JP2020510583A - Caps and closures - Google Patents

Abstract

The present disclosure relates to caps and closures made from ethylene interpolymer products or blends containing ethylene interpolymer products.

Description

  The present disclosure relates to caps and closures comprising at least one ethylene interpolymer product, wherein the at least one ethylene interpolymer product comprises at least one single-site catalyst formulation and at least one heterogeneous catalyst formulation. Manufactured in a continuous solution polymerization process utilizing at least two reactors to produce manufactured caps and closures having improved properties.

  Ethylene interpolymer products are used in cap and closure applications to produce a wide variety of products, such as caps for carbonated or non-carbonated liquids and dispensing closures, including closures with living hinges. You. Such caps and closures are typically manufactured using a conventional injection molding or compression molding process.

  In some embodiments, the ethylene interpolymers disclosed herein having a melt index greater than or equal to 0.3 dg / min and less than or equal to 5.0 dg / min provide G ′ [＠ G ″ that are advantageous in the compression molding process. = 500 Pa], that is, G ′ [＠ G ″ = 500 Pa] of 40 Pa or more and 70 Pa or less. In some embodiments, the ethylene interpolymers disclosed herein having a melt index greater than 5.0 dg / min and less than or equal to 20.0 dg / min have advantageous G '[＠ G' in injection molding processes. '= 500 Pa], that is, G ′ [ΔG ″ = 500 Pa] of 1 Pa or more and 35 Pa or less. Further, the ethylene interpolymers disclosed herein having a melt index greater than 0.3 dg / min and less than or equal to 8 dg / min have G ′ [＠ G ″ = 500 Pa], an advantage in continuous compression molding processes, ie, , G ′ [＠ G ″ = 500 Pa] of 80 Pa or more and 120 Pa or less.

  In the cap and closure market, there is always a need to develop new ethylene interpolymers with improved properties. Non-limiting examples of such needs include stiffer caps and closures (higher modulus), which allow for the manufacture of thinner and lighter caps and closures, i. Reduced source); increased cap and closure upper working temperature, which is advantageous for hot filling applications; higher heat deflection temperature (HDT); higher crystals, which allows for production of caps and closures at higher production rates Increasing rates, eg more parts per hour; improved environmental stress crack resistance (ESCR), especially for caps and closures used in chemically harsh environments.

  In some embodiments, the disclosed ethylene interpolymer products are produced in a solution polymerization process in which the catalyst components, solvents, monomers, and hydrogen are fed to multiple reactors under pressure. For ethylene homopolymerization, or ethylene copolymerization, the solution reactor temperature may range from about 80 ° C. to about 300 ° C., while the pressure generally ranges from about 3 MPag to about 45 MPag, and The ethylene interpolymer 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. Solution processes can be operated under a wide range of process conditions that allow for the production of various ethylene interpolymers. After the reactor, the polymerization reaction is quenched by the addition of a catalyst deactivator to prevent further polymerization and passivated by the addition of an acid scavenger. After passivation, the polymer solution is sent to a polymer recovery operation where the ethylene interpolymer is separated from the process solvent, unreacted residual ethylene, and unreacted optional α-olefin (s). Is done. Further, the ethylene interpolymer products disclosed herein are synthesized utilizing at least two reactors using at least one single-site catalyst formulation and at least one heterogeneous catalyst formulation. You.

  The present disclosure relates to caps and closures comprising at least one ethylene interpolymer product, wherein the at least one ethylene interpolymer product comprises at least one single-site catalyst formulation and at least one heterogeneous catalyst formulation. Manufactured in a continuous solution polymerization process utilizing at least two reactors to produce manufactured caps and closures having improved properties.

Embodiments of the present disclosure provide an ethylene interpolymer production comprising: (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. includes a cap and closure having at least one layer containing an object, the ethylene interpolymer products is greater dilution index than 0 (dilution index) having _{Y d.}

Another embodiment of the present disclosure provides an ethylene interpolymer comprising: (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. It includes a cap and closure having at least one layer containing the polymer product, the ethylene interpolymer product has a dilution index Y _d of less than 0.

Disclosed herein are:
(I) a first ethylene interpolymer;
(Ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer;
A cap and closure comprising at least one layer comprising an ethylene interpolymer product comprising:
The first ethylene interpolymer has the formula:
^{_{(L A) a M (Pl}} ) b (Q) n
(Wherein, L ^A is unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl, and is selected from the group consisting of substituted fluorenyl;
M is a metal selected from titanium, hafnium, and zirconium;
Pl is a phosphinimine ligand;
Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a _C1-10 hydrocarbyl radical, a _C1-10 alkoxy radical, and a _C5-10 aryloxide radical;
Each of the above hydrocarbyl, alkoxy, and aryl oxide radicals are unsubstituted or substituted by halogen atoms, C _1-18 alkyl radicals, C _1-8 alkoxy radicals, C _6-10 aryl or aryloxy radicals. no, or amide radical is substituted by C _1-8 alkyl radical of up to two, or not substituted, or be further substituted by phosphide radicals substituted by C _1-8 alkyl radical of up to two Often;
a is 1; b is 1; n is 1 or 2; (a + b + n) is equal to the valency of metal M);
Produced using a single-site catalyst formulation comprising component (i) defined by:
Said second ethylene interpolymer is produced using a first in-line Ziegler-Natta catalyst formulation;
The third ethylene interpolymer is produced using the first in-line Ziegler-Natta catalyst formulation or the second in-line Ziegler-Natta catalyst formulation;
The ethylene interpolymer products has a dilution index Y _d of less than 0;
The ethylene interpolymer product has a melt index of about 0.3 to about 7 dg / min, the melt index being measured according to ASTM D1238 (2.16 kg load and 190 ° C.)
The ethylene interpolymer product has a G ′ [＠G ″ = 500 Pa] of 80 Pa to 120 Pa.

  This embodiment provides an ethylene interpolymer product comprising (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. A cap and closure having at least one layer containing the ethylene interpolymer having a terminal vinyl unsaturation of 0.03 or more per 100 carbon atoms.

  Embodiments of the present disclosure provide an ethylene interpolymer production comprising: (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. A cap and a closure having at least one layer containing the product, the ethylene interpolymer product having more than 3 parts per million (ppm) total catalytic metal.

Further embodiments include (i) a first ethylene interpolymer, (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. A cap and a closure having at least one layer containing an ethylene interpolymer product comprising a polymer having a dilution index Y _d greater than 0 and a dilution index Y _d greater than 0 per 100 carbon atoms. It has a terminal vinyl unsaturation of 03 or greater or a total catalytic metal of 3 parts per million (ppm) or greater or a dimensionless coefficient _Xd greater than zero.

A further embodiment provides an ethylene interpolymer product comprising (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. A cap and closure having at least one layer containing said ethylene interpolymer product having a dilution index Y _{d of} less than 0 and a terminal vinyl unsaturation of 0.03 or more per 100 carbon atoms or 3 million parts per million. It has a total catalyst metal at or above the rate (ppm) or a dimensionless coefficient _Xd of less than zero.

An additional embodiment provides an ethylene interpolymer product comprising: (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. Wherein the ethylene interpolymer product comprises at least 0.03 terminal vinyl unsaturation per 100 carbon atoms and a total of 3 parts per million (ppm) or more. It has a dimensionless coefficient _Xd greater than zero for the catalytic metal or zero.

Embodiments include an ethylene interpolymer product comprising (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. A cap and closure having at least one layer, wherein the ethylene interpolymer product has a total catalyst metal of greater than 3 parts per million (ppm) and a dimensionless coefficient _{Xd of} greater than zero.

A further embodiment provides an ethylene interpolymer product comprising (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. A cap and closure having at least one layer containing the ethylene interpolymer product having a dilution index Y _d greater than 0 and a terminal vinyl unsaturation of 0.03 or more per 100 carbon atoms and 3 million It has a fraction (ppm) or more of total catalytic metal or dimensionless coefficient _Xd greater than zero.

A further embodiment provides an ethylene interpolymer product comprising (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. A cap and closure having at least one layer containing the ethylene interpolymer product having a dilution index Y _{d of} less than 0 and a terminal vinyl unsaturation of 0.03 or more per 100 carbon atoms and 3 million parts per million. It has a total catalyst metal at or above the rate (ppm) or a dimensionless coefficient _Xd of less than zero.

An additional embodiment provides an ethylene interpolymer product comprising: (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. Wherein the ethylene interpolymer product has a dimensionless coefficient _Xd greater than 0 and a total catalyst metal greater than 3 parts per million (ppm) and greater than 0. having a dilution index _{Y d} or 100 terminal vinyl unsaturation of more than 0.03 per carbon atom.

Additional embodiments provide an ethylene interpolymer product comprising: (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. Wherein the ethylene interpolymer product has a dimensionless coefficient _Xd of less than 0 and a total catalyst metal of 3 parts per million (ppm) or more and a dilution of less than 0. with the indices _{Y d} or 100 terminal vinyl unsaturation of 0.03 or more per carbon atoms.

Embodiments include an ethylene interpolymer product comprising (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. And a closure having at least one layer having a dilution index Y _d greater than 0, a dimensionless coefficient X _d greater than 0, and a total index of 3 parts per million (ppm) or greater. It has a terminal metal unsaturation of 0.03 or more per catalytic metal and 100 carbon atoms.

Embodiments include an ethylene interpolymer product comprising (i) a first ethylene interpolymer, (ii) a second ethylene interpolymer, and (iii) optionally a third ethylene interpolymer. The ethylene interpolymer product having a dilution index Y _d of less than 0, a dimensionless coefficient X _{d of} less than 0, and a total catalyst of 3 parts per million (ppm) or more. It has a terminal vinyl unsaturation of 0.03 or more per metal and 100 carbon atoms.

The ethylene interpolymer products disclosed herein have a melt index of about 0.3 to about 20 dg / min, a density of about 0.948 to about 0.968 g / cm ³ , and a M of about 2 to about 25. _w / M _n , and an ethylene interpolymer product having a CDBI ₅₀ of about 54% to about 98%, the melt index is measured according to ASTM D1238 (2.16 kg load and 190 ° C.), and the density is ASTM D792. It is measured according to.

Furthermore, the disclosed ethylene interpolymer product has a (i) from about 0.01 to about 200 dg / min melt index and about the density of 0.855 g / cm ³ ~ about 0.975 g / cm ^3, from about 15 has a first ethylene interpolymer to about 60 percent by weight, the (ii) from about 0.3 to about 1000 dg / min melt index and about density of 0.89 g / cm ³ to about 0.975 g / cm ^3, a second ethylene interpolymer of about 30 to about 85 percent by weight, (iii) optionally, from about 0.5 to about 2000 dg / min density of melt index and from about 0.89 to about 0.975 g / cm ³ From about 0 to about 30 weight percent of a third ethylene interpolymer having a weight percentage of The weight is the weight of the first, second, or third ethylene polymer divided by the weight of the ethylene interpolymer product.

  Embodiments of the present disclosure include a cap and a closure comprising one or more ethylene interpolymer products synthesized in a solution polymerization process, wherein the ethylene interpolymer products comprise from 0 to about 1.0 mole percent of one of the ethylene interpolymer products. The above α-olefin may be contained.

  Further, the first ethylene interpolymer is synthesized using a single site catalyst formulation, and the second ethylene interpolymer is synthesized using a first heterogeneous catalyst formulation. Embodiments of the cap and closure include a plurality of ethylene interpolymer products wherein the third ethylene interpolymer is synthesized using the first heterogeneous catalyst formulation or the second heterogeneous catalyst formulation. Is also good.

