WO2018146649A1 - Caps and closures - Google Patents
Caps and closures Download PDFInfo
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- WO2018146649A1 WO2018146649A1 PCT/IB2018/050855 IB2018050855W WO2018146649A1 WO 2018146649 A1 WO2018146649 A1 WO 2018146649A1 IB 2018050855 W IB2018050855 W IB 2018050855W WO 2018146649 A1 WO2018146649 A1 WO 2018146649A1
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- WIPO (PCT)
- Prior art keywords
- ethylene interpolymer
- ethylene
- metal
- closure
- cap
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D41/00—Caps, e.g. crown caps or crown seals, i.e. members having parts arranged for engagement with the external periphery of a neck or wall defining a pouring opening or discharge aperture; Protective cap-like covers for closure members, e.g. decorative covers of metal foil or paper
-
- 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
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/08—Presence of a deactivator
-
- 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
- C08F2420/00—Metallocene catalysts
- C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor
-
- 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
- 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
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- caps and closures comprising at least one ethylene interpolymer product manufactured in a continuous solution polymerization process utilizing at least two reactors employing at least one single-site catalyst formulation and at least one heterogeneous catalyst formulation to produce manufactured caps and closures having improved properties.
- Ethylene interpolymer products are used in caps and closure applications to produce a wide variety of manufactured articles, e.g. caps for carbonated or non- carbonated fluids, as well as dispensing closures including closures with a living- hinge functionality. Such caps and closures are typically produced using
- Non limiting examples of needs include: stiffer caps and closures (higher modulus) that allow the
- the ethylene interpolymer products disclosed are produced in a solution polymerization process, where catalyst components, solvent, monomers and hydrogen are fed under pressure to more than one reactor.
- solution reactor temperatures can range from about 80°C to about 300°C while pressures generally range from about 3MPag to about 45MPag and the ethylene interpolymer produced remains dissolved in the solvent.
- the residence time of the solvent in the reactor is relatively short, for example, from about 1 second to about 20 minutes.
- the solution process can be operated under a wide range of process conditions that allow the production of a wide variety of ethylene interpolymers. Post reactor, the polymerization reaction is quenched to prevent further polymerization, by adding a catalyst deactivator, and passivated, by adding an acid scavenger.
- the polymer solution is forwarded to a polymer recovery operation where the ethylene interpolymer is separated from process solvent, unreacted residual ethylene and unreacted optional a-olefin(s).
- the ethylene interpolymer products disclosed herein are synthesized using at least two reactors employing at least one single-site catalyst formulation and at least one
- caps and closures comprising at least one ethylene interpolymer product manufactured in a continuous solution polymerization process utilizing at least two reactors employing at least one single-site catalyst formulation and at least one heterogeneous catalyst formulation to produce manufactured caps and closures having improved properties.
- Embodiment of this disclosure include caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer product has a Dilution Index, Yd, greater than 0.
- caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer product has a Dilution Index, Yd, less than 0.
- caps or closures comprising at least one layer comprising an ethylene interpolymer product comprising:
- said first ethylene interpolymer is produced using a single site catalyst formulation comprising a component (i) defined by the formula:
- L A is selected from unsubstituted cyclopentadienyl, substituted
- M is a metal selected from titanium, hafnium and zirconium
- PI is a phosphinimine ligand
- Q is independently selected from a hydrogen atom, a halogen atom, a C1 -10 hydrocarbyl radical, a C1 -10 alkoxy radical and a C5-10 aryl oxide radical; wherein each of said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted or further substituted by a halogen atom, a CM S alkyl radical, a C1 -8 alkoxy radical, a C6-10 aryl or aryloxy radical, an amido radical which is unsubstituted or substituted by up to two C1 -8 alkyl radicals or a phosphido radical which is unsubstituted or substituted by up to two C1 -8 alkyl radicals;
- said second ethylene interpolymer is produced using a first in-line Ziegler- Natta catalyst formulation
- Embodiments of this include caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer has > 0.03 terminal vinyl
- Embodiments of this disclosure include caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer product has > 3 parts per million (ppm) of a total catalytic metal.
- caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer product has a Dilution Index, Yd, greater than 0 and > 0.03 terminal vinyl unsaturations per 1 00 carbon atoms or > 3 parts per million (ppm) of a total catalytic metal or a Dimensionless Modulus, Xd, > 0.
- caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer product has a Dilution Index, Yd, less than 0 and > 0.03 terminal vinyl unsaturations per 100 carbon atoms or > 3 parts per million (ppm) of a total catalytic metal or a Dimensionless Modulus, Xd, ⁇ 0.
- Yd Dilution Index
- ppm parts per million
- Additional embodiments include caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer product has > 0.03 terminal vinyl unsaturations per 1 00 carbon atoms and > 3 parts per million (ppm) of a total catalytic metal or a Dimensionless Modulus, Xd, > 0.
- Embodiments include caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer product has > 3 parts per million (ppm) of a total catalytic metal and a Dimensionless Modulus, Xd, > 0.
- caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer product has a Dilution Index, Yd, greater than 0 and > 0.03 terminal vinyl unsaturations per 100 carbon atoms and > 3 parts per million (ppm) of a total catalytic metal or a Dimensionless Modulus, Xd, > 0.
- Yd Dilution Index
- ppm parts per million
- caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer product has a Dilution Index, Yd, less than 0 and > 0.03 terminal vinyl unsaturations per 100 carbon atoms and > 3 parts per million (ppm) of a total catalytic metal or a Dimensionless Modulus, Xd, ⁇ 0.
- Yd Dilution Index
- ppm parts per million
- Additional embodiments include caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer product has a Dimensionless Modulus, Xd, > 0 and > 3 parts per million (ppm) of a total catalytic metal and a Dilution Index, Yd, greater than 0 or > 0.03 terminal vinyl unsaturations per 1 00 carbon atoms.
- Xd Dimensionless Modulus
- ppm parts per million
- Yd Dilution Index
- Additional embodiments include caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer product has a Dimensionless Modulus, Xd, ⁇ 0 and > 3 parts per million (ppm) of a total catalytic metal and a Dilution Index, Yd, less than 0 or > 0.03 terminal vinyl unsaturations per 100 carbon atoms.
- ppm parts per million
- Embodiments also include caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer product has a Dilution Index, Yd, greater than 0, a Dimensionless Modulus, Xd, > 0, > 3 parts per million (ppm) of a total catalytic metal and > 0.03 terminal vinyl unsaturations per 100 carbon atoms.
- Yd Dilution Index
- Xd a Dimensionless Modulus
- ppm parts per million
- Embodiments also include caps and closures having at least one layer containing an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; where the ethylene interpolymer product has a Dilution Index, Yd, less than 0, a Dimensionless Modulus, Xd, ⁇ 0, > 3 parts per million (ppm) of a total catalytic metal and > 0.03 terminal vinyl unsaturations per 100 carbon atoms.
- Yd Dilution Index
- Xd Dimensionless Modulus
- ppm parts per million
- the ethylene interpolymer products disclosed here have a melt index from about 0.3 to about 20 dg/minute, a density from about 0.948 to about 0.968 g/cm 3 , a Mw/Mn from about 2 to about 25 and a CDBI50 from about 54% to about 98%; where melt index is measured according to ASTM D1238 (2.16 kg load and 190°C) and density is measured according to ASTM D792.
- the disclosed ethylene interpolymer products contain: (i) from about 15 to about 60 weight percent of a first ethylene interpolymer having a melt index from about 0.01 to about 200 dg/minute and a density from about 0.855 g/cm 3 to about 0.975 g/cm 3 ; (ii) from about 30 to about 85 weight percent of a second ethylene interpolymer having a melt index from about 0.3 to about 1000 dg/minute and a density from about 0.89 g/cm 3 to about 0.975 g/cm 3 ; and (iii) optionally from about 0 to about 30 weight percent of a third ethylene interpolymer having a melt index from about 0.5 to about 2000 dg/minute and a density from about 0.89 to about 0.975 g/cm 3 ; where weight percent is the weight of the first, second or third ethylene polymer divided by the weight of ethylene interpolymer product.
- Embodiments of this disclosure include caps and closures comprising one or more ethylene interpolymer product synthesized in a solution polymerization process; where the ethylene interpolymer product may contain from 0 to about 1 .0 mole percent of one or more a-olefins.
- first ethylene interpolymer is synthesized using a single-site catalyst formulation and the second ethylene interpolymer is synthesized using a first heterogeneous catalyst formulation.
- caps and closures may contain ethylene interpolymers products where a third ethylene interpolymer is synthesized using a first heterogeneous catalyst formulation or a second
- the second ethylene interpolymer may be synthesized using a first in-line Ziegler Natta catalyst formulation or a first batch Ziegler-Natta catalyst formulation; optionally, the third ethylene interpolymer is synthesized using the first in-line Ziegler Natta catalyst formulation or the first batch Ziegler-Natta catalyst
- the optional third ethylene interpolymer may be synthesized using a second in-line Ziegler Natta catalyst formulation or a second batch Ziegler-Natta catalyst formulation.
- Embodiments of this disclosure include caps and closures containing an ethylene interpolymer product, where the ethylene interpolymer product has ⁇ 1 part per million (ppm) of a metal A; where metal A originates from the single-site catalyst formulation; non-limiting examples of metal A include titanium, zirconium or hafnium.
- Metals B and C are independently selected from the following non-limiting examples:
- Metals B and C may be the same metal.
- caps and closures contain ethylene interpolymer products where the first ethylene interpolymer has a first M w /M n , the second ethylene interpolymer has a second M w /M n and the optional third ethylene has a third M w /M n ; where the first M w /M n is lower than the second M w /M n and the optional third Mw/Mn.
- Embodiments also include ethylene interpolymer products where the blending of the second ethylene interpolymer and the third ethylene interpolymer form an ethylene interpolymer blend having a fourth M w /M n ; where the fourth M w /M n is not broader than the second M w /M n .
- Additional ethylene interpolymer product embodiments are characterized as having both the second M w /M n and the third Mw/Mn less than about 4.0.
- caps and closures include ethylene interpolymer products where the first ethylene interpolymer has a first CDBI50 from about 70 to about 98%, the second ethylene interpolymer has a second CDBI50 from about 45 to about 98% and the optional third ethylene interpolymer has a third CDBI50 from about 35 to about 98%.
- Other embodiments include ethylene interpolymer products where the first CDBI50 is higher than the second CDBI50; optionally the first CDBI50 is higher than the third CDBI50.
- Comparatives Q and R are comparative caps and closure HDPE resins available from NOVA Chemicals Inc.; CCs153 (0.9530 gem 3 , 1 .4 dg/min) and CCs757 (0.9589 g/cm 3 , 6.7 dg/min), respectively, produced in a dual reactor solution process using a single-site catalyst.
