoxysilane
- MFR Melt Flow Rate
- Flexural Modulus The Flexural Modulus is measured according to ASTM D790A, using a crosshead speed of 1.27 mm/min (0.05 in/min), and a support span of 50.8 mm (2.0 in) using an Instron Machine.
- Tensile Strength The Tensile Strength at yield, elongation at yield and elongation at break were measured as per ASTM D 638, with a crosshead speed of 50.8 mm/min (2.0 in/min), and a gauge length of 50.8 mm (2.0 in), using an Instron Machine.
- Notched Izod Impact Strength The Notched Izod Impact Strength is measured as per ASTM D256 at room temperature (21 °C), using an equipment made by Empire Technologies Inc.
- HDT Heat Distortion Temperature
- Polydispersity Index The Polydispersity Index is obtained from oscillatory shear data, from the cross-over modulus and frequency as measured at 190°C as described in Zeichner GR, Patel PD (1981), "A Comprehensive study of polypropylene melt rheology”; Proceedings of the 2nd World Congress of Chemical Engineering, Montreal, Canada. Polymerization of Example 1 :
- Example 1 was produced in a pilot plant conditions, in a continuous stirred tank reactor (CSTR).
- the magnesium chloride supported titanium catalyst sold commercially as Avant ZN-168M is utilized with an external donor blend of propyltriethoxysilane and dicyclopentyldimethoxysilane.
- the catalyst composition preparation is carried out continuously in situ by contacting the catalyst solids, triethylaluminum, and the external electron donor system under the conditions known in the art to yield active, stereospecific catalyst for polymerization of propylene.
- the activated catalyst was continuously fed to a prepolymerization reactor where it was polymerized in propylene to a productivity of approximately 100 to 300 g-polymer/g-cat.
- the prepolymerized catalyst was then continuously fed to a continuously stirred tank reactor and polymerization continued at a reactor temperature of 70°C to yield homopolymer.
- the hydrogen (chain transfer agent) concentration used in the reactor as show in Table 2.
- the reactor slurry was continuously removed from the polymerization reactor and the homopolymer granules are continuously separated from the liquid propylene.
- the granules were passed through a dryer to remove the residual monomer and collected in Gaylord boxes. Examples 2-7 were produced in the same way with varying hydrogen levels in the reactor to achieve the desired melt flow rate (MFR).
- the homopolymer granules from the reactor were stabilized with 0.090 wt% IrganoxTM 1010, 0.045 wt% UltranoxTM 626A, and 0.10 wt% sodium benzoate (fine form), and pelletized on a twin screw extruder (Werner Pfliederer 30 mm). The pellets were then injection molded using ASTM test specimens and the physical properties tested as per ASTM guidelines.
- Comparative Example 1 is Borealis DaployTM WB 135HMS, a commercial grade- post reactor grafted polypropylene.
- Comparative Example 2 is a commercial grade polymer made with methylcyclohexyl dimethoxy silane (MCMS) external donor and a commercial Ziegler-Natta catalyst solids THC-C series supplied by Toho Titanium Co.
- Comparative Example 3 is exemplary of the polymer produced according to U.S. Patent No. 6,087,459, made under pilot plant conditions to provide a direct comparison of the polymers produced according to the '459 patent to the instant disclosure. The data is shown in Table 3.
- FIG. 1 shows the branching index g' of Example 2, indicating no evidence of long chain branching.
- long chain branched polymers have a branching index g' which decreases significantly lower than 1, yet as is shown in FIG. 1, the g' value remains close to 1.
- the branching index (g' v i s , also referred to herein as g') is calculated using the output of the SEC-DRI-LS-VIS method (described in page 37 of U.S. Patent No. 7,807,769 for g') as follows.
- the average intrinsic viscosity, [r ⁇ ] mg , of the sample is calculated by:
- FIG. 2 shows the complex viscosity vs. angular frequency for Example 2 in comparison to Comparative Examples 1 and 2. All shear/viscosity rheological experiments were conducted with an Anton Paar MCR500 Rheometer equipped with a 25 mm diameter parallel-plate fixture. Disk samples were prepared by compression molding to a thickness of 2.5 mm and diameter of 25 mm. The gap between the two parallel plates was maintained at 1.90 mm for all measurements.
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US14/434,825 US9453093B2 (en) | 2012-10-31 | 2013-10-08 | Broad molecular weight distribution polypropylene resins |
BR112015009432-5A BR112015009432B1 (en) | 2012-10-31 | 2013-10-08 | WIDE MOLECULAR WEIGHT DISTRIBUTION POLYPROPYLENE RESINS |
EP13851219.9A EP2914637B1 (en) | 2012-10-31 | 2013-10-08 | Broad molecular weight distribution polypropylene resins |
CN201380056585.2A CN104768980B (en) | 2012-10-31 | 2013-10-08 | The acrylic resin of wide molecular weight distribution |
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US20150252127A1 (en) | 2015-09-10 |
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CN104768980B (en) | 2018-04-13 |
BR112015009432B1 (en) | 2021-03-30 |
US9453093B2 (en) | 2016-09-27 |
EP2914637A4 (en) | 2016-05-11 |
BR112015009432A2 (en) | 2017-07-04 |
EP2914637B1 (en) | 2017-12-13 |
BR112015009432A8 (en) | 2019-09-17 |
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