  The second ethylene interpolymer can 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 a first in-line Ziegler-Natta catalyst formulation or a first batch Ziegler-Natta catalyst formulation. The optional third ethylene interpolymer can be synthesized using a second in-line Ziegler-Natta catalyst formulation or a second batch Ziegler-Natta catalyst formulation.

  Embodiments of the present disclosure include a cap and a closure containing an ethylene interpolymer product, the ethylene interpolymer product having less than 1 part per million (ppm) of metal A; Non-limiting examples of Metal A, derived from a site catalyst formulation, include titanium, zirconium or hafnium.

  Further embodiments include caps and closures containing an ethylene interpolymer product having metal B and optionally metal C; the total amount of metallurgical B and metal C is from about 3 to about 11 parts per million (ppm). Yes; Metal B is from the first heterogeneous catalyst formulation and Metal C is from the optional second heterogeneous catalyst formulation. Metals B and C are independently selected from the non-limiting examples of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium or osmium. Metals B and C may be the same metal.

Additional embodiments of the cap and closure include an ethylene interpolymer product, wherein the first ethylene interpolymer has a first M _w / M _n and the second ethylene interpolymer is a second ethylene interpolymer. has a _M w / _{M n,} the third ethylene optionally have a _M w / _{M n;} first _M w / _{M n} is in the second _M w / _{M n} and optionally a 3, lower than _Mw / _Mn . Embodiment, by blending the second ethylene interpolymers and third ethylene interpolymers are ethylene interpolymer blend formed with a fourth M _{w /} M _n, the fourth M _{w /} M _n , No greater than the second M _w / M _n . Additional ethylene interpolymer product embodiments are characterized in that both the second _Mw / _Mn and the third _Mw / _Mn have less than about 4.0.

Further, embodiments of the caps and closures wherein the first ethylene interpolymer has a first CDBI ₅₀ of about 70 to about 98% and the second ethylene interpolymer has a second CDBI of about 45 to about 98%. It has a CDBI _50, a third ethylene interpolymer optional have a third CDBI ₅₀ of about 35 to about 98%, comprises ethylene interpolymer products. Other embodiments include first CDBI ₅₀ is higher than the second CDBI _50, optionally, the first CDBI ₅₀ is high ethylene interpolymer products from third CDBI _50.

  Embodiments also include caps and closures having a melt index of from 0.4 dg / min to 5.0 dg / min and a G '[' G "= 500 Pa] of from 40 Pa to 70 Pa. Additional embodiments include caps and closures having a melt index greater than 5.0 dg / min and less than or equal to 20 dg / min and a G '[' G "= 500 Pa] of 1 Pa or more and 35 Pa or less. Additional embodiments include caps and closures having a melt index greater than 0.3 dg / min and less than or equal to 7 dg / min and a G '[' G "= 500 Pa] of 80 Pa or more and 120 Pa or less.

  Finally, a process for manufacturing any of the cap and closure embodiments described above is disclosed, the process including at least one compression molding step or one injection molding step.

  The following figures are provided for the purpose of illustrating selected embodiments of the present disclosure, and it is understood that the illustrated embodiments do not limit the present disclosure.

FIG. 1 plots G ′ [＠ G ″ = 500 Pa] versus the melt index of the ethylene interpolymer products of Examples 1001 and 1002, Examples 81 and 91, and Comparative Examples Q, V, R, Y, and X. is there. Examples 1001 and 1002 and Examples 81 and 91 (black symbols) are examples of the ethylene interpolymer products disclosed herein. Comparative Examples Q and R are from NOVA Chemicals Inc. Comparative cap and closure HDPE resin available from Co., Ltd .; CCs 153 (0.9530 gcm ³ , 1.4 dg / min) and CCs 757 (0.9589 g / cm ³ , 6.7 dg / min), respectively. It was produced in the double reactor solution process used. Comparative Example V is, Dow Chemical Company available from commercial cap and closure HDPE resins, Continuum DMDA-1250 NT 7 ( 0.957g / cm 3, 1.5dg / min), and Ziegler - Using Natta catalyst It is produced in a double reactor gas phase process. Comparative Examples X and Y, INEOS Olefins & Polymers USA available from commercial cap and closure HDPE resins; ^{respectively, INEOS HDPE J50-1000-178 (0.951g / cm} 3, 11dg / min) and INEOS HDPE J60- 800-178 (0.961 g / cm ³ , 7.9 dg / min). FIG. 2 is a plot of the dilution index (Y _d ) (the dilution factor has a dimension of degrees (°)) and the dimensionless coefficient (X _d ) of the following example: Comparative Example S (open triangle, Y _d) = X _d = 0) are ethylene interpolymers (see rheology), including ethylene interpolymers synthesized using in-line Ziegler-Natta catalyst in a solution process; Examples 6, 101, 102, 103, 110, 115, 200, 201 (filled circles, Y _d > 0 and X _d <0) are the first ethylene interpolymer synthesized using a single-site catalyst formulation in a solution process and an in-line Ziegler-Natta catalyst formulation An ethylene interpolymer product described in the present disclosure, comprising: a second ethylene interpolymer synthesized using the product; 0,130, and 131 (closed _{squares, Y d> 0, X d} > 0) is an ethylene interpolymer products described in this disclosure; Comparative Examples D and E (white _diamonds, Y d <0, X _d > 0) are the first ethylene interpolymer synthesized using a single-site catalyst formulation and the second ethylene interpolymer synthesized using a batch Ziegler-Natta catalyst formulation in a solution process. Comparative Example A (open squares, Y _d > 0 and X _d <0) comprises a first and a second synthesized using a single-site catalyst formulation in a solution process. Ethylene interpolymer. FIG. 3 shows a typical Van Gump Palmen (VGP) plot of phase angle [°] versus complex modulus [kPa]. 4, omega in order to obtain _c a (ω _c = 0.01ω _x), the storage modulus of a two Dekedoshifuto at the crossover frequency omega _x and phase angle (decade shift) (G ') and loss modulus (G '') Is plotted. FIG. 5 shows the amount of terminal vinyl unsaturation per 100 carbon atoms in the ethylene interpolymer product of the present disclosure (vinyl terminal / 100C) (filled circles) for Comparative Examples B, C, E, E2, G, H , H2, I, and J (open triangles). FIG. 6 shows the amounts (solid circles) of total catalyst metals (ppm) in the ethylene interpolymer product of the present disclosure in Comparative Examples B, C, E, E2, G, H, H2, I, and J (open triangles). Compared to

[Best Mode for Carrying Out the Invention]
<Definition of terms>
Unless otherwise specified, or unless otherwise specified, all numbers or expressions relating to the amounts of components, extrusion conditions, etc. used in the specification and claims are, in all cases, the term "about". Should be understood as being modified by Thus, unless different semantics are specified, the numerical parameters set forth in the following specification and the appended claims are approximations that may vary depending on the desired properties sought by various embodiments. is there. Without attempting to limit the application of the doctrine of equivalents to at least the claims, each numerical parameter is interpreted at least in light of the number of reported significant digits and by applying ordinary rounding techniques. Should. The numerical values stated in the examples are reported as accurately as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in its respective test measurement.

  It is to be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, the range "1 to 10" is all subranges therebetween, including the listed minimum 1 and the listed maximum 10, that is, all sub-ranges having a minimum of 1 or more and a maximum of 10 or less. It is intended to include subranges. Because the disclosed numerical ranges are continuous, they include all values between the minimum and maximum values. Unless explicitly stated otherwise, the various numerical ranges specified in this application are approximate.

  All composition ranges expressed herein are, in fact, limited to, and do not exceed, 100 percent in total (volume percent or weight percent). Where multiple components in a composition may be present, the sum of the maximum amounts of each component may exceed 100 percent, but as will be readily appreciated by those skilled in the art, It is understood that the amounts fit a maximum of 100 percent.

  In order to form a more thorough understanding of the present disclosure, the following terms are defined and should be used in conjunction with the accompanying figures and descriptions of the various embodiments.

The terms “dilution index (Y _d )” and “dimensionless coefficient (X _d )” are based on rheological measurements and are fully described in this disclosure.

  The term G '[' G "= 500 Pa] (Pa) is a rheological measurement, i.e. the value of the storage modulus G '(Pa) where the loss modulus G" is equal to 500 Pa.

  As used herein, the term “monomer” refers to a small molecule that can chemically react with itself or other monomers to form a polymer.

  As used herein, the term “α-olefin” describes a monomer having a straight hydrocarbon chain containing 3 to 20 carbon atoms with a double bond at one end of the chain. Used to

  As used herein, the term “ethylene polymer” refers to the ethylene monomer and optionally one or more additional, independent of the particular catalyst or particular process used to produce the ethylene polymer. Refers to the macromolecule produced from the monomer. In the field of polyethylene, one or more additional monomers are termed "comonomer (s)" and often comprise an alpha-olefin. The term "homopolymer" refers to a polymer containing 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), very low density polyethylene (ULDPE), plastomers and elastomers. Including. The term ethylene polymer also includes polymers produced in the high pressure polymerization process, non-limiting examples include low density polyethylene (LDPE), ethylene vinyl acetate copolymer (EVA), ethylene alkyl acrylate copolymer, ethylene acrylic acid copolymer and ethylene acrylic Includes metal salts of acids (commonly called ionomers). The term ethylene polymer also includes block copolymers, which may include two to four comonomers. The term ethylene polymer also includes combinations or blends of the ethylene polymers described above.

  The term "ethylene interpolymer" refers to a subset of polymers within the group of "ethylene polymers" excluding polymers produced in a high pressure polymerization process; however, non-limiting examples of polymers produced in a high pressure process include: LDPE and EVA, the latter being a copolymer of ethylene and vinyl acetate.

  The term "heterogeneous ethylene interpolymer" refers to a subset of the polymers within the group of ethylene interpolymers produced using the heterogeneous catalyst formulation; a non-limiting example of a heterogeneous catalyst formulation is , Ziegler-Natta or chromium catalysts.

The term "homogeneous ethylene interpolymer" refers to a subset of the polymers within the group of ethylene interpolymers produced using metallocene or single-site catalysts. Typically, a homogeneous ethylene interpolymer has a narrow molecular weight distribution, eg, a gel permeation chromatography (GPC) M _w / M _n value of less than 2.8, where M _w and M _n are each a weight average molecular weight And the number average molecular weight. On the other hand, the _Mw / _Mn of a heterogeneous ethylene interpolymer is typically greater than the _Mw / _Mn of a homogeneous ethylene interpolymer. In general, a homogeneous ethylene interpolymer also has a narrow comonomer distribution, ie, each macromolecule within the molecular weight distribution has a similar comonomer content. In many cases, the composition distribution width index "CDBI" is used to quantify how the comonomer is distributed within the ethylene interpolymer and to distinguish ethylene interpolymers produced by different catalysts or processes. used. “CDBI ₅₀ ” is defined as the percentage of ethylene interpolymers whose composition is within 50% of the median comonomer composition, as defined by Exxon Chemical Patents Inc. No. 5,206,075, assigned to the assignee of the present invention. The CDBI _{50 of the} ethylene interpolymer can be calculated from a TREF curve (temperature-elution fractionation), and the TREF method is described in Wild et al. , J. et al. Polym. Sci. , Part B, Polym. Phys. , Vol. 20 (3), pages 441-455. Typically, the homogeneous ethylene interpolymer has a CDBI ₅₀ of greater than about 70%. On the other hand, the CDBI ₅₀ of a heterogeneous ethylene interpolymer containing an α-olefin is generally lower than the CDBI ₅₀ of a homogeneous ethylene interpolymer.