- Comparative V is a commercial caps and closure HDPE resin available from The Dow Chemical Company, Continuum
- DMDA-1250 NT 7 (0.957 g/cm 3 , 1 .5 dg/min), produced in a dual reactor gas phase process using a Ziegler-Natta catalyst.
- Comparative X and Y are a commercial caps and closure HDPE resins available from INEOS Olefins & Polymers USA; INEOS HDPE J50-1000-178 (0.951 g/cm 3 , 1 1 dg/min) and INEOS HDPE J60-800- 178 (0.961 g/cm 3 , 7.9 dg/min), respectively.
- interpolymer comprising an ethylene interpolymer synthesized using an inline Ziegler-Natta catalyst in a solution process (rheological reference);
- Examples 6, 101 , 102, 103, 1 10, 1 15, 200, 201 are ethylene interpolymer products as described in this disclosure comprising a first ethylene interpolymer synthesized using a single-site catalyst formulation and a second ethylene interpolymer synthesized using an in-line Ziegler-Natta catalyst formulation in a solution process;
- Examples 120, 130 and 131 are ethylene interpolymer products as described in this disclosure.
- Comparatives D and E are ethylene interpolymers comprising a first ethylene interpolymer synthesized using a single-site catalyst formation and a second ethylene interpolymer synthesized using a batch Ziegler-Natta catalyst formulation in a solution process; and
- Comparative A (open square, Yd > 0 and Xd ⁇ 0) is an ethylene interpolymer comprising a first and second ethylene interpolymer synthesized using a single-site catalyst formation in a solution process.
- Figure 3 illustrates a typical Van Gurp Palmen (VGP) plot of phase angle [°] versus complex modulus [kPa].
- Figure 5 compares the amount of terminal vinyl unsaturations per 100 carbon atoms (terminal vinyl/100 C) in the ethylene interpolymer products of this disclosure (solid circles) with Comparatives B, C, E, E2, G, H, H2, I and J (open triangles).
- Figure 6 compares the amount of total catalytic metal (ppm) in the ethylene interpolymer products of this disclosure (solid circles) with Comparatives B, C, E, E2, G, H, H2, I and J (open triangles).
- any numerical range recited herein is intended to include all sub-ranges subsumed therein.
- a range of to 10 is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 1 0; that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
- compositional ranges expressed herein are limited in total to and do not exceed 1 00 percent (volume percent or weight percent) in practice. Where multiple components can be present in a composition, the sum of the maximum amounts of each component can exceed 1 00 percent, with the understanding that, and as those skilled in the art readily understand, that the amounts of the components actually used will conform to the maximum of 1 00 percent.
- the term "monomer” refers to a small molecule that may chemically react and become chemically bonded with itself or other monomers to form a polymer.
- a-olefin is used to describe a monomer having a linear hydrocarbon chain containing from 3 to 20 carbon atoms having a double bond at one end of the chain.
- ethylene polymer refers to macromolecules produced from ethylene monomers and optionally one or more additional monomers; regardless of the specific catalyst or specific process used to make the ethylene polymer.
- the one or more additional monomers are called “comonomer(s)” and often include a-olefins.
- the term “homopolymer” refers to a polymer that contains only one type of monomer.
- Common ethylene polymers include high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultralow density polyethylene (ULDPE), plastomer and elastomers.
- ethylene polymer also includes polymers produced in a high pressure polymerization processes; non-limiting examples include low density polyethylene (LDPE), ethylene vinyl acetate copolymers (EVA), ethylene alkyl acrylate
- ethylene polymer also includes block copolymers which may include 2 to 4 comonomers.
- ethylene polymer also includes combinations of, or blends of, the ethylene polymers described above.
- ethylene interpolymer refers to a subset of polymers within the "ethylene polymer” group that excludes polymers produced in high pressure polymerization processes; non-limiting examples of polymers produced in high pressure processes include LDPE and EVA (the latter is a copolymer of ethylene and vinyl acetate).
- heterogeneous ethylene interpolymers refers to a subset of polymers in the ethylene interpolymer group that are produced using a heterogeneous catalyst formulation; non-limiting examples of which include Ziegler- Natta or chromium catalysts.
- homogeneous ethylene interpolymer refers to a subset of polymers in the ethylene interpolymer group that are produced using metallocene or single-site catalysts.
- homogeneous ethylene interpolymers have narrow molecular weight distributions, for example gel permeation chromatography (GPC) Mw/Mn values of less than 2.8; M w and M n refer to weight and number average molecular weights, respectively.
- GPC gel permeation chromatography
- M w and M n refer to weight and number average molecular weights, respectively.
- the M w /M n of heterogeneous ethylene interpolymers are typically greater than the M w /M n of homogeneous ethylene interpolymers.
- homogeneous ethylene interpolymers also have a narrow comonomer distribution, i.e. each macromolecule within the molecular weight distribution has a similar comonomer content.
- composition distribution breadth index "CDBI" is used to quantify how the
- comonomer is distributed within an ethylene interpolymer, as well as to differentiate ethylene interpolymers produced with different catalysts or processes.
- CDBI50 is defined as the percent of ethylene interpolymer whose composition is within 50% of the median comonomer composition; this definition is consistent with that described in U.S. Patent 5,206,075 assigned to Exxon Chemical Patents Inc.
- the CDBI50 of an ethylene interpolymer can be calculated from TREF curves (Temperature Rising Elution Fractionation); the TREF method is described in Wild, et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441 -455.
- the CDBI50 of homogeneous ethylene interpolymers are greater than about 70%.
- the CDBI50 of ⁇ -olefin containing heterogeneous ethylene interpolymers are generally lower than the CDBI50 of homogeneous ethylene interpolymers.
- linear homogeneous ethylene interpolymers have less than about 0.01 long chain branches per 1000 carbon atoms; while substantially linear ethylene interpolymers have greater than about 0.01 to about 3.0 long chain branches per 1000 carbon atoms.
- a long chain branch is macromolecular in nature, i.e. similar in length to the macromolecule that the long chain branch is attached to.
- homogeneous ethylene interpolymer refers to both linear homogeneous ethylene interpolymers and substantially linear homogeneous ethylene interpolymers.
- polyolefin includes ethylene polymers and propylene polymers; non-limiting examples of propylene polymers include isotactic, syndiotactic and atactic propylene homopolymers, random propylene copolymers containing at least one comonomer and impact polypropylene copolymers or heterophasic polypropylene copolymers.
- thermoplastic refers to a polymer that becomes liquid when heated, will flow under pressure and solidify when cooled.
- Thermoplastic polymers include ethylene polymers as well as other polymers commonly used in the plastic industry; non-limiting examples of other polymers commonly used include barrier resins (EVOH), tie resins, polyethylene terephthalate (PET), polyamides and the like.
- the term "monolayer” refers a cap or closure where the wall structure comprises a single layer.
- hydrocarbyl As used herein, the terms "hydrocarbyl", “hydrocarbyl radical” or
- hydrocarbyl group refers to linear or cyclic, aliphatic, olefinic, acetylenic and aryl (aromatic) radicals comprising hydrogen and carbon that are deficient by one hydrogen.
- an "alkyl radical” includes linear, branched and cyclic paraffin radicals that are deficient by one hydrogen radical; non-limiting examples include methyl (-CH3) and ethyl (-CH2CH3) radicals.
- alkenyl radical refers to linear, branched and cyclic hydrocarbons containing at least one carbon- carbon double bond that is deficient by one hydrogen radical.
- R1 and its superscript form “ R1” refers to a first reactor in a continuous solution polymerization process; it being understood that R1 is distinctly different from the symbol R 1 ; the latter is used in chemical formula, e.g.
- R2 and it's superscript form “ R2 " refers to a second reactor
- R3 and it's superscript form “ R3 " refers to a third reactor.
- Organometallic catalyst formulations that are efficient in polymerizing olefins are well known in the art.
- at least two catalyst formulations are employed in a continuous solution polymerization process.
- One of the catalyst formulations is a single-site catalyst formulation that produces a first ethylene interpolymer.
- the other catalyst formulation is a heterogeneous catalyst formulation that produces a second ethylene interpolymer.
- a third ethylene interpolymer is produced using the heterogeneous catalyst
- the at least one homogeneous ethylene interpolymer and the at least one heterogeneous ethylene interpolymer are solution blended and an ethylene interpolymer product is produced.
- the catalyst components which make up the single site catalyst formulation are not particularly limited, i.e. a wide variety of catalyst components can be used.
- One non-limiting embodiment of a single site catalyst formulation comprises the following three or four components: a bulky ligand-metal complex; an alumoxane co-catalyst; an ionic activator and optionally a hindered phenol.
- Table 2A of this disclosure “(i)” refers to the amount of "component (i)", i.e. the bulky ligand-metal complex added to R1 ; "(ii)” refers to "component (ii)", i.e.
- Non-limiting examples of component (i) are represented by formula (I):
- (L A ) represents a bulky ligand
- M represents a metal atom
- PI represents a phosphinimine ligand
- Q represents a leaving group
- a is 0 or 1
- b is 1 or 2
- (a+b) 2
- n is 1 or 2
- the sum of (a+b+n) equals the valance of the metal M.
- Non-limiting examples of the bulky ligand L A in formula (I) include
- Additional non-limiting examples include, cyclopentaphenanthreneyl ligands, unsubstituted or substituted indenyl ligands, benzindenyl ligands, unsubstituted or substituted fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands, phosphinimine, pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and the like, including hydrogenated versions thereof, for example tetrahydroindenyl ligands.
- L A may be any other ligand structure capable of ⁇ -bonding to the metal M, such embodiments include both n 3 -bonding and n, 5 -bonding to the metal M.
- L A may comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, sulfur and phosphorous, in combination with carbon atoms to form an open, acyclic, or a fused ring, or ring system, for example, a heterocyclopentadienyl ancillary ligand.
- L A includes bulky amides, phosphides, alkoxides, aryloxides, imides, carbolides, borollides, porphyrins, phthalocyanines, corrins and other polyazomacrocycles.
- Non-limiting examples of metal M in formula (I) include Group 4 metals, titanium, zirconium and hafnium.
- the phosphinimine ligand, PI is defined by formula (II):
- R p groups are independently selected from: a hydrogen atom; a halogen atom; C1 -20 hydrocarbyl radicals which are unsubstituted or substituted with one or more halogen atom(s); a C1-8 alkoxy radical; a Ce- ⁇ aryl radical; a Ce- ⁇ aryloxy radical; an amido radical; a silyl radical of formula -Si(R s )3, wherein the R s groups are independently selected from, a hydrogen atom, a C1 -8 alkyl or alkoxy radical, a Ce- ⁇ aryl radical, a Ce- ⁇ aryloxy radical, or a germanyl radical of formula - Ge(R G )3, wherein the R G groups are defined as R s is defined in this paragraph.
- the leaving group Q is any ligand that can be abstracted from formula (I) forming a catalyst species capable of polymerizing one or more olefin(s).