  It is well known to those skilled in the art that homogeneous ethylene interpolymers are often further subdivided into "linear homogeneous ethylene interpolymers" and "substantially linear homogeneous ethylene interpolymers". These two subgroups differ in the amount of long chain branching, and more specifically, the linear homogeneous ethylene interpolymer has less than about 0.01 long chain branches per 1000 carbon atoms, while Substantially linear ethylene interpolymers have long chain branches from greater than about 0.01 to about 3.0 per 1000 carbon atoms. Long chain branches are macromolecules in nature, that is, they are similar in length to the macromolecule to which the long chain branch binds. Hereinafter, in the present disclosure, the term "homogeneous ethylene interpolymer" refers to both linear homogenous ethylene interpolymers and substantially linear homogenous ethylene interpolymers.

  As used herein, the term "polyolefin" includes ethylene polymers and propylene polymers, and non-limiting examples of propylene polymers include isotactic, syndiotactic and atactic propylene homopolymers, random polymers containing at least one comonomer. Includes propylene copolymers, as well as high impact polypropylene copolymers or heterophase polypropylene copolymers.

  The term "thermoplastic" refers to a polymer that becomes liquid when heated, flows under pressure, and solidifies when cooled. Thermoplastic polymers include ethylene polymers and other polymers commonly used in the plastics industry; non-limiting examples of other polymers commonly used in film applications include barrier resins (EVOH), binder resins, Including polyethylene terephthalate (PET), polyamide and the like.

  As used herein, the term "monolayer" refers to caps and closures whose wall structure comprises a single layer.

  As used herein, the term "hydrocarbyl", "hydrocarbyl radical", or "hydrocarbyl group" includes hydrogen and carbon and contains one hydrogen-deficient straight or cyclic, aliphatic, olefin, Refers to acetylene and aryl (aromatic) radicals.

As used herein, for example, "alkyl radical", in which one linear hydrogen radical is insufficient, including branched and cyclic paraffin radicals, but are not limited, methyl (-CH ₃₎ and ethyl (- CH ₂ CH ₃ ) radicals. The term "alkenyl radical" refers to straight, branched and cyclic hydrocarbons containing at least one carbon-carbon double bond deficient in one hydrogen radical.

As used herein, "R1" form ^"R1" terms and the superscript letter refers to the first reactor in a continuous solution polymerization process; R1 is distinctly different symbol R ^1; the latter, Used in chemical formulas, for example, represents a hydrocarbyl group. Similarly, the term "R2" and its superscript form " ^R2 " refers to the second reactor; the term "R3" and its superscript form " ^R3 " refers to the third reactor. Point to.

<Catalyst>
Organometallic catalyst formulations that are efficient in the polymerization of olefins are also well known in the art. In the embodiments disclosed herein, at least two catalyst formulations are used in a continuous solution polymerization process. One of the catalyst formulations is a single site catalyst formulation that produces a first ethylene interpolymer. Another catalyst formulation is a heterogeneous catalyst formulation that produces a second ethylene interpolymer. Optionally, a third ethylene interpolymer is produced using the heterogeneous catalyst formulation used to produce the second ethylene interpolymer, or using a different heterogeneous catalyst formulation. , A third ethylene interpolymer may be produced. In a continuous solution process, at least one homogeneous ethylene interpolymer and at least one heterogeneous ethylene interpolymer are solution blended to produce an ethylene interpolymer product.

<Single site catalyst compound>
The catalyst components that make up the single-site catalyst formulation are not particularly limited, ie, various catalyst components may be used. One non-limiting embodiment of a single-site catalyst formulation includes the following three or four components: a bulky ligand-metal complex; an alumoxane cocatalyst; an ionic activator and optionally a hindered phenol. . In Table 2A of the present disclosure: "(i)" refers to "component (i)", i.e., the amount of bulky ligand-metal complex added to R1, and "(ii)" refers to "component (i). ii) ”, ie, refers to the alumoxane cocatalyst,“ (iii) ”refers to“ component (iii) ”, ie, the ionic activator, and“ (iv) ”refers to“ component (iv) ”, ie, optional. Refers to the hindered phenol of choice.

A non-limiting example of component (i) is represented by formula (I):
^{_{(L A) a M (PI}} ) b (Q) n (I)
Wherein, (L ^A) represents a bulky ligand, M represents a metal atom, PI represents a phosphinimine ligand, Q is a leaving group, a is 0 or 1, b is 1 or 2, (a + b) = 2, n is 1 or 2, and the sum of (a + b + n) is equal to the valence of the metal M.

Wherein non-limiting examples of bulky ligands L ^A in (I) are unsubstituted or substituted cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom substituted and / or heteroatom-containing cycloalkyl Includes pentadienyl-type ligand. Additional non-limiting examples are cyclopentaphenanthrenyl ligand, unsubstituted or substituted indenyl ligand, benzindenyl ligand, unsubstituted or substituted fluorenyl ligand, octahydrofluorenyl ligand, Cyclooctatetraenediyl ligand, cyclopentacyclododecene ligand, azenyl ligand, azulene ligand, pentalene ligand, phosphoyl ligand, phosphinimine, pyrrolyl ligand, pyrozolyl ligand Carbazolyl ligands, borabenzene ligands, and the like (including their hydrogenated forms, such as tetrahydroindenyl ligands). In another embodiment, L ^A may be any other ligand structure capable of binding eta to the metal M, such embodiments, to the metal M eta ³ binding and eta ⁵ Includes both bonds. In another embodiment, L ^A is one or more hetero atoms together with the carbon atoms, for example, comprise nitrogen, silicon, boron, germanium, sulfur and phosphorous, opening, acyclic, or fused ring or ring A system, for example, a heterocyclopentadienyl ancillary ligand, may be formed. Other non-limiting embodiments of L ^A comprises bulky amides, phosphides, alkoxides, aryloxides, imides, Karuborido, Bororido, porphyrins, phthalocyanines, choline and other polyazo macrocycle.

  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) 3 P = N-}} (II)
Wherein the R ^p group is a hydrogen atom; a halogen atom; a C _1-20 hydrocarbyl radical which is unsubstituted or substituted with one or more halogen atom (s); a C _1-8 alkoxy radical; _6-10 aryl radical; C _6-10 aryloxy radical; amide radical; formula —Si (R ^s ) ₃ (wherein the R ^s group is a hydrogen atom, a C _1-8 alkyl or alkoxy radical, a C _6-10 A silyl radical of the aryl radical, independently selected from C _6-10 aryloxy radicals, or a formula —Ge (R ^G ) ₃ , where R ^s is defined in this paragraph for the R ^G group. Independently defined from the germanyl radical.

The leaving group Q is any ligand which can be removed from formula (I) to form a catalytic species capable of polymerizing one or more olefins. An equivalent term for Q is "activatable ligand", ie, equivalent to the term "leaving group". In some embodiments, Q is a monoanionic labile ligand having a sigma bond to M. Depending on the oxidation state of the metal, the value for n is 1 or 2 so that formula (I) represents a neutral bulky ligand-metal complex. Non-limiting examples of Q ligands include a hydrogen atom, a halogen, a C _1-20 hydrocarbyl radical, a C _1-20 alkoxy radical, a C _5-10 aryloxide radical, wherein these radicals are linear, branched or cyclic. It may be of the formula or may be further substituted by a halogen atom, a C _1-10 alkyl radical, a C _1-10 alkoxy radical, a C _6-10 aryl or an aryloxy radical. Further non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylate, dienes, hydrocarbyl radicals having 1 to 20 carbon atoms. In another embodiment, the two Q ligands may form part of a fused ring or ring system.

  Further embodiments of component (i) of the single-site catalyst formulation include structural, optical or enantiomeric (meso and racemic isomers) of the bulky ligand-metal complexes described in Formula (I) above. Body) as well as mixtures thereof.

Component (ii), the second single-site catalyst component, is an alumoxane cocatalyst that activates component (i) to a cationic complex. An equivalent term for "alumoxane" is "aluminoxane", although the exact structure of this cocatalyst is not clear, but experts on the subject of the present application generally recognize that it contains a repeating unit of general formula (III) Are recognized as oligomer species:
_{(R) 2 AlO- (Al (} R) -O) n -Al (R) 2 (III)
Wherein the R groups may be the same or different linear, branched or cyclic hydrocarbyl radicals containing from 1 to 20 carbon atoms, and n is from 0 to about 50. A non-limiting example of an alumoxane is methylaluminoxane (or MAO), wherein each R group in formula (III) is a methyl radical.

The third catalyst component (iii) for single-site catalyst formation is an ionic activator. Generally, ionic activators comprise a cation and a bulky anion, the latter being substantially non-coordinating. A non-limiting example of an ionic activator is a tetracoordinate boron ionic activator having four ligands attached to the boron atom. Non-limiting examples of boron ionic activators include the following formulas (IV) and (V) shown below:
_{^{[R 5] + [B (}} R 7) 4] - (IV)
Wherein B represents a boron atom, R ⁵ is an aromatic hydrocarbyl (eg, triphenylmethyl cation), and each R ⁷ is a fluorine atom, a C atom substituted or unsubstituted by a fluorine atom. _A phenyl radical substituted or unsubstituted with 3 to 5 substituents selected from _1-4 alkyl or alkoxy radicals; and -Si (R ⁹ ) ₃ wherein each R ⁹ is hydrogen Independently selected from an atom and a silyl radical of (C _1-4 alkyl radical)); and a compound of formula (V):
[(R ⁸ ) _t ZH] ⁺ [B (R ⁷ ) ₄ ] ⁻ (V)
(Wherein B is a boron atom, H is a hydrogen atom, Z is a nitrogen or phosphorus atom, t is 2 or 3, R ⁸ is a C _1-8 alkyl radical, Selected from a phenyl radical, which is unsubstituted or substituted by up to three C _1-4 alkyl radicals, or one R ⁸ together with the nitrogen atom may form an anilinium radical , R ⁷ are as defined in formula (IV) above).

A non-limiting example of R ⁷ in both formulas (IV) and (V) is a pentafluorophenyl radical. In general, the boron ionic activator can be described as a salt of tetra (perfluorophenyl) boron, non-limiting examples include anilinium, carbonium of tetra (perfluorophenyl) boron with anilinium and trityl (or triphenylmethylium), Includes oxonium, phosphonium and sulfonium salts. Additional non-limiting examples 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, tributylammonium tetra (m, m-dimethylphenyl) boron, Tributylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tri (n-butyl) ammonium tetra (o-tri ) Boron, N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) n-butylboron, N, N-2 , 4,6-pentamethylanilinium tetra (phenyl) boron, di- (isopropyl) ammonium tetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) boron, triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) ) Phosphonium tetra (phenyl) boron, tri (dimethylphenyl) phosphonium tetra (phenyl) boron, tropylium tetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl volley Benzene (diazonium) tetrakis pentafluorophenyl borate, tropylium tetrakis (2,3,5,6-tetrafluorophenyl) borate, triphenylmethylium tetrakis (2,3,5,6-tetrafluorophenyl) borate, benzene (Diazonium) tetrakis (3,4,5-trifluorophenyl) borate, tropylium tetrakis (3,4,5-trifluorophenyl) borate, benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate , Tropylium tetrakis (1,2,2-trifluoroethenyl) borate, triphenylmethylium tetrakis (1,2,2-trifluoroethenyl) borate, benzene (diazonium) tetrakis (1,2,2-trifluoroethenyl) B) borate, tropylium tetrakis (2,3,4,5-tetrafluorophenyl) borate, triphenylmethyliumtetrakis (2,3,4,5-tetrafluorophenyl) borate and benzene (diazonium) tetrakis (2 , 3,4,5-tetrafluorophenyl) borate. Commercially available ionic activators that are readily available include N, N-dimethylanilinium tetrakispentafluorophenyl borate and triphenylmethylium tetrakispentafluorophenyl borate.

  An optional fourth catalyst component for single-site catalyst formation is component (iv), which is a hindered phenol. Non-limiting examples of hindered phenols include butylated phenol antioxidants, butylated hydroxytoluene, 2,4-di-tertbutyl-6-ethylphenol, 4,4'-methylenebis (2,6-di-tert- 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.

  To produce an active single-site catalyst formulation, the amounts and molar ratios of the three or four components (i) to (iv) are optimized as described below.

<Heterogeneous catalyst formulation>
Some heterogeneous catalyst formulations are well known to those skilled in the art and include, by way of non-limiting example, Ziegler-Natta catalyst formulations and chromium catalyst formulations.

  In the present disclosure, embodiments include in-line and batch Ziegler-Natta catalyst formulations. The term "in-line Ziegler-Natta catalyst formulation" refers to the continuous synthesis of a small amount of active Ziegler-Natta catalyst and the immediate injection of the catalyst into at least one continuously operated reactor, where the catalyst comprises: The ethylene and one or more optional α-olefins are polymerized to form an ethylene interpolymer. The terms "batch Ziegler-Natta catalyst formulation" or "batch Ziegler-Natta precatalyst" refer to a much more external or continuous separate solution polymerization process in one or more mixing vessels. Refers to the synthesis of large amounts of catalyst or procatalyst. Once prepared, the batch Ziegler-Natta catalyst formulation, or batch Ziegler-Natta precatalyst, is transferred to a catalyst storage tank. The term "precatalyst" refers to an inert catalyst formulation (inactive with respect to ethylene polymerization), wherein the precatalyst is converted to an active catalyst by adding an alkylaluminum cocatalyst. Optionally, the precursor catalyst is pumped from the storage tank to at least one continuously operated reactor where an active catalyst is formed, polymerizing ethylene and one or more optional α-olefins to form an ethylene interpolymer. Form. The pre-catalyst may be converted to an active catalyst within the reactor or outside the reactor.

  A variety of chemical compounds can be used to synthesize active Ziegler-Natta catalyst formulations. The following describes various chemical compounds that can be combined to produce an active Ziegler-Natta catalyst formulation. It will be understood by those skilled in the art that embodiments in the present disclosure are not limited to the specific chemical compounds disclosed.

  Activated Ziegler-Natta catalyst formulations can be formed from magnesium compounds, chloride compounds, metal compounds, alkylaluminum cocatalysts and aluminum alkyls. In Table 2A of the present disclosure, “(v)” refers to the magnesium compound that is “component (v)”, and the term “(vi)” refers to the chloride compound that is “component (vi)”; “(Vii)” indicates a metal compound that is “component (vii)”, “(viii)” indicates an alkylaluminum cocatalyst that is “component (viii)”, and “(ix)” indicates a “component (vii)”. (Ix) ". As will be appreciated by those skilled in the art, the Ziegler-Natta catalyst formulation may contain additional components, a non-limiting example of an additional component is an electron donor such as an amine or ether.

A non-limiting example of an active in-line Ziegler-Natta catalyst formulation can be prepared as follows. In a first step, a solution of a magnesium compound (component (v)) is reacted with a solution of a chloride compound (component (vi)) to form a magnesium chloride carrier suspended in the solution. Non-limiting examples of magnesium compounds include Mg (R ¹ ) ₂ , wherein the R ¹ group is the same or different, straight-chain, branched or cyclic hydrocarbyl radical containing 1 to 10 carbon atoms. There may be. Non-limiting examples of chloride compound comprises R 2 ^Cl, wherein, R ² contains hydrogen atoms, or 1 to 10 carbon atoms, represents a straight-chain, branched or cyclic hydrocarbyl radicals. In the first step, the solution of the magnesium compound may also contain an aluminum alkyl (component (ix)). Non-limiting examples of aluminum alkyl includes Al (R ^{₃₎ 3,} wherein, R ³ groups, containing 1 to 10 carbon atoms, the same or different, a straight-chain, branched or cyclic hydrocarbyl radicals There may be. In the second step, a solution of the metal compound (component (vii)) is added to a solution of magnesium chloride, and the metal compound is supported on magnesium chloride. Non-limiting examples of suitable metal compounds include M (X) _n or MO (X) _n , wherein M is a metal selected from Groups 4-8 of the Periodic Table, or Groups 4-8. Wherein O represents oxygen, X represents chloride or bromide, and 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 can be prepared by reacting metal alkyls with alcohols), and mixtures containing mixtures of halide, alkyl and alkoxide ligands. Includes ligand metal compounds. In a third step, a solution of the alkylaluminum cocatalyst (component (viii)) is added to the metal compound supported on magnesium chloride. A variety of alkylaluminum cocatalysts are preferred, as represented by formula (VI):
Al (R ⁴ ) _p (OR ⁵ ) _q (X) _r (VI)
Wherein the R ⁴ groups can be the same or different hydrocarbyl groups having 1 to 10 carbon atoms, the OR ⁵ groups can be the same or different, alkoxy or aryloxy groups, ⁵ is a hydrocarbyl group having 1 to 10 carbon atoms bonded to oxygen, X is chloride or bromide, and (p + q + r) = 3, where p is greater than 0. Non-limiting examples of commonly used alkylaluminum cocatalysts include trimethylaluminum, triethylaluminum, tributylaluminum, dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide, dimethylaluminum chloride or bromide, diethylaluminum chloride or bromide , Dibutylaluminum chloride or bromide, and ethylaluminum dichloride or dibromide.

Active-line Ziegler - for synthesizing Natta catalyst formulation, the processes described in the above paragraph, can be performed in various solvents, non-limiting examples of the solvent include linear or branched C ₅ -C ₁₂ Contains alkanes or mixtures thereof. To produce an active in-line Ziegler-Natta catalyst formulation, the amounts and molar ratios of the five components (v) to (ix) are optimized as described below.

  Additional embodiments of heterogeneous catalyst formulations include those where the "metal compound" is a chromium compound, non-limiting examples include silyl chromate, chromium oxide and chromocene. In some embodiments, the chromium compound is supported on a metal oxide such as silica or alumina. The chromium-containing heterogeneous catalyst formulation may also include a cocatalyst, non-limiting examples of cocatalysts include trialkylaluminum, alkylaluminoxane and dialkoxyalkylaluminum compounds and the like.

<Solution polymerization process: In-line heterogeneous catalyst compound>
The ethylene interpolymer products disclosed herein and useful for making flexible and rigid articles have been produced in a continuous solution polymerization process.
This solution process is fully described in Canadian Patent Application No. CA2,868,640, filed October 21, 2014, entitled "Solution Polymerization Process," and is incorporated herein by reference in its entirety. Be incorporated.

  Embodiments of this process include at least two continuous stirred tank reactors, R1 and R2, and an optional tubular reactor R3. Feeds (solvent, ethylene, at least two catalyst blends, optional hydrogen and optional α-olefin) are continuously fed to at least two reactors. The single-site catalyst formulation is injected into R1, and the first heterogeneous catalyst formulation is injected into R2 and optionally R3. Optionally, a second heterogeneous catalyst formulation is injected into R3. The single-site catalyst formulation comprises an ionic activator (component (iii)), a bulky ligand-metal complex (component (i)), an alumoxane cocatalyst (component (ii)) and an optional hinder, respectively. Dophenol (component (iv)).

  R1 and R2 may be operated in a serial mode or a parallel mode. More specifically, in series mode, in parallel mode where 100% of the effluent from R1 flows directly into R2, R1 and R2 are operated independently, and the effluent from R1 and R2 is downstream of the reactor. Are combined.

  The heterogeneous catalyst formulation is injected into R2. In one embodiment, a first in-line Ziegler-Natta catalyst formulation is injected into R2. The first in-line Ziegler-Natta catalyst formulation comprises (aluminum alkyl) / (magnesium compound) or (ix) / (v); (chloride compound) / (magnesium compound) or (vi) / (v); Alkyl aluminum cocatalyst) / (metal compound) or (viii) / (vii); and the molar ratio of (aluminum alkyl) / (metal compound) or (ix) / (vii), and the reaction and equilibration of these compounds By optimizing the time required to perform the first heterogeneous catalyst assembly. Within the first heterogeneous catalyst assembly, the time between the addition of the chloride compound and the addition of the metal compound (component (vii)) is controlled, which is hereinafter referred to as HUT-1 (first retention time). Called. The time between the addition of component (vii) and the addition of component (viii), which is an alkylaluminum cocatalyst, is also controlled, hereinafter referred to as HUT-2 (second retention time). Further, the time between the addition of the alkylaluminum cocatalyst to R2 and the injection of the in-line Ziegler-Natta catalyst formulation is controlled, hereinafter referred to as HUT-3 (third retention time). Optionally, 100% of the alkylaluminum cocatalyst may be injected directly into R2. Optionally, a portion of the alkylaluminum cocatalyst may be injected into the first heterogeneous catalyst assembly, and the remaining portion may be injected directly into R2. The amount of in-line heterogeneous catalyst formulation added to R2 is expressed as parts per million (ppm) of the metal compound (component (vii)) in the reactor solution, hereinafter referred to as "R2 (vii) (ppm)". Called. Injection of the in-line heterogeneous catalyst blend into R2 produces a second ethylene interpolymer and a second output stream (exiting R2). Optionally, the second output stream is deactivated by adding a catalyst deactivator. If the second output stream is not deactivated, the second output stream enters the reactor R3. One embodiment of a preferred R3 design is a tubular reactor. Optionally, one or more of the following fresh feeds can be injected into R3; solvent, ethylene, hydrogen, α-olefin and first or second heterogeneous catalyst formulation; Supplied from a 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) to (ix)), molar ratios and retention times may be different for the first and second heterogeneous catalyst formulations. It may be different in a heterogeneous catalyst assembly. The second heterogeneous catalyst assembly produces an efficient catalyst by optimizing the retention time and the molar ratio of catalyst components.

  In R3, a third ethylene interpolymer may or may not be formed. The third ethylene interpolymer does not form when a catalyst deactivator is added upstream of R3. A third ethylene interpolymer forms when a catalyst deactivator is added downstream of R3. The optional third ethylene interpolymer may be formed using various modes of operation (provided that no catalyst deactivator is added upstream). Non-limiting examples of modes of operation include: (a) whether the residual ethylene, the remaining optional α-olefin and the residual active catalyst entering R3 react to form a third ethylene interpolymer; Or (b) fresh process solvent, fresh ethylene and optionally fresh α-olefin are added to R3 and the remaining active catalyst entering R3 forms a third ethylene interpolymer, or (c) A) a second in-line heterogeneous catalyst formulation is added to R3 to polymerize the remaining ethylene and any remaining α-olefins to form a third ethylene interpolymer, or A process solvent, ethylene, an optional α-olefin, and a second in-line heterogeneous catalyst formulation are added to R3 to form a third ethylene interpolymer. To form.

  In the in-line mode, R3 produces a third output stream (a streak exiting R3) containing a first ethylene interpolymer, a second ethylene interpolymer, and optionally a third ethylene interpolymer. A catalyst deactivator may be added to the third output stream to form a deactivation solution, provided that the catalyst deactivator is added upstream of R3. No agent is added.

  The passivating solution passes through a vacuum device, a heat exchanger, and a passivating agent is added to form a passivating solution. The passivating solution passes through a series of vapor / liquid separators, and finally the ethylene interpolymer product enters the polymer recovery. Non-limiting examples of polymer recovery operations include one or more gear pumps, single or twin screw extruders that extrude the molten ethylene interpolymer product through a pelletizer.