- An equivalent term for Q is an "activatable ligand", i.e. equivalent to the term “leaving group”.
- Q is a monoanionic labile ligand having a sigma bond to M.
- the value for n is 1 or 2 such that formula (I) represents a neutral bulky ligand-metal complex.
- Non-limiting examples of Q ligands include a hydrogen atom, halogens, C1 -20 hydrocarbyl radicals, C1 -20 alkoxy radicals, C5-10 aryl oxide radicals; these radicals may be linear, branched or cyclic or further substituted by halogen atoms, C1 -10 alkyl radicals, C1 -10 alkoxy radicals, Ce- ⁇ aryl or aryloxy radicals.
- Further non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms. In another embodiment, two Q ligands may form part of a fused ring or ring system.
- component (i) of the single site catalyst formulation include structural, optical or enantiomeric isomers (meso and racemic isomers) and mixtures thereof of the bulky ligand-metal complexes described in formula (I) above.
- the second single site catalyst component, component (ii) is an alumoxane co-catalyst that activates component (i) to a cationic complex.
- An equivalent term for "alumoxane” is "aluminoxane”; although the exact structure of this co-catalyst is uncertain, subject matter experts generally agree that it is an oligomeric species that contain repeating units of the general formula (III):
- R groups may be the same or different linear, branched or cyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n is from 0 to about 50.
- a non-limiting example of an alumoxane is methyl aluminoxane (or MAO) wherein each R group in formula (III) is a methyl radical.
- the third catalyst component (iii) of the single site catalyst formation is an ionic activator.
- ionic activators are comprised of a cation and a bulky anion; wherein the latter is substantially non-coordinating.
- Non-limiting examples of ionic activators are boron ionic activators that are four coordinate with four ligands bonded to the boron atom.
- Non-limiting examples of boron ionic activators include the following formulas (IV) and (V) shown below:
- R 5 is an aromatic hydrocarbyl (e.g. triphenyl methyl cation) and each R 7 is independently selected from phenyl radicals which are unsubstituted or substituted with from 3 to 5 substituents selected from fluorine atoms, C-1 -4 alkyl or alkoxy radicals which are unsubstituted or substituted by fluorine atoms; and a silyl radical of formula -Si(R 9 )3, where each R 9 is
- R 8 is selected from Ci-s alkyl radicals, phenyl radicals which are unsubstituted or substituted by up to three Ci-4 alkyl radicals, or one R 8 taken together with the nitrogen atom may form an anilinium radical and R 7 is as defined above in formula (IV).
- R 7 is a non-limiting example of R 7
- boron ionic activators may be described as salts of tetra(perfluorophenyl) boron; non-limiting examples include anilinium, carbonium, oxonium, phosphonium and sulfonium salts of
- ionic activators include: triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)-boron,
- tripropylammonium tetra(o,p-dimethylphenyl)boron tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(m,m- dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o- tolyl)boron, ⁇ , ⁇ -dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, ⁇ , ⁇ -diethylanilinium tetra(phenyl)n-butylboron, N,N-2,4,6- pentamethylanilinium tetra(phenyl)
- tetra(pentafluorophenyl)boron dicyclohexylammonium tetra(phenyl)boron, triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropillium tetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate, benzene(diazonium)tetrakispentafluorophenyl borate, tropillium
- tetrafluorophenyl)-borate Readily available commercial ionic activators include ⁇ , ⁇ -dimethylanilinium tetrakispentafluorophenyl borate, and triphenylmethylium tetrakispentafluorophenyl borate.
- the optional fourth catalyst component of the single site catalyst formation is a hindered phenol, component (iv).
- Non-limiting example of hindered phenols include butylated phenolic antioxidants, butylated hydroxytoluene, 2,4-di- tertiarybutyl-6-ethyl phenol, 4,4'-methylenebis (2,6-di-tertiary-butylphenol), 1 ,3, 5- trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and octadecyl-3- (3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate.
- heterogeneous catalyst formulations are well known to those skilled in the art, including, as non-limiting examples, Ziegler-Natta and chromium catalyst formulations.
- embodiments include an in-line and batch Ziegler-Natta catalyst formulations.
- in-line Ziegler-Natta catalyst formulation refers to the continuous synthesis of a small quantity of active Ziegler-Natta catalyst and immediately injecting this catalyst into at least one continuously operating reactor, where the catalyst polymerizes ethylene and one or more optional a-olefins to form an ethylene interpolymer.
- batch Ziegler-Natta catalyst formulation or "batch Ziegler-Natta procatalyst” refer to the synthesis of a much larger quantity of catalyst or procatalyst in one or more mixing vessels that are external to, or isolated from, the continuously operating solution polymerization process.
- the batch Ziegler-Natta catalyst formulation or batch Ziegler-Natta procatalyst, is transferred to a catalyst storage tank.
- the term "procatalyst” refers to an inactive catalyst formulation (inactive with respect to ethylene polymerization); the procatalyst is converted into an active catalyst by adding an alkyl aluminum co- catalyst. As needed, the procatalyst is pumped from the storage tank to at least one continuously operating reactor, where an active catalyst is formed and polymerizes ethylene and one or more optional a-olefins to form an ethylene interpolymer. The procatalyst may be converted into an active catalyst in the reactor or external to the reactor.
- a wide variety of chemical compounds can be used to synthesize an active Ziegler-Natta catalyst formulation.
- the following describes various chemical compounds that may be combined to produce an active Ziegler-Natta catalyst formulation.
- Those skilled in the art will understand that the embodiments in this disclosure are not limited to the specific chemical compound disclosed.
- An active Ziegler-Natta catalyst formulation may be formed from: a magnesium compound, a chloride compound, a metal compound, an alkyl aluminum co-catalyst and an aluminum alkyl.
- Table 2A of this disclosure “(v)” refers to "component (v)” the magnesium compound; the term “(vi)” refers to the “component (vi)” the chloride compound; “(vii)” refers to “component (vii)” the metal compound; “(viii)” refers to “component (viii)” alkyl aluminum co-catalyst; and “(ix)” refers to “component (ix)” the aluminum alkyl.
- Ziegler-Natta catalyst formulations may contain additional components; a non-limiting example of an additional component is an electron donor, e.g. amines or ethers.
- a non-limiting example of an active in-line Ziegler-Natta catalyst formulation can be prepared as follows.
- a solution of a magnesium compound (component (v)) is reacted with a solution of the chloride compound (component (vi)) to form a magnesium chloride support suspended in solution.
- magnesium compounds include Mg(R 1 )2; wherein the R 1 groups may be the same or different, linear, branched or cyclic hydrocarbyl radicals containing 1 to 10 carbon atoms.
- Non-limiting examples of chloride compounds include R 2 CI; wherein R 2 represents a hydrogen atom, or a linear, branched or cyclic hydrocarbyl radical containing 1 to 10 carbon atoms.
- magnesium compound may also contain an aluminum alkyl (component (ix)).
- aluminum alkyl include AI(R 3 )3, wherein the R 3 groups may be the same or different, linear, branched or cyclic hydrocarbyl radicals containing from 1 to 10 carbon atoms.
- a solution of the metal compound (component (vii)) is added to the solution of magnesium chloride and the metal compound is supported on the magnesium chloride.
- Non-limiting examples of suitable metal compounds include M(X) n or MO(X) n ; where M represents a metal selected from Group 4 through Group 8 of the Periodic Table, or mixtures of metals selected from Group 4 through Group 8; O represents oxygen ; and X represents chloride or bromide; n is an integer from 3 to 6 that satisfies the oxidation state of the metal.
- Additional non-limiting examples of suitable metal compounds include Group 4 to Group 8 metal alkyls, metal alkoxides (which may be prepared by reacting a metal alkyl with an alcohol) and mixed-ligand metal compounds that contain a mixture of halide, alkyl and alkoxide ligands.
- R 4 groups may be the same or different, hydrocarbyl groups having from 1 to 1 0 carbon atoms;
- the OR 5 groups may be the same or different, alkoxy or aryloxy groups wherein R 5 is a hydrocarbyl group having from 1 to 1 0 carbon atoms bonded to oxygen;
- Non-limiting examples of commonly used alkyl aluminum co-catalysts include trimethyl aluminum, triethyl aluminum, tributyl aluminum, dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminum butoxide, dimethyl aluminum chloride or bromide, diethyl aluminum chloride or bromide, dibutyl aluminum chloride or bromide and ethyl aluminum dichloride or dibromide.
- heterogeneous catalyst formulations include formulations where the "metal compound" is a chromium compound; non-limiting examples include silyl chromate, chromium oxide and chromocene.
- the chromium compound is supported on a metal oxide such as silica or alumina.
- Heterogeneous catalyst formulations containing chromium may also include co-catalysts; non-limiting examples of co-catalysts include
- Embodiments of this process includes at least two continuously stirred reactors, R1 and R2 and an optional tubular reactor R3. Feeds (solvent, ethylene, at least two catalyst formulations, optional hydrogen and optional a-olefin) are feed to at least two reactor continuously.
- a single site catalyst formulation is injected into R1 and a first heterogeneous catalyst formation is injected into R2 and optionally R3.
- a second heterogeneous catalyst formulation is injected into R3.
- the single site catalyst formulation includes an ionic activator (component (iii)), a bulky ligand-metal complex (component (i)), an alumoxane co-catalyst (component (ii)) and an optional hindered phenol (component (iv)), respectively.
- R1 and R2 may be operated in series or parallel modes of operation. To be more clear, in series mode 100% of the effluent from R1 flows directly into R2. In parallel mode, R1 and R2 operate independently and the effluents from R1 and R2 are combined downstream of the reactors.
- a heterogeneous catalyst formulation is injected into R2.
- a first in-line Ziegler-Natta catalyst formulation is injected into R2.
- a first in-line Ziegler-Natta catalyst formation is formed within a first heterogeneous catalyst assembly by optimizing the following molar ratios: (aluminum
- the time between the addition of component (vii) and the addition of the alkyl aluminum co-catalyst, component (viii), is also controlled; hereafter HUT-2 (the second Hold-Up-Time).
- HUT-3 the third Hold-Up-Time
- the alkyl aluminum co-catalyst may be injected directly into R2.
- a portion of the alkyl aluminum co-catalyst may be injected into the first heterogeneous catalyst assembly and the remaining portion injected directly into R2.
- the quantity of in-line heterogeneous catalyst formulation added to R2 is expressed as the parts-per-million (ppm) of metal compound (component (vii)) in the reactor solution, hereafter "R2 (vii) (ppm)". Injection of the in-line
- a second exit stream exiting R2
- the second exit stream is deactivated by adding a catalyst deactivator. If the second exit stream is not deactivated the second exit stream enters reactor R3.
- a suitable R3 design is a tubular reactor.