  Embodiments of the articles of manufacture disclosed herein can be formed from ethylene interpolymer products synthesized using a batch Ziegler-Natta catalyst. Typically, a first batch Ziegler-Natta catalyst is injected into R2 and the alkylaluminum co-catalyst is activated to activate the precursor catalyst in R2. To form Optionally, a second batch Ziegler-Natta precatalyst is injected into R3.

<Additional solution polymerization process parameters>
Examples of various solvents as a process solvent be used, but are not limited, includes straight, branched or cyclic C ₅ -C ₁₂ alkanes. Non-limiting examples of α-olefins include C ₃ -C ₁₀ α-olefins. It is well known to those skilled in the art that the reactor feed stream (solvent, monomer, α-olefin, hydrogen, catalyst formulation, etc.) must be essentially free of catalyst deactivation poisons. Non-limiting examples include trace amounts of oxygenates, such as water, fatty acids, alcohols, ketones and aldehydes. Such poisons are removed from the reactor feed stream using standard purification procedures; non-limiting examples of purification procedures include molecular sieve beds, alumina beds for purification of solvents, ethylene and α-olefins, etc. And an oxygen removal catalyst.

In operation of a continuous solution polymerization process, the total amount of ethylene fed to the process may be split or distributed between the three reactors R1, R2 and R3. This manipulated variable is called ethylene partition (ES), ie, “ES ^R1 ”, “ES ^R2 ” and “ES ^R3 ” refer to the weight percent of ethylene injected into R 1, R 2 and R 3 respectively, However, ES ^R1 + ES ^R2 + ES ^R3 = 100%. 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 added to reactor 1, and the R2 ethylene concentration (wt%) and the R3 ethylene concentration (wt%) are also Defined similarly. The total amount of ethylene converted in each reactor is monitored. The term “Q ^R1 ” refers to the percentage of ethylene added to R1 that is converted by the catalyst formulation to an ethylene interpolymer. Similarly, Q ^R2 and Q ^R3 has been converted to the ethylene interpolymer in each reactor, representing the percentage of ethylene added to R2 and R3. The term “Q ^T ” refers to the overall or total ethylene conversion throughout the continuous solution polymerization plant, ie, Q ^T = 100 × [weight of ethylene in interpolymer product] / ([ [Weight of ethylene] + [weight of unreacted ethylene]). Optionally, α-olefins may be added to the continuous solution polymerization process. If added, the α-olefin may be distributed or distributed between R1, R2 and R3. This manipulated variable is referred to as comonomer distribution (CS), ie, “CS ^R1 ”, “CS ^R2 ” and “CS ^R3 ” represent the weight percent of α-olefin comonomer injected into R1, R2 and R3, respectively. Where CS ^R1 + CS ^R2 + CS ^R3 = 100%.

  In the continuous polymerization process described, the polymerization is stopped by adding a catalyst deactivator. The catalyst deactivator substantially stops the polymerization reaction by changing the active catalyst species to an inactive form. Suitable deactivators are well known in the art, and non-limiting examples include amines (eg, US Pat. No. 4,803,259 to Zboril et al.), Alkali metal salts or alkaline earth metals of carboxylic acids. Salts (eg, US Pat. No. 4,105,609 to Machan et al.), Water (eg, US Pat. No. 4,731,438 to Bernier et al.), Hydrotalcite, alcohol and carboxylic acids (eg, Miyata). U.S. Patent No. 4,379,882), or combinations thereof (U.S. Patent No. 6,180,730 to Sibtain et al.).

  Prior to entering the gas-liquid separator, a passivating agent or acid remover is added to the passivating solution. Suitable passivating agents are well known in the art; non-limiting examples include alkali metal or alkaline earth metal salts of carboxylic acids, or hydrotalcite.

  In the present disclosure, the number of solution reactors is not particularly critical, but a continuous solution polymerization process includes at least two reactors that use at least one single-site catalyst formulation and at least one heterogeneous catalyst formulation.

<First ethylene interpolymer>
The first ethylene interpolymer is produced by a single site catalyst formulation. If the optional α-olefin is not added to reactor 1 (R1), the ethylene interpolymer produced in R1 is an ethylene homopolymer. When an α-olefin is added, the weight ratio of ((α-olefin) / (ethylene)) ^R1 is one parameter for controlling the density of the first ethylene interpolymer. The symbol “σ ¹ ” refers to the density of the first ethylene interpolymer produced within R1. The upper limit of the sigma ¹ is about 0.975 g / cm ^3, a number of the cases of about 0.965 g / cm ^3, in other cases may be about 0.955 g / cm ^3. The lower limit for σ 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 .

Methods for determining the CDBI ₅₀ (Composition Distribution Branching Index) of ethylene interpolymers are well known to those skilled in the art. CDBI ₅₀ expressed as a percentage is defined as the percentage of ethylene interpolymers whose comonomer composition is within 50% of the central comonomer composition. Also, the CDBI ₅₀ of the ethylene interpolymer produced using the single-site catalyst formulation is higher than the CDBI ₅₀ of the α-olefin containing ethylene interpolymer produced using the heterogeneous catalyst formulation, It is well known to those skilled in the art. The upper limit of CDBI ₅₀ for the first ethylene interpolymer (produced using a single-site catalyst formulation) is about 98%, in other cases about 95%, and in other cases about 90%. You may. The lower limit of CDBI ₅₀ for the first ethylene interpolymer may be about 70%, in other cases about 75%, and in other cases about 80%.

As is well known to those skilled in the art, the M _w / M _n of ethylene interpolymers produced using single-site catalyst formulations is higher than ethylene interpolymers produced using heterogeneous catalyst formulations. Low. Thus, in a disclosed embodiment, the first ethylene interpolymer has a lower M _w / M _n compared to the second ethylene interpolymer, and the second ethylene interpolymer has a heterogeneous catalyst formulation. Is generated using The upper limit of _Mw / _Mn for the first ethylene interpolymer may be about 2.8, in other cases about 2.5, and in other cases about 2.2. The lower limit of _Mw / _Mn for the first ethylene interpolymer may be about 1.7, in other cases about 1.8, and in other cases about 1.9.

  The first ethylene interpolymer contains catalyst residues that reflect the chemical composition of the single-site catalyst formulation used. One skilled in the art will understand that the catalyst residue is typically quantified by parts per million of the metal in the first ethylene interpolymer, however, the metal is the metal in component (i) I.e., the metal in the "bulk ligand-metal complex", hereinafter (and in the claims) this metal is referred to as "metal A". As listed above in the present disclosure, non-limiting examples of Metal A include Group 4 metals, titanium, zirconium and hafnium. The upper limit for ppm of metal A in the first ethylene interpolymer may be about 1.0 ppm, in other cases about 0.9 ppm, and in other cases about 0.8 ppm. The lower limit for 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 the R1 is can vary over a wide range, since melt index called I ₂ ¹ to allow the continuous solution process for producing a significantly different first ethylene interpolymer (melt index, Measured at 190 ° C. using a 2.16 kg load according to the procedure outlined in ASTM D1238). The amount of hydrogen added to R1 is expressed as parts per million (ppm) of hydrogen in R1 relative to the total mass in reactor R1, hereinafter referred to as H ₂ ^R1 (ppm). The upper limit of the I ₂ ¹ is about 200 dg / min, about 100 dg / min in some cases, from about 50 dg / min in other cases, in yet other cases may be about 1 dg / min. The lower limit of I ₂ ¹ is from about 0.01 dg / min, about 0.05Dg / min in some cases, in other cases from about 0.1 dg / min, in yet other cases to about 0.5 dg / Minutes.

  The upper limit of 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 even in other cases about 50 wt%. Good. The lower limit for 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 other cases about 30 wt%.

<Second ethylene interpolymer>
By adding (or bringing in) fresh α-olefin to reactor 2 (R2), if the optional α-olefin is not added to R2, the ethylene interpolymer formed in R2 is an ethylene homopolymer It is. When an optional α-olefin is present in ^R2 , the weight ratio of ((α-olefin) / (ethylene)) ^R2 is used to control the density of the second ethylene interpolymer produced in R2. One parameter. Hereinafter, the symbol “σ ² ” refers to the density of the ethylene interpolymer generated in R2. The upper limit of the sigma ² is from about 0.975 g / cm ^3, a number of the cases of about 0.965 g / cm ^3, in other cases may be about 0.955 g / cm ^3. Depending on the heterogeneous catalyst formulation used, the lower limit for σ ² is 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. It may be.

The heterogeneous catalyst formulation is used to produce a second ethylene interpolymer. When the second ethylene interpolymer contains an α-olefin, the CDBI ₅₀ of the second ethylene interpolymer is greater than the CDBI ₅₀ of the first ethylene interpolymer produced using the single-site catalyst formulation. Low. In one embodiment of the present disclosure, the upper limit of the CDBI ₅₀ of the second ethylene interpolymer (containing the α-olefin) is about 70%, in other cases about 65%, and in other cases about 60%. %. In one embodiment of the present disclosure, the lower limit of the CDBI ₅₀ of the second ethylene interpolymer (containing the α-olefin) is about 45%, in other cases about 50%, and in other cases about 55%. %. If no α-olefin is added to the continuous solution polymerization process, the second ethylene interpolymer is an ethylene homopolymer. Even in the case of a homopolymer containing no α-olefin, the CDBI ₅₀ can be measured using TREF. In the case of a homopolymer, the upper limit of the CDBI ₅₀ of the second ethylene interpolymer may be about 98%, in other cases about 96%, and in other cases about 95%. The lower limit for CDBI ₅₀ may be about 88%, in other cases about 89%, and in other cases about 90%. As the α-olefin content in the second ethylene interpolymer approaches zero, the listed CDBI ₅₀ limits for the second ethylene interpolymer (containing the α-olefin) and the second ethylene interpolymer, It is well known to those skilled in the art that there is a smooth transition between the listed CDBI ₅₀ limits of ethylene interpolymers. Typically, the CDBI ₅₀ of the first ethylene interpolymer is higher than the CDBI _{50 of} the second ethylene interpolymer.

_M w / _{M n} of the second ethylene interpolymer is higher than _M w / _{M n} of the first ethylene interpolymer. The upper limit for the _Mw / _Mn of the second ethylene interpolymer is about 4.4, in other cases about 4.2, and in other cases about 4.0, the second ethylene. The lower limit of M _w / M _{n for} the interpolymer may be about 2.2. A M _w / M _n of 2.2 is observed when the melt index of the second ethylene interpolymer is high, or when the melt index of the ethylene interpolymer product is high, for example, greater than 10 g / 10 min. . In other cases, the lower limit of _Mw / _Mn for 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 the heterogeneous catalyst formulation. One skilled in the art will understand that the heterogeneous catalyst residue is typically quantified by the parts per million of metal in the second ethylene interpolymer, but the metal is added to component (vii). Refers to the metal of origin, i.e., the "metal compound"; hereinafter (and in the claims) this metal is referred to as "metal B". As listed above in this disclosure, non-limiting examples of Metal B include a metal selected from Group 4 to Group 8, or a mixture of metals selected from Group 4 to Group 8 of the Periodic Table. The upper limit for ppm of metal B in the second ethylene interpolymer may be about 12 ppm, in other cases about 10 ppm, and in other cases about 8 ppm. The lower limit for ppm of metal B in the second ethylene interpolymer may be about 0.5 ppm, in other cases about 1 ppm, and in other cases about 3 ppm. Without wishing to be bound by any particular theory, in serial mode operation, the chemical environment in the second reactor will either deactivate the single-site catalyst formulation or reduce In operation, the chemical environment within stream R2 inactivates single-site catalyst formation.

The amount of hydrogen added to R2 is can vary over a wide range, thereby, continuous solution process can melt index called after I ₂ ² generates a significantly different second ethylene interpolymer. The amount of hydrogen added is expressed as parts per million of hydrogen in R2 with respect to the total mass of the reactor R2 (ppm), it is hereinafter referred to as _H ² R2 (ppm). The upper limit of the I ₂ ² is about 1000 dg / min, about 750Dg / min in some cases, about 500 dg / min in other cases, in yet other cases may be about 200 dg / min. The lower limit of the I ₂ ² is about 0.3 dg / min, about 0.4 dg / min in some cases, in other cases from about 0.5 dg / min, in yet other cases about 0.6Dg / Minutes.

  The upper limit of 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 even in other cases about 70 wt%. Good. The lower limit for 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 other cases about 50 wt%.

<Third ethylene interpolymer>
If a catalyst deactivator is added upstream of R3, no third ethylene interpolymer is formed in R3. If no catalyst deactivator is added and the optional α-olefin is not present, the third ethylene interpolymer formed in R3 is an ethylene homopolymer. If no catalyst deactivator is added and the optional α-olefin is present in ^R3 , the weight ratio of ((α-olefin) / (ethylene)) ^R3 determines the density of the third ethylene interpolymer I do. In a continuous solution polymerization process, ((α-olefin) / (ethylene)) ^R3 is one of the control parameters used to produce a third ethylene interpolymer having the desired density. Hereinafter, the symbol “σ ³ ” refers to the density of the ethylene interpolymer generated in R3. The upper limit of the sigma ³ is about 0.975 g / cm ^3, a number of the cases of about 0.965 g / cm ^3, in other cases may be about 0.955 g / cm ^3. Depending on the heterogeneous catalyst formulation used, the lower limit for σ ³ is 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. It may be. Optionally, a second heterogeneous catalyst formulation may be added to R3.

Typically, the upper limit of the CDBI ₅₀ of the optional third ethylene interpolymer (containing the α-olefin) is about 65%, in other cases about 60%, and in other cases about 55%. %. The CDBI ₅₀ of the optional third α-olefin containing ethylene interpolymer is lower than the CDBI _{50 of} the first ethylene interpolymer produced using the single site catalyst formulation. Typically, the lower limit of the CDBI ₅₀ of the optional third ethylene interpolymer (containing an α-olefin) is about 35%, in other cases about 40%, and in other cases about 45%. %. If the α-olefin is not added to the continuous solution polymerization process, the optional third ethylene interpolymer is an ethylene homopolymer. For ethylene homopolymers, the upper limit for CDBI ₅₀ may be about 98%, in other cases about 96%, and in other cases about 95%. The lower limit for CDBI ₅₀ may be about 88%, in other cases about 89%, and in other cases about 90%. Typically, the CDBI ₅₀ of the first ethylene interpolymer is higher than the CDBI _{50 of} the third ethylene interpolymer and the second ethylene interpolymer.

The upper limit of _Mw / _{Mn for} the optional third ethylene interpolymer may be about 5.0, in other cases about 4.8, and in other cases about 4.5. The lower limit of _Mw / _{Mn for} the optional third ethylene interpolymer may be about 2.2, in other cases about 2.4, and in other cases about 2.6. _M w / _{M n} of the third ethylene interpolymer of optional higher than _M w / _{M n} of the first ethylene interpolymer. When blended together, the second and third ethylene interpolymer has a fourth _M w / _{M n} not wider than _M w / _{M n} of the second ethylene interpolymer.

  The catalyst residue in the optional third ethylene interpolymer reflects the chemical composition of the heterogeneous catalyst formulation (s) used, ie, the first and optional second heterogeneous catalyst formulations. . The chemical composition of the first and second heterogeneous catalyst formulations may be the same or different, for example, where the first component (vii) and the second component (vii) are the first and second heterogeneous catalyst formulations. It may be used to synthesize a catalyst formulation. As listed above, "Metal B" refers to a metal derived from the first component (vii). Hereinafter, “metal C” refers to a metal derived 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 a metal selected from Group 4 to Group 8 of the periodic table, or a mixture of metals selected from Group 4 to Group 8. The upper limit of 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 other cases about 8 ppm. The lower limit of 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 other cases about 3 ppm.

Optionally, hydrogen may be added to R3. By adjusting the amount of hydrogen in R3 which are later referred to as H ₂ ^{R3 (ppm),} a continuous solution process can generate widely differing third ethylene interpolymer melt index called after I ₂ ^3. The upper limit of I ₂ ³ is about 2000 dg / min, about 1500Dg / min in some cases, from about 1000 dg / min in other cases, in yet other cases may be about 500 dg / min. The lower limit of I ₂ ³ is about 0.5 dg / min, about 0.6Dg / min in some cases, in other cases from about 0.7 dg / min, in yet other cases to about 0.8 dg / Minutes.

  The upper limit for the weight percent (wt%) of the optional third ethylene interpolymer in the ethylene interpolymer product is about 30 wt%, in other cases about 25 wt%, and in other cases about 20 wt%. There may be. The lower limit for 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 other cases about 10 wt%.

<Ethylene interpolymer product>
An upper limit for the density of an ethylene interpolymer product suitable for a cap or closure is about 0.970 g / cm ³ , in some cases about 0.969 g / cm ³ , and in others about 0.968 g / cm ³ . ^It may be ^three . A lower limit for the density of an ethylene interpolymer product suitable for a cap or closure is about 0.945 g / cm ³ , in some cases about 0.947 g / cm ³ , and in others about 0.948 g / cm ³ . ^It may be ^three .

The upper limit for the CDBI ₅₀ of the ethylene interpolymer product may be about 97%, in other cases about 90%, and in other cases about 85%. An ethylene interpolymer product having a CDBI ₅₀ of 97% can occur when the α-olefin is not added to the continuous solution polymerization process, where the ethylene interpolymer product is an ethylene homopolymer. The lower limit of the CDBI ₅₀ of the ethylene interpolymer may be about 50%, in other cases about 55%, and in other cases about 60%.

The upper limit for 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 for the _Mw / _Mn of the ethylene interpolymer product may be 2.0, in other cases about 2.2, and in other cases about 2.4.

  The catalyst residue in the ethylene interpolymer product is used in the single site catalyst formulation used in R1, the first heterogeneous catalyst formulation used in R2, and optionally in R3. It reflects the chemical composition of the first, or optionally, the first and second heterogeneous catalyst formulations. In the present disclosure, catalyst residues were quantified by measuring the parts per million of the catalytic metal in the ethylene interpolymer product. Further, the elemental amounts (ppm) of magnesium, chlorine and aluminum were quantified. The catalytic metal is derived from two or, optionally, three sources; specifically, 1) "Metal A" is derived from component (i) used to form the single-site catalyst formulation. , (2) "Metal B" is derived from the first component (vii) used to form the first heterogeneous catalyst formulation, and (3) optionally "Metal C" is Derived from the second component (vii) used to form the optional second heterogeneous catalyst formulation. Metals A, B and C may be the same or different. In the present disclosure, the term “total catalyst metal” is equal to the sum of catalyst metals A + B + C. Further, in the present disclosure, the terms “first total catalyst metal” and “second total catalyst metal” are produced using a different catalyst formulation than the first ethylene interpolymer product of the present disclosure. Used to distinguish the comparison "polyethylene composition".

  The upper limit for 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 for 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 of ppm of (metal B + metal C) in the ethylene interpolymer product may be about 11 ppm, in other cases about 9 ppm, and in other cases about 7 ppm. The lower limit of 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 other cases about 3 ppm.

In some embodiments, an ethylene interpolymer can be produced when the catalytic metals (Metal A, Metal B, and Metal C) are the same metal, a non-limiting example of a catalytic metal is titanium. In such embodiments, the ppm of (Metal B + Metal C) in the ethylene interpolymer product is calculated using the following equation (VII):
^{ppm (B + C) = (} (ppm (A + B + C) - (f A × ppm A)) / (1-f A) (VII)
Where ppm ^{(B + C)} is the calculated ppm of (metal B + metal C) in the ethylene interpolymer product and ppm ^{(A + B + C)} is the experimentally determined catalyst in the ethylene interpolymer product. The total ppm of residue, ie, (ppm of metal A + ppm of metal B + ppm of metal C); f ^A represents the weight fraction of the first ethylene interpolymer in the ethylene interpolymer product and f ^A Can vary from about 0.15 to about 0.6, and ppm ^A represents ppm of metal A in the first ethylene interpolymer. In equation (VII), ppm ^A is assumed to be 0.35 ppm.

  Embodiments of the ethylene interpolymer product disclosed herein have lower catalyst residues as compared to the polyethylene polymer described in US Pat. No. 6,277,931. The higher catalyst residue in US Pat. No. 6,277,931 increases the complexity of the continuous solution polymerization process, where an example of increased complexity is additional purification to remove catalyst residue from the polymer Including steps. On the other hand, in the present disclosure, catalyst residues are not removed. In the present disclosure, the upper limit of “total catalytic metal”, ie, the total ppm of (ppm of metal A + ppm of metal B + ppm of optional metal C) in the ethylene interpolymer product is about 11 ppm, in other cases May be about 9 ppm, and in other cases about 7. The lower limit of the total ppm of catalyst residues (metal A + metal B + optional metal C) in the ethylene interpolymer product is about 0.5 ppm, in other cases about 1 ppm, and in other cases about 3 ppm. You may.

  The upper limit for the melt index of the ethylene interpolymer product is about 15 dg / min, in some cases about 14 dg / min, in other cases about 12 dg / min, and in other cases about 10 dg / min. You may. The lower limit of the melt index of the ethylene interpolymer product is about 0.5 dg / min, in some cases about 0.6 dg / min, in other cases about 0.7 dg / min, and in other cases, about 0.7 dg / min. It may be about 0.8 dg / min.

  For the ethylene interpolymer product of Area III, as shown in FIG. 1, the upper limit of the melt index of the ethylene interpolymer product is about 8 dg / min, in some cases about 7 dg / min, in other cases May be about 5 dg / min, and in still other cases about 3 dg / min. The lower limit of the melt index of the ethylene interpolymer product is about 0.3 dg / min, in some cases about 0.4 dg / min, in some cases about 0.5 dg / min, in other cases It may be about 0.6 dg / min, and in other cases about 0.7 dg / min.

Table 1 shows the computer generated ethylene interpolymer products. The simulation was based on a basic kinetic model (with specific rate constants for each catalyst formulation) and feed and reactor conditions. The simulation was based on a solution pilot plant configuration described below, which was used to generate the example ethylene interpolymer product disclosed herein. Simulation Example 13 was synthesized using a single site catalyst formulation (PIC-1) at R1 and an in-line Ziegler-Natta catalyst formulation at R2 and R3. Table 1 discloses non-limiting examples of density, melt index and molecular weight of the first, second and third ethylene interpolymers produced in three reactors (R1, R2 and R3); These three interpolymers are combined to produce Simulation Example 13 (ethylene interpolymer product). As shown in Table 1, the simulation example 13 product had a density of 0.9169 g / cm ³ , a melt index of 1.0 dg / min, a branching frequency of 12.1 (C ₆ branches per 1000 carbon atoms). (1-octene comonomer)) and a M _w / M _n of 3.11. Simulation Example 13, respectively 0.31Dg / min, first 1.92Dg / min and 4.7Dg / min, second and third melt index, respectively ^{0.9087g / cm 3, 0.9206g / cm} 3 and first 0.9154g / cm ^3, the second and third density, respectively 2.03M _w / _M n, first 3.29M _w / _{M n} and 3.28M _w / _{M n,} second and A first, second and third CDB ₅₀ with a third M _w / M _n and 90 to 95%, 55 to 60%, and 45 to 55%, respectively, of the first, second and third CDBIs ₅₀ ; Including ethylene interpolymer. The simulated production rate for simulation example 13 was 90.9 kg / hr and the R3 exit temperature was 217.1 ° C.