- one or more of the following fresh feeds may be injected into R3; solvent, ethylene, hydrogen, ⁇ -olefin and a first or second heterogeneous catalyst formulation; the latter is supplied from a second heterogeneous catalyst assembly.
- the chemical composition of the first and second heterogeneous catalyst formulations may be the same, or different, i.e. the catalyst components ((v) through (ix)), mole ratios and hold-up-times may differ in the first and second heterogeneous catalyst assemblies.
- heterogeneous catalyst assembly generates an efficient catalyst by optimizing holdup-times and the molar ratios of the catalyst components.
- a third ethylene interpolymer may, or may not, form.
- a third ethylene interpolymer will not form if a catalyst deactivator is added upstream of reactor R3.
- a third ethylene interpolymer will be formed if a catalyst deactivator is added downstream of R3.
- the optional third ethylene interpolymer may be formed using a variety of operational modes (with the proviso that catalyst deactivator is not added upstream).
- Non-limiting examples of operational modes include: (a) residual ethylene, residual optional a-olefin and residual active catalyst entering R3 react to form the third ethylene interpolymer, or; (b) fresh process solvent, fresh ethylene and optionally fresh a-olefin are added to R3 and the residual active catalyst entering R3 forms the third ethylene interpolymer, or; (c) a second in-line heterogeneous catalyst formulation is added to R3 to polymerize residual ethylene and residual optional ⁇ -olefin to form the third ethylene interpolymer, or; (d) fresh process solvent, ethylene, optional a-olefin and a second in-line heterogeneous catalyst formulation are added to R3 to form the third ethylene interpolymer.
- R3 produces a third exit stream (the stream exiting R3) containing the first ethylene interpolymer, the second ethylene interpolymer and optionally a third ethylene interpolymer.
- a catalyst deactivator may be added to the third exit stream producing a deactivated solution, with the proviso a catalyst deactivator is not added if a catalyst deactivator was added upstream of R3.
- the deactivated solution passes through a pressure let down device, a heat exchanger and a passivator is added forming a passivated solution.
- passivated solution passes through a series of vapor liquid separators and ultimately the ethylene interpolymer product enters polymer recover.
- Non-limiting examples of polymer recovery operations include one or more gear pump, single screw extruder or twin screw extruder that forces the molten ethylene interpolymer product through a pelletizer.
- Embodiments of the manufactured articles disclosed herein may also be formed from ethylene interpolymer products synthesized using a batch Ziegler- Natta catalyst.
- a first batch Ziegler-Natta procatalyst is injected into R2 and the procatalyst is activated within R2 by injecting an alkyl aluminum co-catalyst forming a first batch Ziegler-Natta catalyst.
- a second batch Ziegler- Natta procatalyst is injected into R3.
- a variety of solvents may be used as the process solvent; non-limiting examples include linear, branched or cyclic Cs to C12 alkanes.
- Non-limiting examples of a-olefins include C3 to C10 a-olefins. It is well known to individuals of ordinary experience in the art that reactor feed streams (solvent, monomer, oc- olefin, hydrogen, catalyst formulation etc.) must be essentially free of catalyst deactivating poisons; non-limiting examples of poisons include trace amounts of oxygenates such as water, fatty acids, alcohols, ketones and aldehydes. Such poisons are removed from reactor feed streams using standard purification practices; non-limiting examples include molecular sieve beds, alumina beds and oxygen removal catalysts for the purification of solvents, ethylene and a-olefins, etc.
- ES Ethylene Split
- the ethylene concentration in each reactor is also controlled.
- the R1 ethylene concentration is defined as the weight of ethylene in reactor 1 divided by the total weight of everything added to reactor 1 ; the R2 ethylene concentration (wt%) and R3 ethylene concentration (wt%) are defined similarly.
- Q R1 refers to the percent of the ethylene added to R1 that is converted into an ethylene interpolymer by the catalyst formulation.
- Q R2 and Q R3 represent the percent of the ethylene added to R2 and R3 that was converted into ethylene interpolymer, in the respective reactor.
- Q T represents the total or overall ethylene
- a-olefin may be added to the continuous solution polymerization process. If added, a-olefin may be proportioned or split between R1 , R2 and R3. This operational variable is referred to as the Comonomer Split (CS), i.e.
- CS Comonomer Split
- a catalyst deactivator substantially stops the polymerization reaction by changing active catalyst species to inactive forms.
- Suitable deactivators are well known in the art, non-limiting examples include: amines (e.g. U.S. Pat. No. 4,803,259 to Zboril et al.); alkali or alkaline earth metal salts of carboxylic acid (e.g. U.S. Pat. No. 4,105,609 to Machan et al.); water (e.g. U.S. Pat. No. 4,731 ,438 to Bernier et al.); hydrotalcites, alcohols and carboxylic acids (e.g. U.S. Pat. No. 4,379,882 to Miyata); or a combination thereof (U.S. Pat. No. 6,180,730 to Sibtain et al.).
- a passivator or acid scavenger Prior to entering the vapor/liquid separator, a passivator or acid scavenger is added to deactivated solution.
- Suitable passivators are well known in the art, non- limiting examples include alkali or alkaline earth metal salts of carboxylic acids or hydrotalcites.
- the number of solution reactors is not particularly important, with the proviso that the continuous solution polymerization process comprises at least two reactors that employ at least one single-site catalyst formulation and at least one heterogeneous catalyst formulation.
- the first ethylene interpolymer is produced with a single-site catalyst formulation. If the optional a-olefin is not added to reactor 1 (R1 ), then the ethylene interpolymer produced in R1 is an ethylene homopolymer. If an a-olefin is added, the following weight ratio is one parameter to control the density of the first ethylene interpolymer: ((a-olefin)/(ethylene)) R1 .
- the upper limit on ⁇ 1 may be about 0.975 g/cm 3 ; in some cases about 0.965 g/cm 3 ; and in other cases about 0.955 g/cm 3 .
- the lower limit on ⁇ 1 may be about 0.855 g/cm 3 ; in some cases about 0.865 g/cm 3 ; and in other cases about 0.875 g/cm 3 .
- CDBIso Composition Distribution Branching Index
- the upper limit on the CDBI50 of the first ethylene interpolymer may be about 98%, in other cases about 95% and in still other cases about 90%.
- the lower limit on the CDBI50 of the first ethylene interpolymer may be about 70%, in other cases about 75% and in still other cases about 80%.
- the first ethylene interpolymer has a lower M w /M n relative to the second ethylene interpolymer, where the second ethylene
- the interpolymer is produced with a heterogeneous catalyst formulation.
- the upper limit on the M w /M n of the first ethylene interpolymer may be about 2.8, in other cases about 2.5 and in still other cases about 2.2.
- the lower limit on the M w /M n the first ethylene interpolymer may be about 1 .7, in other cases about 1 .8 and in still other cases about 1 .9.
- the first ethylene interpolymer contains catalyst residues that reflect the chemical composition of the single-site catalyst formulation used.
- catalyst residues are typically quantified by the parts per million of metal in the first ethylene interpolymer, where metal refers to the metal in component (i), i.e. the metal in the "bulky ligand-metal complex;” hereafter (and in the claims) this metal will be referred to "metal A".
- metal A include Group 4 metals, titanium, zirconium and hafnium.
- the upper limit on the ppm of metal A in the first ethylene interpolymer may be about 1 .0 ppm, in other cases about 0.9 ppm and in still other cases about 0.8 ppm.
- the lower limit on the ppm of metal A in the first ethylene interpolymer may be about 0.01 ppm, in other cases about 0.1 ppm and in still other cases about 0.2 ppm.
- the amount of hydrogen added to R1 can vary over a wide range allowing the continuous solution process to produce first ethylene interpolymers that differ greatly in melt index, hereafter I2 1 (melt index is measured at 190°C using a 2.16 kg load following the procedures outlined in ASTM D1238).
- the quantity of hydrogen added to R1 is expressed as the parts-per-million (ppm) of hydrogen in R1 relative to the total mass in reactor R1 ; hereafter H2 R1 (ppm).
- the upper limit on I2 1 may be about 200 dg/min, in some cases about 100 dg/min; in other cases about 50 dg/min; and in still other cases about 1 dg/min.
- the lower limit on I2 1 may be about 0.01 dg/min; in some cases about 0.05 dg/min; in other cases about 0.1 dg/min ; and in still other cases about 0.5 dg/min.
- the upper limit on the weight percent (wt%) of the first ethylene interpolymer in the ethylene interpolymer product may be about 60 wt%, in other cases about 55 wt% and in still other cases about 50 wt%.
- the lower limit on the wt% of the first ethylene interpolymer in the ethylene interpolymer product may be about 15 wt%, in other cases about 25 wt%, and in still other cases about 30 wt%.
- ethylene interpolymer produced in R2 is an ethylene homopolymer. If an optional a-olefin is present in R2, the following weight ratio is one parameter to control the density of the second ethylene interpolymer produced in R2: ((a-olefin)/(ethylene)) R2 .
- ⁇ 2 refers to the density of the ethylene interpolymer produced in R2.
- the upper limit on ⁇ 2 may be about 0.975 g/cm 3 ; in some cases about 0.965 g/cm 3 ; and in other cases about 0.955 g/cm 3 .
- the lower limit on ⁇ 2 may be about 0.89 g/cm 3 ; in some cases about 0.90 g/cm 3 ; and in other cases about 0.91 g/cm 3 .
- a heterogeneous catalyst formulation is used to produce the second ethylene interpolymer. If the second ethylene interpolymer contains an a-olefin, the CDBI50 of the second ethylene interpolymer is lower relative to the CDBI50 of the first ethylene interpolymer that was produced with a single-site catalyst formulation.
- the upper limit on the CDBI50 of the second ethylene interpolymer may be about 70%, in other cases about 65% and in still other cases about 60%.
- the lower limit on the CDBI50 of the second ethylene interpolymer (that contains an a-olefin) may be about 45%, in other cases about 50% and in still other cases about 55%.
- the second ethylene interpolymer is an ethylene homopolymer.
- a homopolymer which does not contain a-olefin, one can still measure a CDBI50 using TREF.
- the upper limit on the CDBI50 of the second ethylene interpolymer may be about 98%, in other cases about 96% and in still other cases about 95%.
- the lower limit on the CDBI50 may be about 88%, in other cases about 89% and in still other cases about 90%.
- the CDBI50 of the first ethylene interpolymer is higher than the CDBI50 of the second ethylene interpolymer.
- the Mw/Mn of second ethylene interpolymer is higher than the M w /M n of the first ethylene interpolymer.
- the upper limit on the M w /M n of the second ethylene interpolymer may be about 4.4, in other cases about 4.2 and in still other cases about 4.0.
- the lower limit on the M w /M n of the second ethylene interpolymer may be about 2.2.
- M w /M n 's of 2.2 are observed when the melt index of the second ethylene interpolymer is high, or when the melt index of the ethylene interpolymer product is high, e.g. greater than 10 g/10 minutes.