<Ethylene interpolymer product suitable for cap and closure>
Table 2A~2C are summarizes was used in the preparation of the following ethylene interpolymer product solution pilot plant process conditions: Example 81 and Comparative Example 20, the target target and about 0.953 g / cm ³ Example 91 and Comparative Example 30 had a target melt index of about 0.958 g / cm ³ and a target melt index of about 7.0 dg / min. Examples 1001 and 1002 had a target target 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 produced 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 produced using a single site catalyst formulation in both reactors 1 and 2. The yield of Example 81 was 15% higher than Comparative Example 20. The yield of Example 91 was 26% higher than Comparative Example 30. The examples (81, 91, 1001 and 1002) and the comparative examples (20 and 30) are all produced in reactors 1 and 2 arranged in series, ie the effluent from reactor 1 is Flowed directly into In all cases, the comonomer used was 1-octene.

Table 3 compares the physical properties of Example 81 with Comparative Examples Q and V. Comparative Example Q is a NOVA Chemicals Inc. called CCs153-A (0.9530 g / cm ³ and 1.4 dg / min) produced in a dual reactor solution process using a single site catalyst. Commercially available cap and closure ethylene interpolymers available from Comparative Example V is Continuum DMDA-1250 NT 7 (0.9550 g / cm ³ , 1.5 dg / min) produced in a double reactor gas phase process using a batch Ziegler-Natta catalyst and Dow Commercially available cap and closure ethylene interpolymer available from Chemical Company. It was produced in a dual reactor gas phase process using a batch Ziegler-Natta catalyst formulation.

  As shown in FIG. 1, the rectangle defined by area I defines an area with a melt index in the range of about 0.4 dg / min to 5 dg / min. Within Area I, the disclosed ethylene interpolymer product example 81 has a value of G '[' G "= 500 Pa] which is desirable in the manufacture of caps and closures using a compression molding process. Specifically, Example 81 has G ′ [＠G ″ = 500 Pa] values of 40 Pa or more and 70 Pa or less, and these values are intermediate between Comparative Example Q and Comparative Example V. Specifically, the polymer melt elasticity, as measured by the storage modulus G ', affects the compression molding manufacturing process. In general, the higher the G ', the greater the die swell of the polymer melt. A melt index of less than 5 for the ethylene interpolymer aids in producing caps and closures using a continuous compression molding (CCM) process. The CCM uses a nozzle of a specified diameter to extrude a specified amount of polymer melt, followed by high speed knife cutting to form a molten pellet. Next, the pellets are placed in a mold and compression molded to form a closure. The proper die expansion characteristics of Example 81 (controlled by proper selection of the G 'value) are advantageous for nozzle selection and die expansion control, thereby reducing undesirable phenomena such as, for example, pellet bounce. Reduce or eliminate and improve the CCM process.

Table 3 compares the physical properties of Example 91 with Comparative Examples R, Y, and X. Comparative Example R is a NOVA Chemicals Inc. called CCs 757 (0.9530 g / cm ³ and 1.4 dg / min) produced in a dual reactor solution process using a single site catalyst. Commercially available cap and closure ethylene interpolymers available from Comparative Examples Y and X are commercially available cap and closure ethylene interpolymers available from INEOS Olefins & Polymers USA, INEOS HDPE J50-1000-178 and INEOS HDPE J60-800-178, respectively.

  As shown in FIG. 1, the rectangle defined by Area II defines an area with a melt index ranging from more than 5 dg / min to 20 dg / min. Within Area II, the disclosed ethylene interpolymer product example 91 has a value of G '[' G "= 500 Pa] which is desirable in the manufacture of caps and closures using an injection molding process. Specifically, Example 91 has G ′ [＠ G ″ = 500 Pa] values of 1 Pa or more and 35 Pa or less, and these values are lower than Comparative Examples R, Y, and X. In particular, higher melt indices (5 to 20 dg / min) aid in making caps and closures in the injection molding process. That is, a higher melt index reduces residual stress (crystallization within the part) that can be caused by surface distortion within the cap or closure. Low melt elasticity, as indicated by lower G 'values, increases the degree of polymer chain relaxation, dissipates residual stress, and can produce caps and closures of the required shape and size. Indeed, caps and closures having expected or "as designed" dimensions are advantageous in downstream processing; for example, in downstream processes where the bottle is filled and the cap or closure is attached to the bottle. Current commercially available polyethylene materials that combine the properties of homogeneous and heterogeneous ethylene interpolymers do not exist in the 5 to 20 melt index range.

  Table 3 compares the properties of Examples 1001 and 1002 with all other Examples and Comparative Examples disclosed herein.

  As shown in FIG. 1, the rectangle defined by area III defines an area with a melt index ranging from more than 0.3 dg / min to 8 dg / min. Within Area III, the disclosed ethylene interpolymer product examples 1001 and 1002 have values of G '[' G "= 500 Pa] that are desirable for continuous compression molding or injection molding. Specifically, Examples 1001 and 102 and similar materials have G ′ [＠ G ″ = 500 Pa] values of 80 Pa or more and 120 Pa or less, and these values fall within the ranges of Areas I and II and Comparative Examples. It is different from the example that enters.

<Dilution index (Y _d ) of ethylene interpolymer product>
In FIG. 2, the dilution index (Y _d , having a dimension of ° (degrees)) and the dimensionless coefficient (X _d ) are measured for some of the ethylene interpolymer products disclosed herein (closed symbols). Plotted for the embodiments, and comparative ethylene interpolymer products, ie, Comparative Examples A, D, E, and S. FIG. 2 further defines the following three quadrants.
Type I: Y _d > 0 and X _d <0;
Type II: Y _d > 0 and X _d > 0, and Type III: Y _d <0 and X _d > 0.

  Type IV polymers are not shown in FIG. 2, but are illustrated in Examples 1001 and 1002 shown in Table 4; Type IV ethylene interpolymer products have Yd <0 and Xd <0. As shown in FIG. 1, Type IV ethylene interpolymer products are classified in Area III. The Area III ethylene interpolymer product has a continuous compression molding in view of the melt index of more than 0.3 dg / min and 8 dg / min and the G ′ [＠ G ″ = 500 Pa] of 80 Pa or more and 120 Pa or less. Is advantageous.

<Area III>
The data plotted in FIG. 2 is also tabulated in Table 4. In FIG. 2, Comparative Example S (open triangles) was used as a rheological reference in the dilution index test protocol. Comparative Example S is an ethylene interpolymer product comprising an ethylene interpolymer synthesized using an in-line Ziegler-Natta catalyst in one solution reactor, ie, SCLAIR® FP120-C (NOVA Chemicals Corporation (NOVA Chemicals Corporation)). (Ethylene / 1-octene interpolymer available from Calgary, Alberta, Canada). Comparative Examples D and E (white diamond, Y _d <0, X _d > 0) were first ethylene interpolymers synthesized using a single-site catalyst formulation employing a dual reactor solution process And a second ethylene interpolymer synthesized using a batch Ziegler-Natta catalyst formulation, ie, ELITE® 5100G and ELITE® 5400G, respectively (both Is an ethylene / 1-octene interpolymer available from Dow Chemical Company (Midland, Michigan, USA). Comparative Example A (open squares, Y _d > 0 and X _d <0) is an ethylene containing first and second ethylene interpolymers synthesized using a single site catalyst formulation in a dual reactor solution process. An interpolymer product, SURPASS® FPs117-C, which is an ethylene / 1-octene interpolymer available from NOVA Chemicals Corporation of Calgary, Alberta, Canada.

The following defines the dilution index (Y _d ) and the dimensionless coefficient (X _d ). In addition to having a molecular weight, a molecular weight distribution, and a branched structure, a blend of ethylene interpolymers can exhibit a hierarchical structure in the molten phase. In other words, the ethylene interpolymer component may or may not be uniform at the molecular level, depending on the miscibility of the interpolymer and the physical history of the blend. Such a hierarchical physical structure in the melt is expected to have a strong effect on flow, and thus on processing and conversion, and the final properties of the manufactured product. The nature of this hierarchical physical structure between the interpolymers can be characterized.

The hierarchical physical structure of ethylene interpolymers can be characterized using melt rheology. A convenient method may be based on a small amplitude frequency sweep test. The results of such rheology are referred to as van Gurp-Palmen plots (M. Van Gurp, J. Palmen, Rheol. Bull. (1998) 67 (1): 5-8 and Dealy J, Plazek D. Rhol. Bull. (2009) 78 (2): 16-31) as a function of the complex modulus G ^* . For a typical ethylene interpolymer, the phase angle δ increases toward its upper limit of 90 °, and G ^* is sufficiently low. A typical VGP plot is shown in FIG. The VGP plot is a property of the resin structure. The rise in δ in the 90 ° direction is monotonic for ideally linear monodisperse interpolymers. The δ (G ^* ) of a branched interpolymer or a blend containing a branched interpolymer may indicate an inflection point that reflects the topology of the branched interpolymer (S. Trinkle, P. Walter, C. Friedrich, Rheo. Acta ( 2002) 41: 103-113). The deviation of the phase angle δ from a monotonic rise is due to the low inflection point (eg δ ≦ 20 °), to the presence of long chain branches, or to the high inflection point (eg δ ≧ 70 °) The presence of a blend containing at least two interpolymers having different branching structures may indicate a deviation from an ideal linear interpolymer.

No inflection point is observed for commercially available linear low density polyethylene, except for some commercial polyethylenes that contain small amounts of linear branches (LCB). To use the VGP plot despite the presence of LCB, as the alternative, the frequency omega _c is the crossover frequency omega _c, more 2 decades lower point, i.e., is the use of ω _c = 0.01ω _x. The crossover point is taken as a reference because it is known to be a characteristic point associated with the MI, density, and other specifications of the ethylene interpolymer. Crossover modulus is related to the plateau modulus for a given molecular weight distribution (S. Wu. J Polym Sci, Polym Phys Ed (1989) 27: 723, MR Nobile, F. Cocchini. Rheol Acta). (2001) 40: 111). A two decade shift in the phase angle δ is to find a comparable point where the individual viscoelastic responses of the components can be detected. This two decade shift is shown in FIG. The complex modulus G _c ^{* at} this point is determined by the following formula to minimize variations due to overall molecular weight, molecular weight distribution, and short chain branching:

As crossover elastic modulus

Is normalized to As a result, ω _c = 0.01ω _x , that is,

And the coordinates of this low frequency point for VGP at δ _c characterize the contribution by the blend. Like the inflection point,

The closer the point is to the upper limit in the 90 ° direction, the more the blend behaves as if it were a more ideal single component.

As an alternative to avoid interference due to the molecular weight, molecular weight distribution, and short branching of the ethylene δ _c interpolymer component, the coordinates (G _c ^* , δ _c ) can be calculated by forming the following two parameters Compared to a reference sample.
"Dilution index (Y _d )"

"Dimensionless coefficient (X _d )"

The constants C ₀ , C ₁ , and C ₂ are determined by fitting the VGP data δ (G ^* ) of the reference sample to the following equation.