- the lower limit on the Mw/Mn of the second ethylene interpolymer may be about 2.4 and in still other cases about 2.6.
- the second ethylene interpolymer contains catalyst residues that reflect the chemical composition of heterogeneous catalyst formulation.
- heterogeneous catalyst residues are typically quantified by the parts per million of metal in the second ethylene interpolymer, where the metal refers to the metal originating from component (vii), i.e. the "metal compound”; hereafter (and in the claims) this metal will be referred to as "metal B".
- metal B include metals selected from Group 4 through Group 8 of the Periodic Table, or mixtures of metals selected from Group 4 through Group 8.
- the upper limit on the ppm of metal B in the second ethylene interpolymer may be about 12 ppm, in other cases about 10 ppm and in still other cases about 8 ppm.
- the lower limit on the ppm of metal B in the second ethylene interpolymer may be about 0.5 ppm, in other cases about 1 ppm and in still other cases about 3 ppm. While not wishing to be bound by any particular theory, in series mode of operation it is believed that the chemical environment within the second reactor deactivates the single site catalyst formulation, or; in parallel mode of operation the chemical environment within R2 deactivates the single site catalyst formation.
- the amount of hydrogen added to R2 can vary over a wide range which allows the continuous solution process to produce second ethylene interpolymers that differ greatly in melt index, hereafter I2 2 .
- the quantity of hydrogen added is expressed as the parts-per-million (ppm) of hydrogen in R2 relative to the total mass in reactor R2; hereafter H2 R2 (ppm).
- the upper limit on I2 2 may be about 1000 dg/min; in some cases about 750 dg/min; in other cases about 500 dg/min; and in still other cases about 200 dg/min.
- the lower limit on I2 2 may be about 0.3 dg/min, in some cases about 0.4 dg/min, in other cases about 0.5 dg/min, and in still other cases about 0.6 dg/min.
- the upper limit on the weight percent (wt%) of the second ethylene interpolymer in the ethylene interpolymer product may be about 85 wt%, in other cases about 80 wt% and in still other cases about 70 wt%.
- the lower limit on the wt % of the second ethylene interpolymer in the ethylene interpolymer product may be about 30 wt%; in other cases about 40 wt% and in still other cases about 50 wt%.
- a third ethylene interpolymer is not produced in R3 if a catalyst deactivator is added upstream of R3. If a catalyst deactivator is not added and optional a-olefin is not present then the third ethylene interpolymer produced in R3 is an ethylene homopolymer. If a catalyst deactivator is not added and optional ⁇ -olefin is present in R3, the following weight ratio determines the density of the third ethylene interpolymer: ((a-olefin)/(ethylene)) R3 . In the continuous solution polymerization process ((a-olefin)/(ethylene)) R3 is one of the control parameter used to produce a third ethylene interpolymer with a desired density.
- ⁇ 3 refers to the density of the ethylene interpolymer produced in R3.
- the upper limit on ⁇ 3 may be about 0.975 g/cm 3 ; in some cases about 0.965 g/cm 3 ; and in other cases about 0.955 g/cm 3 .
- the lower limit on ⁇ 3 may be about 0.89 g/cm 3 , in some cases about 0.90 g/cm 3 ; and in other cases about 0.91 g/cm 3 .
- a second heterogeneous catalyst formulation may be added to R3.
- the upper limit on the CDBI50 of the optional third ethylene interpolymer may be about 65%, in other cases about 60% and in still other cases about 55%.
- the CDBI50 of an a-olefin containing optional third ethylene interpolymer will be lower than the CDBI50 of the first ethylene interpolymer produced with the single-site catalyst formulation.
- the lower limit on the CDBI50 of the optional third ethylene interpolymer may be about 35%, in other cases about 40% and in still other cases about 45%. If an a-olefin is not added to the continuous solution polymerization process the optional third ethylene interpolymer is an ethylene homopolymer.
- the upper limit on the CDBI50 may be about 98%, in other cases about 96% and in still other cases about 95%.
- the lower limit on the CDBI50 may be about 88%, in other cases about 89% and in still other cases about 90%.
- the CDBI50 of the first ethylene interpolymer is higher than the CDBI50 of the third ethylene interpolymer and second ethylene interpolymer.
- the upper limit on the M w /M n of the optional third ethylene interpolymer may be about 5.0, in other cases about 4.8 and in still other cases about 4.5.
- the lower limit on the M w /M n of the optional third ethylene interpolymer may be about 2.2, in other cases about 2.4 and in still other cases about 2.6.
- the M w /M n of the optional third ethylene interpolymer is higher than the M w /M n of the first ethylene
- the second and third ethylene interpolymer When blended together, the second and third ethylene interpolymer have a fourth M w /M n which is not broader than the M w /M n of the second ethylene interpolymer.
- the catalyst residues in the optional third ethylene interpolymer reflect the chemical composition of the heterogeneous catalyst formulation(s) used, i.e. the first and optionally a second heterogeneous catalyst formulation.
- the chemical compositions of the first and second heterogeneous catalyst formulations may be the same or different; for example a first component (vii) and a second component (vii) may be used to synthesize the first and second heterogeneous catalyst formulation.
- metal B refers to the metal that originates from the first component (vii).
- metal C refers to the metal that originates from the second component (vii).
- Metal B and optional metal C may be the same, or different.
- Non-limiting examples of metal B and metal C include metals selected from Group 4 through Group 8 of the Periodic Table, or mixtures of metals selected from Group 4 through Group 8.
- the upper limit on the ppm of (metal B + metal C) in the optional third ethylene interpolymer may be about 12 ppm, in other cases about 10 ppm and in still other cases about 8 ppm.
- the lower limit on the ppm of (metal B + metal C) in the optional third ethylene interpolymer may be about 0.5 ppm, in other cases about 1 ppm and in still other cases about 3 ppm.
- H2 R3 Adjusting the amount of hydrogen in R3, hereafter H2 R3 (ppm), allows the continuous solution process to produce third ethylene interpolymers that differ widely in melt index, hereafter I2 3 .
- the upper limit on I2 3 may be about 2000 dg/min; in some cases about 1500 dg/min; in other cases about 1000 dg/min; and in still other cases about 500 dg/min.
- the lower limit on I2 3 may be about 0.5 dg/min, in some cases about 0.6 dg/min, in other cases about 0.7 dg/min, and in still other cases about 0.8 dg/min.
- the upper limit on the weight percent (wt%) of the optional third ethylene interpolymer in the ethylene interpolymer product may be about 30 wt%, in other cases about 25 wt% and in still other cases about 20 wt%.
- the lower limit on the wt% of the optional third ethylene interpolymer in the ethylene interpolymer product may be 0 wt%, in other cases about 5 wt% and in still other cases about 10 wt%.
- the upper limit on the density of the ethylene interpolymer product suitable for caps or closures about 0.970 g/cm 3 ; in some cases about 0.969 g/cm 3 ; and in other cases about 0.968 g/cm 3 .
- the lower limit on the density of the ethylene interpolymer product suitable for caps or closures may be about 0.945 g/cm 3 ; in some cases about 0.947 g/cm 3 ; and in other cases about 0.948 g/cm 3 .
- the upper limit on the CDBI50 of the ethylene interpolymer product may be about 97%, in other cases about 90% and in still other cases about 85%.
- An ethylene interpolymer product with a CDBI50 of 97% may result if an a-olefin is not added to the continuous solution polymerization process; in this case, the ethylene interpolymer product is an ethylene homopolymer.
- the lower limit on the CDBI50 of an ethylene interpolymer may be about 50%, in other cases about 55% and in still other cases about 60%.
- the upper limit on the M w /M n of the ethylene interpolymer product may be about 6, in other cases about 5 and in still other cases about 4.
- the lower limit on the Mw/Mn of the ethylene interpolymer product may be 2.0, in other cases about 2.2 and in still other cases about 2.4.
- the catalyst residues in the ethylene interpolymer product reflect the chemical compositions of: the single-site catalyst formulation employed in R1 ; the first heterogeneous catalyst formulation employed in R2; and optionally the first or optionally the first and second heterogeneous catalyst formulation employed in R3.
- catalyst residues were quantified by measuring the parts per million of catalytic metal in the ethylene interpolymer products.
- the elemental quantities (ppm) of magnesium, chlorine and aluminum were quantified.
- Catalytic metals originate from two or optionally three sources, specifically: 1 ) "metal A” that originates from component (i) that was used to form the single-site catalyst formulation; (2) “metal B” that originates from the first component (vii) that was used to form the first heterogeneous catalyst formulation; and (3) optionally “metal C” that originates from the second component (vii) that was used to form the optional second heterogeneous catalyst formulation.
- Metals A, B and C may be the same or different.
- total catalytic metal is equivalent to the sum of catalytic metals A+B+C.
- first total catalytic metal and “second total catalyst metal” are used to differentiate between the first ethylene interpolymer product of this disclosure and a comparative
- polyethylene composition that were produced using different catalyst formulations.
- the upper limit on the ppm of metal A in the ethylene interpolymer product may be about 0.6 ppm, in other cases about 0.5 ppm and in still other cases about 0.4 ppm.
- the lower limit on the ppm of metal A in the ethylene interpolymer product may be about 0.001 ppm, in other cases about 0.01 ppm and in still other cases about 0.03 ppm.
- the upper limit on the ppm of (metal B + metal C) in the ethylene interpolymer product may be about 1 1 ppm, in other cases about 9 ppm and in still other cases about 7 ppm.
- the lower limit on the ppm of (metal B + metal C) in the ethylene interpolymer product may be about 0.5 ppm, in other cases about 1 ppm and in still other cases about 3 ppm.
- ethylene interpolymers may be produced where the catalytic metals (metal A, metal B and metal C) are the same metal; a non-limiting example would be titanium.
- the ppm of (metal B + metal C) in the ethylene interpolymer product is calculated using equation (VII):
- ppm (B + C) ((pp m (A + B + C) _ (fA x ppm A ))/(1 -f A ) (VII)
- ppm (B+C) is the calculated ppm of (metal B + metal C) in the ethylene interpolymer product
- ppm ⁇ A+B+c) is the total ppm of catalyst residue in the ethylene interpolymer product as measured experimentally, i.e.
- f A represents the weight fraction of the first ethylene interpolymer in the ethylene interpolymer product, f A may vary from about 0.15 to about 0.6; and ppm A represents the ppm of metal A in the first ethylene interpolymer.
- Embodiments of the ethylene interpolymer products disclosed herein have lower catalyst residues relative to the polyethylene polymers described in US 6,277,931 .
- Higher catalyst residues in U.S. 6,277,931 increase the complexity of the continuous solution polymerization process; an example of increased
- the upper limit on the "total catalytic metal,” i.e. the total ppm of (metal A ppm + metal B ppm + optional metal C ppm) in the ethylene interpolymer product may be about 1 1 ppm, in other cases about 9 ppm and in still other cases about 7.
- the lower limit on the total ppm of catalyst residuals (metal A + metal B + optional metal C) in the ethylene interpolymer product may be about
- the upper limit on melt index of the ethylene interpolymer product may be about 15 dg/min; in some cases about 14 dg/min; in other cases about 12 dg/min; and in still other cases about 10 dg/min.
- the lower limit on the melt index of the ethylene interpolymer product may be about 0.5 dg/min, in some cases about 0.6 dg/min; in other cases about 0.7 dg/min; and in still other cases about 0.8 dg/min.
- the upper limit on the melt index of the ethylene interpolymer product may be about 8 dg/min, in some cases about 7 dg/min; in other cases about 5 dg/min; and in still other cases about 3 dg/min.
- interpolymer product may be about 0.3, in some cases about 0.4 dg/min, in some cases about 0.5 dg/min, in other cases about 0.6 dg/min, and in still other cases about 0.7 dg/min.
- Example 13 A computer generated ethylene interpolymer product is illustrated in Table 1 . This simulations was based on fundamental kinetic models (with kinetic constants specific for each catalyst formulation) as well as feed and reactor conditions. The simulation was based on the configuration of the solution pilot plant described below, which was used to produce the examples of ethylene interpolymer products disclosed herein. Simulated Example 13 was synthesized using a single-site catalyst formulation (PIC-1 ) in R1 and an in-line Ziegler-Natta catalyst formulation in R2 and R3.
- PIC-1 single-site catalyst formulation
- R2 and R3 an in-line Ziegler-Natta catalyst formulation
- Table 1 discloses a non-limiting example of the density, melt index and molecular weights of the first, second and third ethylene interpolymers produced in the three reactors (R1 , R2 and R3); these three interpolymers are combined to produce Simulated Example 13 (the ethylene polymer product). As shown in Table 1,
- the Simulated Example 13 product has a density of 0.9169 g/cm 3 , a melt index of 1 .0 dg/min, a branch frequency of 12.1 (the number of C6-branches per 1000 carbon atoms (1 -octene comonomer)) and a M w /M n of 3.1 1 .
- Simulated Example 13 comprises: a first, second and third ethylene interpolymer having a first, second and third melt index of 0.31 dg/min, 1 .92 dg/min and 4.7 dg/min, respectively; a first, second and third density of 0.9087 g/cm 3 , 0.9206 g/cm 3 and 0.9154 g/cm 3 , respectively; a first, second and third M w /M n of 2.03 M w /M n , 3.29 M w /M n and 3.28 Mw/Mn, respectively; and a first, second and third CDBI50 of 90 to 95%, 55 to 60% and 45 to 55%, respectively.
- the simulated production rate of Simulated Example 13 was 90.9 kg/hr and the R3 exit temperature was 217.1 °C.
- Example 81 and Comparative Example 20 had a target density of about 0.953 g/cm 3 and a target melt index of about 1 .5 dg/min;
- Example 91 and Comparative Example 30 had a target density of about 0.958 g/cm 3 and a target melt index of about 7.0 dg/min;
- Example 1001 and Example 1002 had a target density of about 0.955 g/cm 3 and a target melt index of about 0.6 dg/min.
- Examples 81 , 91 , 1001 and 1002 were manufactured using a single-site catalyst formulation in reactor 1 and an in-line Ziegler-Natta catalyst formulation in reactor 2.
- Comparative Examples 20 and 30 were manufactured using a single-site catalyst formulation in both reactors 1 and 2. The production rate of Example 81 was 15% higher relative to Comparative
- Example 20 The production rate of Example 91 was 26% higher relative to
- Comparative Example 30 Examples (81 , 91 , 1 001 and 1002) and Comparative Examples (20 and 30) were all produced with reactor 1 and 2 configured in series, i.e. the effluent from reactor 1 flowed directly into reactor 2. In all examples the comonomer used was 1 -octene.
- Comparatives Q is a commercial caps and closure ethylene interpolymer available from NOVA Chemicals Inc. designated CCs153-A (0.9530 gem 3 and 1 .4 dg/min), which was produced in a dual reactor solution process using a single-site catalyst.
- Comparative V is a commercial caps and closure ethylene interpolymer available from The Dow Chemical Company, Continuum DMDA-1250 NT 7 (0.9550 g/cm 3 , 1 .5 dg/min), produced in a dual reactor gas phase process using a Ziegler- Natta catalyst, which was produced in a dual reactor gas phase process using a batch Ziegler-Natta catalyst formulation.
- the rectangle defined by Area I defines a melt index region that ranges from about > 0.4 dg/min to ⁇ 5 dg/min.
- the disclosed ethylene interpolymer product, Example 81 has a value of
- CCM continuous compression molding
- Comparative R is a commercial caps and closure ethylene
- Comparatives Y and X are commercial caps and closure ethylene interpolymer available from INEOS Olefins & Polymers USA; INEOS HDPE J50-1000-178 and INEOS HDPE J60-800-178, respectively.
- the rectangle defined by Area II defines a melt index region that ranges from > 5 dg/min to ⁇ 20 dg/min.
- higher melt indexes (5 to 20 dg/min) are useful for cap and closure manufacturing in injection molding processes, i.e. higher melt indexes reduce residual stresses (crystallized into the part) that may cause warped surface within the cap or closure.
- Lower melt elasticity as indicated by lower G' values, increases the degree of polymer chain relaxation, which dissipates residual stresses, allowing the
- caps and closures having the expected dimensions, or the "as designed" dimensions are advantageous in downstream processing; e.g. in downstream processes where bottles are filled and the cap or closure is fitted to the bottle.
- Table 3 compares the physical properties of Examples 1001 and 1002 with all the other Examples and Comparatives disclosed herein.
- the rectangle defined by Area III defines a melt index region that ranges from > 0.3 dg/min to ⁇ 8 dg/min.
- the disclosed ethylene interpolymer product, Examples 1001 and 1002 have a value of
- Example 1001 and 102 and similar materials have a
- G'[@G" 500Pa] values from > 80 Pa to ⁇ 120 Pa, which differs from the Examples that fall into the range of Areas I and II and the Comparatives
- Type I Yd > 0 and Xd ⁇ 0;
- Type II Yd > 0 and Xd > 0;
- Type III Yd ⁇ 0 and Xd > 0.
- Comparative S (open triangle) was used as the rheological reference in the Dilution Index test protocol.
- Comparative S is an ethylene interpolymer product comprising an ethylene interpolymer synthesized using an in-line Ziegler-Natta catalyst in one solution reactor, i.e. SCLAIR® FP120-C which is an ethylene/1 -octene interpolymer available from NOVA Chemicals Corporation (Calgary, Alberta, Canada).
- Comparatives D and E are ethylene interpolymer products comprising a first ethylene interpolymer synthesized using a single-site catalyst formation and a second ethylene interpolymer synthesized using a batch Ziegler-Natta catalyst formulation employing a dual reactor solution process, i.e. ELITE® 51 00G and ELITE 5400G, respectively, both ethylene/1 -octene
- Comparative A open square, Yd > 0 and Xd ⁇ 0 was an ethylene
- interpolymer product comprising a first and second ethylene interpolymer synthesized using a single-site catalyst formation in a dual reactor solution process, i.e. SURPASS FPs1 17-C which is an ethylene/1 -octene interpolymer available from NOVA Chemicals Corporation (Calgary, Alberta, Canada).
- blends of ethylene interpolymers may exhibit a hierarchical structure in the melt phase.
- the ethylene interpolymer components may be, or may not be, homogeneous down to the molecular level depending on interpolymer miscibility and the physical history of the blend.
- Such hierarchical physical structure in the melt is expected to have a strong impact on flow and hence on processing and converting, as well as the end-use properties of manufactured articles.
- the nature of this hierarchical physical structure between interpolymers can be characterized.
- the hierarchical physical structure of ethylene interpolymers can be characterized using melt rheology.
- a convenient method can be based on the small amplitude frequency sweep tests.
- Such rheology results are expressed as the phase angle Sas a function of complex modulus G * , referred to as van Gurp- Palmen plots (as described in M. Van Gurp, J. Palmen, Rheol. Bull. (1 998) 67(1 ): 5- 8; and Dealy J, Plazek D. Rheol. Bull. (2009) 78(2): 1 6-31 ).
- the phase angle ⁇ 5 increases toward its upper bound of 90° with G * becoming sufficiently low.
- a typical VGP plot is shown in Figure 3.
- the VGP plots are a signature of resin architecture.
- the rise of ⁇ 5 toward 90° is monotonic for an ideally linear, monodisperse interpolymer.
- the S ⁇ G * ) for a branched interpolymer or a blend containing a branched interpolymer may show an inflection point that reflects the topology of the branched interpolymer (see S. Trinkle, P. Walter, C. Friedrich, Rheo. Acta (2002) 41 : 1 03-1 13).
- the deviation of the phase angle ⁇ from the monotonic rise may indicate a deviation from the ideal linear interpolymer either due to presence of long chain branching if the inflection point is low (e.g. ⁇ ⁇ 20°) or a blend containing at least two interpolymers having dissimilar branching structure if the inflection point is high (e.g., ⁇ > 70°).
- the cross-over point is taken as the reference as it is known to be a characteristic point that correlates with Ml, density and other specifications of an ethylene interpolymer.
- the cross-over modulus is related to the plateau modulus for a given molecular weight distribution (see S. Wu. J. Polym Sci, Polym Phys Ed (1 989) 27:723; M. R. Nobile, F. Cocchini. Rheol Acta (2001 ) 40:1 1 1 ).
- the two decade shift in phase angle 5 ⁇ s to find the comparable points where the individual viscoelastic responses of constituents could be detected. This two decade shift is shown in Figure 4.
- Vd ⁇ 5 C - (C 0 - C ie c ⁇ ) "Dimensionless Modulus (Xd)"
- the Dilution Index reflects whether the blend behaves like a simple blend of linear ethylene interpolymers (lacking hierarchical structure in the melt) or shows a distinctive response that reflects a hierarchical physical structure within the melt.
- Type I upper left quadrant ethylene interpolymer products of this disclosure (solid symbols) have Yd > 0; in contrast, Type III (lower right quadrant) comparative ethylene interpolymers, Comparative D and E have Yd ⁇ 0.
- the first ethylene interpolymer single-site catalyst
- the second ethylene interpolymer in-line Ziegler Natta catalyst
- the melt comprising a first ethylene interpolymer (single-site catalyst) and a second ethylene interpolymer (batch Ziegler Natta catalyst) possesses a hierarchical structure.
- the ethylene interpolymer products of this disclosure fall into one of two quadrants: Type I with Xd ⁇ 0, or; Type II with Xd > 0.
- the Dimensionless Modulus (Xd) reflects differences (relative to the reference sample) that are related to the overall molecular weight, molecular weight distribution (M w /M n ) and short chain branching.
- the Dimensionless Modulus (Xd) may be considered to be related to the M w /M n and the radius of gyration ( ⁇ Rg> 2 ) of the ethylene interpolymer in the melt.
- increasing Xd has similar effects as increasing M w /M n and/or ⁇ R g > 2 , without the risk of including lower molecular weight fraction and sacrificing certain related properties.
- Comparative A comprises a first and second ethylene interpolymer synthesized with a single-site catalyst
- the solution process disclosed herein enables the manufacture of ethylene interpolymer products having higher Xd.
- Xd increases the macromolecular coils of higher molecular weight fraction are more expanded (conceptually higher ⁇ Rg> 2 ) and upon crystallization the probability of tie chain formation is increased resulting in higher toughness properties.
- the polyethylene art is replete with disclosures that correlate higher toughness (for example improved ESCR and/or PENT in molded articles) with an increasing probability of tie chain formation.
- the upper limit on Yd may be about 20, in some cases about 1 5 and is other cases about 1 3.
- the lower limit on Yd may be about -30, in some cases -25, in other cases -20 and in still other cases -1 5.
- the upper limit on Xd is 1 .0, in some cases about 0.95 and in other cases about 0.9.
- the lower limit on Xd is -2, in some cases -1 .5 and in still other cases -1 .0.
- Figure 5 compares the terminal vinyl/100 C content of the ethylene interpolymers of this disclosure with several Comparatives. The data shown in Figure 5 is also tabulated in Tables 5A and 5B.
- the average terminal vinyl content in the ethylene interpolymer of this disclosure was 0.045 terminal vinyls/100 C; the terminal vinyl unsaturation of Example 81 and 91 were close to this average, i.e. 0.044 and 0.041 terminal vinyl/100 C, respectively.
- the terminal vinyl unsaturation of Example 1001 and 1002 were close to this average, i.e. 0.045 terminal vinyl/100 C.
- the average terminal vinyl content in the Comparative samples was 0.023 terminal vinyls/100 C.
- the Comparatives shown in Figure 5 also comprise a first ethylene interpolymer synthesized with a single-site catalyst formulation and a second ethylene interpolymer synthesized with a heterogeneous catalyst formulation.
- Figure 6 compares the total catalytic metal content of the disclosed ethylene interpolymers with several Comparatives.
- Figure 6 data is also tabulated in Tables 6A and 6B. All of the comparatives in Figure 6 and Tables 6A and 6B are ELITE products available from The Dow Chemical Company (Midland, Michigan, USA), for additional detail see the section above.
- the average total catalytic metal content in the ethylene interpolymers of this disclosure was 7.02 ppm of titanium.
- elemental analysis N.A.A.
- Figure 5 clearly shows that 7.02 ppm of titanium is a reasonable estimate (as reported in Table 3) for residual titanium in Examples 81 and 91 .
- the average total catalytic metal in the Comparative samples shown in Figure 6 was 1 .63 ppm of titanium.
- the ethylene interpolymers of this disclosure are significantly different from the Comparatives, i.e.
- interpolymer products may be used include: deli containers, margarine tubs, trays, cups, lids, bottles, bottle cap liners, pails, crates, drums, bumpers, industrial bulk containers, industrial vessels, material handling containers, playground equipment, recreational equipment, safety equipment, wire and cable applications (power cables, communication cables and conduits), tubing and hoses, pipe applications (pressure pipe and non-pressure pipe, e.g. natural gas distribution, water mains, interior plumbing, storm sewer, sanitary sewer, corrugated pipes and conduit), foamed articles (foamed sheet or bun foam), military packaging (equipment and ready meals), personal care packaging (diapers and sanitary products), cosmetic, pharmaceutical and medical packaging, truck bed liners, pallets and automotive dunnage.
- the rigid manufactured articles summarized in this paragraph contain one or more of the ethylene interpolymer products having improved heat deflection temperature (HDT), faster crystallization rate (reduced ti/2) and higher melt strength.
- HDT heat deflection temperature
- the desired physical properties of rigid manufactured articles depend on the application of interest.
- desired properties include:
- C elasticity
- ESCR environmental stress crack resistance
- PENT slow crack growth resistance
- shore hardness heat deflection
- HDT high temperature
- VICAT softening point VICAT softening point
- IZOD impact strength ARM impact resistance
- Charpy impact resistance Charpy impact resistance
- color whiteness and/or yellowness index
- the ethylene interpolymer products and the caps and closures claimed may optionally include, depending on its intended use, additives and adjuvants.
- additives and adjuvants include, anti-blocking agents, antioxidants, heat stabilizers, slip agents, processing aids, anti-static additives, colorants, dyes, filler materials, light stabilizers, light absorbers, lubricants, pigments, plasticizers, nucleating agents or a mixture of more than one nucleating agent, and combinations thereof.
- each specimen was conditioned for at least 24 hours at 23
- ASTM conditions refers to a laboratory that is maintained at 23 ⁇ 2°C and 50 ⁇ 10% relative humidity.
- Ethylene interpolymer product densities were determined using ASTM D792- 13 (November 1 , 2013). Melt Index
- Ethylene interpolymer product melt index was determined using ASTM D1238 (August 1 , 2013). Melt indexes, I2, le, ho and I21 were measured at 190°C, using weights of 2.16 kg, 6.48 kg, 10 kg and a 21 .6 kg respectively.
- stress exponent or its acronym “S.Ex.” is defined by the following
- melt index was expressed using the units of g/10 minutes or g/10 min or dg/minutes or dg/min. These units are equivalent.
- Condition B was used, with a specimen thickness with the range of 1 .84 to 1 .97 mm
- This method illuminates the molecular weight distributions of ethylene interpolymer products by high temperature gel permeation chromatography (GPC).
- the method uses commercially available polystyrene standards to calibrate the
- the quantity of unsaturated groups, i.e. double bonds, in an ethylene interpolymer product was determined according to ASTM D3124-98 (vinylidene unsaturation, published March 201 1 ) and ASTM D6248-98 (vinyl and trans unsaturation, published July 2012).
- An ethylene interpolymer sample was: a) first subjected to a carbon disulfide extraction to remove additives that may interfere with the analysis; b) the sample (pellet, film or granular form) was pressed into a plaque of uniform thickness (0.5 mm); and c) the plaque was analyzed by FTIR.
- the quantity of comonomer in an ethylene interpolymer product was determined by FTIR (Fourier Transform Infrared spectroscopy) according to ASTM D6645-01 (published January 2010).
- Composition Distribution Branching Index (CDBI) Composition Distribution Branching Index
- interpolymer product (80 to 100 mg) was placed in the reactor of the Polymer Char crystal-TREF unit, the reactor was filled with 35 ml of 1 ,2,4-trichlorobenzene (TCB), heated to 150°C and held at this temperature for 2 hours to dissolve the sample. An aliquot of the TCB solution (1 .5 imL) was then loaded into the Polymer Char TREF column filled with stainless steel beads and the column was equilibrated for 45 minutes at 1 10°C. The ethylene interpolymer product was then crystallized from the TCB solution, in the TREF column, by slowly cooling the column from 1 10°C to 30°C using a cooling rate of 0.09°C per minute.
- TCB 1 ,2,4-trichlorobenzene
- a TREF distribution curve was generated as the ethylene interpolymer product was eluted from the TREF column, i.e. a TREF distribution curve is a plot of the quantity (or intensity) of ethylene interpolymer eluting from the column as a function of TREF elution temperature.
- a CDBI50 was calculated from the TREF distribution curve for each ethylene interpolymer product analyzed.
- the "CDBI50" is defined as the percent of ethylene interpolymer whose composition is within 50% of the median comonomer composition (25% on each side of the median comonomer composition). It is calculated from the TREF composition distribution curve and the normalized cumulative integral of the TREF composition distribution curve.
- a calibration curve is required to convert a TREF elution temperature to comonomer content, i.e. the amount of comonomer in the ethylene interpolymer fraction that elutes at a specific temperature. The generation of such calibration curves are described in the prior art, e.g. Wild, et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441 -455: hereby fully incorporated by reference. Heat Deflection Temperature
- the heat deflection temperature of an ethylene interpolymer product was determined using ASTM D648-07 (approved March 1 , 2007).
- the heat deflection temperature is the temperature at which a deflection tool applying 0.455 MPa (66 PSI) stress on the center of a molded ethylene interpolymer plaque (3.175 mm (0.125 in) thick) causes it to deflect 0.25 mm (0.010 in) as the plaque is heated in a medium at a constant rate.
- NAA Neutron Activation Analysis
- NAA Neutron Activation Analysis
- the average thermal neutron flux within the reactor was 5x10 11 /cm 2 /s.
- samples were withdrawn from the reactor and aged, allowing the radioactivity to decay; short half-life elements were aged for 300 seconds or long half-life elements were aged for several days.
- the gamma-ray spectrum of the sample was recorded using a germanium semiconductor gamma-ray detector (ORTEC ® model GEM55185, Advanced Measurement Technology Inc., Oak Ridge, TN, USA) and a multichannel analyzer (ORTEC model DSPEC Pro). The amount of each element in the sample was calculated from the gamma-ray spectrum and recorded in parts per million relative to the total weight of the ethylene interpolymer sample. The N.A.A.
- interpolymer products were measured according to ASTM E31 3-10 (approved in 2010) using a BYK Gardner Color- View colorimeter.
- a series of small amplitude frequency sweep tests were run on each sample using an Anton Paar MCR501 Rotational Rheometer equipped with the "TruGapTM Parallel Plate measuring system.” A gap of 1 .5 mm and a strain amplitude of 1 0% were used throughout the tests. The frequency sweeps were from 0.05 to 100 rad/s at the intervals of seven points per decade.
- the test temperatures were 1 70°, 1 90°, 21 0° and 230°C. Master curves at 1 90°C were constructed for each sample using the Rheoplus/32 V3.40 software through the Standard TTS (time-temperature superposition) procedure, with both horizontal and vertical shift enabled.
- the Yd and Xd data generated are summarized in Table 4.
- the flow properties of the ethylene interpolymer products e.g., the melt strength and melt flow ratio (MFR) are well characterized by the Dilution Index ( Yd) and the Dimensionless Modulus (Xd) as detailed below.
- MFR melt strength and melt flow ratio
- Yd Dilution Index
- Xd Dimensionless Modulus
- the flow property is a strong function of Yd and d in addition a dependence on the zero-shear viscosity.
- MS melt strength
- the disclosed Examples and the Comparative Examples were found to follow the same equation, confirming that the characteristic VGP point ⁇ ( ⁇ )G * /G * , S c ) and the derived regrouped coordinates (Xd, Yd) represent the structure well:
- polymerization process and catalyst formulations disclosed herein allow the production of ethylene interpolymer products that can be converted into flexible manufactured articles that have a desired balance of physical properties (i.e. several end-use properties can be balanced (as desired) through multidimensional optimization); relative to comparative polyethylenes of comparable density and melt index.
- the rheological data was generated on a
- Rheometrics RDS-II (Rheometrics Dynamic Spectrometer II), which is a Strain Control Rotational Rheometer.
- the ethylene interpolymer sample analyzed was in the form of a compression molded sample disk; the sample disk is placed in the heated chamber of the RDS-II, between two parallel plate test fixtures; one fixture is attached to an actuator and the other to a transducer.
- the testing is carried out over a range of frequencies, typically from 0.05 to 1 00 rad/s, at a fixed strain and a constant temperature of 190°C.
- Sample plaques were prepared as follows: (a) for samples having a melt index less than 1 .0 dg/min, about 5.5 g of ethylene interpolymer was compression molded at 190°C into a 1 .8 mm thick circular plaque and using a circular punch a 2.5 cm diameter sample disk was punched from the circular plaque and loaded into the RDS-II, or; (b) for samples having a melt index greater than or equal to 1 .0 dg/min, about 2.8 g ethylene interpolymer was compression molded at 190°C into a 0.9 mm thick circular plaque and using a circular punch a 2.8 cm diameter sample disk was punched from the circular plaque and loaded into the RDS-II.
- the finished plaque should be bubble-free, impurity-free, and have a smooth surface free of any defect.
- IZOD impact strength (ft-lbs/in) was determined using ASTM D256-05 (published January 2005) using an Izod impact pendulum-like tester.
- Hexane extractables was determined according to the Code of Federal Registration 21 CFR ⁇ 177.1520 Para (c) 3.1 and 3.2, wherein the quantity of hexane extractable material in a sample is determined gravimetrically.
- Embodiments of ethylene interpolymer products disclosed herein were produced in a continuous solution polymerization pilot plant comprising reactors arranged in a series configuration. Methylpentane was used as the process solvent (a commercial blend of methylpentane isomers).
- the volume of the first CSTR reactor (R1 ) was 3.2 gallons (12 L)
- the volume of the second CSTR reactor (R2) was 5.8 gallons (22 L)
- the volume of the tubular reactor (R3) was 4.8 gallons (18 L).
- Examples of ethylene interpolymer products were produced using an R1 pressure from about 14 MPa to about 18 MPa; R2 was operated at a lower pressure to facilitate continuous flow from R1 to R2.
- R1 and R2 were operated in series mode, wherein the first exit stream from R1 flows directly into R2. Both CSTR's were agitated to give conditions in which the reactor contents were well mixed. The process was operated continuously by feeding fresh process solvent, ethylene, 1 -octene and hydrogen to the reactors.
- the single site catalyst components used were: component (i),
- the single site catalyst component solvents used were methylpentane for components (ii) and (iv) and xylene for components (i) and (iii).
- R1 (i) (ppm) The quantity of PIC-1 added to R1 , "R1 (i) (ppm)" is shown in Table 2A; to be clear, in Example 81 in Table 2A, the solution in R1 contained 0.13 ppm of component (i), i.e. PIC-1 .
- the in-line Ziegler-Natta catalyst formulation was prepared from the following components: component (v), butyl ethyl magnesium; component (vi), tertiary butyl chloride; component (vii), titanium tetrachloride; component (viii), diethyl aluminum ethoxide; and component (ix), triethyl aluminum. Methylpentane was used as the catalyst component solvent.
- the in-line Ziegler-Natta catalyst formulation was prepared using the following steps.
- step one a solution of triethylaluminum and dibutylmagnesium ((triethylaluminum)/(dibutylmagnesium) molar ratio of 20) was combined with a solution of tertiary butyl chloride and allowed to react for about 30 seconds (HUT-1 ); in step two, a solution of titanium tetrachloride was added to the mixture formed in step one and allowed to react for about 14 seconds (HUT-2); and in step three, the mixture formed in step two was allowed to reactor for an additional 3 seconds (HUT-3) prior to injection into R2.
- HUT-1 a solution of triethylaluminum and dibutylmagnesium
- the in-line Ziegler-Natta procatalyst formulation was injected into R2 using process solvent, the flow rate of the catalyst containing solvent was about 49 kg/hr.
- the inline Ziegler-Natta catalyst formulation was formed in R2 by injecting a solution of diethyl aluminum ethoxide into R2.
- the quantity of titanium tetrachloride "R2 (vii) (ppm)" added to reactor 2 (R2) is shown in Table 2A; to be clear in Example 81 the solution in R2 contained 3.99 ppm of TiCk
- the mole ratios of the in-line Ziegler- Natta catalyst components are also shown in Table 2A, specifically: R2 (vi)/(v) mole ratio, i.e.
- 100% of the diethyl aluminum ethoxide was injected directly into R2.
- Example 81 single-site catalyst formulation in R1 + in-line Ziegler-Natta catalyst in R2
- the ethylene interpolymer product was produced at a production rate of 93.5 kg/h
- Comparative Example 20 single-site catalyst formulation in both R1 and R2
- the maximum production rate of the comparative ethylene interpolymer product was 74 kg/h.
- Average residence time of the solvent in a reactor is primarily influenced by the amount of solvent flowing through each reactor and the total amount of solvent flowing through the solution process, the following are representative or typical values for the examples shown in Tables 2A-2C: average reactor residence times were: about 61 seconds in R1 , about 73 seconds in R2 and about 50 seconds in R3 (the volume of R3 was about 4.8 gallons (18L)).
- Polymerization in the continuous solution polymerization process was terminated by adding a catalyst deactivator to the third exit stream exiting the tubular reactor (R3).
- the catalyst deactivator used was octanoic acid (caprylic acid), commercially available from P&G Chemicals, Cincinnati, OH, U.S.A.
- a two-stage devolitizing process was employed to recover the ethylene interpolymer product from the process solvent, i.e. two vapor/liquid separators were used and the second bottom stream (from the second V/L separator) was passed through a gear pump/pelletizer combination.
- DHT-4V ® hydrotalcite
- a slurry of DHT-4V in process solvent was added prior to the first V/L separator.
- the molar amount of DHT-4V added was about 10-fold higher than the molar amount of chlorides added to the process; the chlorides added were titanium tetrachloride and tertiary butyl chloride.
- the ethylene interpolymer product Prior to peptization the ethylene interpolymer product was stabilized by adding about 500 ppm of IRGANOX ® 1076 (a primary antioxidant) and about 500 ppm of IRGAFOS ® 168 (a secondary antioxidant), based on weight of the ethylene interpolymer product. Antioxidants were dissolved in process solvent and added between the first and second V/L separators.
- Tables 2B and 2C disclose additional solution process parameters, e.g. ethylene and 1 -octene splits between the reactors, reactor temperatures and ethylene conversions, etc. recorded during the production of Example 81 and Comparative Example 20.
- the single-site catalyst formulation was injected into both reactor R1 and reactor R2 and ES R1 was 45%, i.e. percent of ethylene allocated to reactor 1 .
- the single site catalyst formulation was injected into R1
- the in-line Ziegler-Natta catalyst formulation was injected into R2 and ES R1 was 35%.
- Example1001 0.9550 0.56 1 12 1 .88 0.001 0.000 0.045
- Example 1002 0.9558 0.65 74.6 1 .66 0.001 0.000 0.045
- NAA Neutron Activation Analysis
- Embodiments of the Disclosed Ethylene Interpolymers as well as
- NAA Neutron Activation Analysis
- Example 200 0.9250 1 .04 6.3 90.1 190 104
- caps and closures comprising at least one ethylene interpolymer product manufactured in a continuous solution polymerization process utilizing at least two reactors employing at least one single-site catalyst formulation and at least one heterogeneous catalyst formulation to produce manufactured caps and closures having improved properties.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Closures For Containers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PE2019001577A PE20191366A1 (en) | 2017-02-13 | 2018-02-12 | LIDS AND CLOSURES |
EP18707429.9A EP3580246A1 (en) | 2017-02-13 | 2018-02-12 | Caps and closures |
MX2019009550A MX2019009550A (en) | 2017-02-13 | 2018-02-12 | Caps and closures. |
JP2019543364A JP6828177B2 (en) | 2017-02-13 | 2018-02-12 | Caps and closures |
CN201880024674.1A CN110753708B (en) | 2017-02-13 | 2018-02-12 | Cover and cover |
BR112019016671-8A BR112019016671B1 (en) | 2017-02-13 | 2018-02-12 | COVER AND SEAL COMPRISING AN ETHYLENE INTERPOLYMER PRODUCT AND PROCESS FOR MANUFACTURING SAID COVER AND SEAL |
KR1020197026037A KR102259579B1 (en) | 2017-02-13 | 2018-02-12 | caps and closures |
AU2018217985A AU2018217985A1 (en) | 2017-02-13 | 2018-02-12 | Caps and closures |
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CA2957706A CA2957706C (en) | 2017-02-13 | 2017-02-13 | Caps and closures |
CA2957706 | 2017-02-13 |
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WO2018146649A1 true WO2018146649A1 (en) | 2018-08-16 |
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PCT/IB2018/050855 WO2018146649A1 (en) | 2017-02-13 | 2018-02-12 | Caps and closures |
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JP (1) | JP6828177B2 (en) |
KR (1) | KR102259579B1 (en) |
CN (1) | CN110753708B (en) |
AU (1) | AU2018217985A1 (en) |
BR (1) | BR112019016671B1 (en) |
CA (1) | CA2957706C (en) |
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JP2022500277A (en) * | 2018-09-10 | 2022-01-04 | ノヴァ ケミカルズ(アンテルナショナル)ソシエテ アノニム | Equipped and recyclable packaging |
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CN115926034A (en) * | 2022-11-28 | 2023-04-07 | 浙江石油化工有限公司 | Preparation method of high-strength waterproof polyethylene film |
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- 2018-02-12 BR BR112019016671-8A patent/BR112019016671B1/en active IP Right Grant
- 2018-02-12 CN CN201880024674.1A patent/CN110753708B/en active Active
- 2018-02-12 EP EP18707429.9A patent/EP3580246A1/en active Pending
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- 2018-02-12 KR KR1020197026037A patent/KR102259579B1/en active IP Right Grant
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JP2022500277A (en) * | 2018-09-10 | 2022-01-04 | ノヴァ ケミカルズ(アンテルナショナル)ソシエテ アノニム | Equipped and recyclable packaging |
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BR112019016671A2 (en) | 2020-04-14 |
CA2957706A1 (en) | 2018-08-13 |
CN110753708A (en) | 2020-02-04 |
CN110753708B (en) | 2022-06-24 |
JP6828177B2 (en) | 2021-02-10 |
KR102259579B1 (en) | 2021-06-02 |
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CA2957706C (en) | 2020-12-15 |
JP2020510583A (en) | 2020-04-09 |
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AU2018217985A1 (en) | 2019-08-29 |
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BR112019016671B1 (en) | 2023-03-21 |
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