G _r ^* is the complex modulus of this reference sample at its δ _c = δ (0.01ω _x ). Ethylene having a density of 0.920 g / cm ³ and a melt index (MI or I ₂ ) of 1.0 dg / min when synthesized using an in-line Ziegler-Natta catalyst using one solution reactor. The interpolymer is considered a reference sample and the constant is
C ₀ = 93.43 °
C ₁ = 1.316 °
C ₂ = 0.2945
G _r ^* = is 9432Pa.

  The values of these constants may be different if the rheology test protocol is different from that specified herein.

These coordinates (X _d , Y _d ), rearranged from (G _c ^* , δ _c ), allow a comparison between the ethylene interpolymer products disclosed herein and comparative examples.
The value of the rearranged G _c ^* [kPa] disclosed in Table 4 is the value of the formula for calculating the dimensionless coefficient (X _d )

Is equivalent to the term

The dilution index (Y _d ) indicates that the blend behaves like a simple blend of linear ethylene interpolymers (lacking the hierarchy in the melt) or reflects a hierarchical physical structure within the melt Reflect the response. As Y _d is low, the sample showed more different responses ethylene interpolymers comprising a blend, the more Y _d is high, the sample behaves more like a single component or a single ethylene interpolymer.

Returning to FIG. 2, the type I (upper left quadrant) ethylene interpolymer product of the present disclosure (filled symbols) has Y _d > 0, while the comparative ethylene interpolymer of type III (lower right quadrant) Comparative Examples D and E have Y _d <0. For Type I ethylene interpolymer products (solid circles), the first ethylene interpolymer (single-site catalyst) and the second ethylene interpolymer (in-line Ziegler-Natta catalyst) are simple two-ethylene interpolymers. It behaves like a blend, with no hierarchical structure in the melt. However, in the case of Comparative Examples D and E (white diamond), the melts comprising the first ethylene interpolymer (single site catalyst) and the second ethylene interpolymer (batch Ziegler-Natta catalyst) have a hierarchical structure.

The ethylene interpolymer products of the present disclosure fall into one of two quadrants, Type I with X _d <0 or Type II with X _d > 0. The dimensionless coefficient (X _d ) reflects the overall molecular weight, molecular weight distribution (M _w / M _n ), and the differences (compared to the reference sample) associated with single-chain branching. Without wishing to be bound by theory, conceptually, the dimensionless coefficient (X _d ) is determined by the M _w / M _n and the radius of gyration (<R _g >) of the ethylene interpolymer in the melt. ^It is considered to be related to ² ). Conceptually, increasing _Xd has a similar effect to increasing _Mw / _Mn and / or < _Rg > ² without risk of sacrificing certain relevant properties, including low molecular weight fractionation. .

Compared to Comparative Example A (Comparative Example A includes first and second ethylene interpolymers synthesized using a single site catalyst), the solution process disclosed herein is more Enables the production of ethylene interpolymer products with high _Xd . Without wishing to be bound by theory, as _Xd increases, the higher molecular weight fraction of the polymeric coil expands (conceptually higher <R _g > ² ) and, during crystallization, the tie chain formation Probability increases, resulting in higher toughness. There is a great deal of disclosure in the field of polyethylene related to higher toughness (eg, improved ESCR and / or PENT in molded parts) with an increased probability of tie chain formation.

In dilute index test protocol, the upper limit of Y _d is about 20, in some cases may be about 15, in other cases is about 13. The lower limit of Y _d is about -30, in some cases -25, in other cases -20 may be -15 in yet other cases.

In the dilution index test protocol, the upper limit for _Xd is 1.0, in some cases about 0.95, and in other cases about 0.9. The lower limit for _Xd is -2, in some cases -1.5, and in other cases -1.0.

<Terminal vinyl unsaturation of ethylene interpolymer product>
The ethylene interpolymer products of the present disclosure have at least 0.03 terminal vinyl groups per 100 carbon atoms as determined by Fourier Transform Infrared (FTIR) spectroscopy according to ASTM D3124-98 and ASTM D6248-98 ( It is further characterized by terminal vinyl unsaturation (≧ 0.03 terminal vinyl / 100C).

  FIG. 5 compares the terminal vinyl / 100C content of the ethylene interpolymer of the present disclosure with some comparative examples. The data shown in FIG. 5 is also tabulated in Tables 5A and 5B. All comparative examples in FIG. 5 and Tables 5A and 5B are ELITE products available from Dow Chemical Company (Midland, Michigan, USA), where the ELITE product is an ethylene interpolymer produced in a dual reactor solution process. And interpolymers synthesized using a single-site catalyst and interpolymers synthesized using a batch Ziegler-Natta catalyst. Comparative Example B is ELITE 5401G, Comparative Example C is ELITE 5400G, Comparative Examples E and E2 are ELITE 5500G, Comparative Example G is ELITE 5960, Comparative Examples H and H2 are ELITE 5100G, Example I is ELITE 5940G and Comparative Example J is ELITE 5230G.

As shown in FIG. 5, the average terminal vinyl content in the ethylene interpolymer of the present disclosure is 0.045 terminal vinyl / 100C, and the terminal vinyl unsaturation of Examples 81 and 91 is close to this average, ie, 0.044 and 0.041 terminal vinyl / 100C, respectively. The terminal vinyl unsaturation of Examples 1001 and 1002 was close to this average, ie, 0.045 terminal vinyl / 100C. On the other hand, the average terminal vinyl content of the comparative example sample was 0.023 terminal vinyl / 100C. Similar to Examples 81 and 91, the comparative example shown in FIG. 5 shows that the first ethylene interpolymer synthesized with the single-site catalyst formulation and the second ethylene interpolymer synthesized with the heterogeneous catalyst formulation also Including. Statistically, at the 99.999% confidence level, the ethylene interpolymer of the present disclosure is significantly different from the comparative example of FIG. 5, ie, the t-test assuming equal variance shows two populations (0.045 And 0.023 terminal vinyl / 100C) differ significantly at the 99.999% confidence level (t (obs) = 12.891> 3.510t (crit two tail) or p-value = 4.84 × 10 ⁻¹⁷ < 0.001α (99.999% reliability)).

<Catalyst residue (all catalyst metals)>
The ethylene interpolymer products of the present disclosure are further characterized as having ≧ 3 parts per million (ppm) total catalytic metal (Ti), wherein the amount of catalytic metal is neutron activation as specified herein. Determined by analysis (NAA).

  FIG. 6 compares the total catalytic metal content of the disclosed ethylene interpolymer with some comparative examples. The data in FIG. 6 is also tabulated in Tables 6A and 6B. Figure 6 and all of the comparative examples in Tables 6A and 6B are ELITE products available from Dow Chemical Company (Midland, Michigan, USA); see the section above for additional details.

As shown in FIG. 6, the average total catalytic metal content in the ethylene interpolymer of the present disclosure was 7.02 ppm titanium. Elemental analysis (NAAA) is not complete for Examples 81 and 91, but FIG. 5 shows a reasonable estimate of 7.02 ppm titanium for Examples 81 and 91 residual titanium. This is clearly indicated (as reported in Table 3). On the other hand, the average total catalytic metal in the comparative sample shown in FIG. 6 was 1.63 ppm of titanium. Statistically, at the 99.999% confidence level, the ethylene interpolymers of the present disclosure are significantly different from the comparative examples, ie, the t-test assuming equal variance shows two populations (7.02 and 1.. The average of the 63 ppm titanium) is significantly different at the 99.999% confidence level, ie, t (obs) = 12.71> 3.520 t (crit two tail) or p-value = 1.69 × 10 ^{−. 16} <0.001α (99.999% reliability).

<Hard product>
There is a need for an ethylene interpolymer product having a density, melt index and G ′ [＠ G ″ = 500 Pa] that are optimized for the compression molding process. Further, there is a need for an ethylene interpolymer product having a density, melt index and G ′ [＠ G ″ = 500 Pa] optimized for the injection molding process. There is also a need to improve the stiffness of caps and closures while maintaining or increasing environmental stress crack resistance (ESCR). Various embodiments of the ethylene interpolymer products disclosed herein are suitable to meet some or all of these needs.

Additional non-limiting examples in which the disclosed ethylene interpolymer products may be used include deli containers, margarine containers, trays, cups, lids, bottles, bottle cap liners, pails, crates, drums, bumpers, industrial bulk containers Industrial tanks, material handling containers, playground equipment, recreational equipment, safety equipment, wire and cable applications (power cables, communication cables and conduits), pipes and hoses, pipe applications (pressure and non-pressure pipes, e.g., , Natural gas distribution, water mains, indoor plumbing, rainwater pipes, sewer pipes, corrugated pipes and conduits), foamed articles (foamed sheets or vanforms), military packaging (instruments and portable foods), personal care packaging (diapers and sanitary products) ), Cosmetics, pharmaceutical and medical packaging, truck bed liners, pallets, and car loads Including the can. The rigid article summarized in this paragraph provides one or more ethylene interpolymers with improved hot deflection temperature (HDT), faster crystallization rate (decreased t _1/2 ), and higher melt strength Including things. Such rigid articles can be manufactured using conventional injection molding, compression molding and blow molding techniques.

  The desired properties of the rigid article of manufacture depend on the intended use. Non-limiting examples of desired properties include modulus (G '), stiffness, flexural modulus (1% and 2% secant modulus), tensile toughness, environmental stress crack resistance (ESCR), slow crack growth resistance (PENT). , Abrasion resistance, Shore hardness, heat deflection temperature (HDT), VICAT softening point, IZOD impact strength, ARM impact resistance, Charpy impact resistance, and color (whiteness and / or yellowness index).

<Additives and adjuvants>
The claimed ethylene interpolymer products and caps and closures may optionally include additives and adjuvants, depending on the intended use. Non-limiting examples of additives and adjuvants include antiblocking agents, antioxidants, heat stabilizers, slip agents, processing aids, antistatic additives, colorants, dyes, fillers, light stabilizers, light absorbers, Including lubricants, pigments, plasticizers, nucleating agents or mixtures of nucleating agents, and combinations thereof.

<Test method>
Each specimen was conditioned at 23 ± 2 ° C. and 50 ± 10% relative humidity for at least 24 hours prior to testing, and subsequent testing was performed at 23 ± 2 ° C. and 50 ± 10% relative humidity. As used herein, the term “ASTM conditions” refers to a laboratory maintained at 23 ± 2 ° C. and 50 ± 10% relative humidity. Specimens to be tested were conditioned in this laboratory for at least 24 hours prior to testing. ASTM refers to American Society for Testing and Materials.

<Density>
The density of the ethylene interpolymer product was determined using ASTM D792-13 (November 1, 2013).

<Melt index>
The melt index of the ethylene interpolymer product was determined using ASTM D1238 (August 1, 2013). Melt indices I ₂ , I ₆ , I ₁₀ and I ₂₁ were measured at 190 ° C. using 2.16 kg, 6.48 kg, 10 kg and 21.6 kg weights, respectively. As used herein, the term “stress exponent” or its acronym “S.Ex.” is defined by the following relationship:
S. Ex. = Log (I ₆ / I ₂ ) / log (6480/2160)
Where I ₆ and I ₂ are the melt flow rates measured at 190 ° C. using loads of 6.48 kg and 2.16 kg, respectively. In this disclosure, the melt index was expressed using units of g / 10 min, or g / 10 min, or dg / min, or dg / min. These units are equivalent.

<Environmental stress crack resistance (ESCR)>
ESCR was determined according to ASTM D1693-13 (November 1, 2013). With a specimen thickness in the range of 0.0725 to 0.0775 inches and a notch depth in the range of 0.012 to 0.015 inches, Condition B was used. The concentration of Igepal used was 10% by volume.

The molecular weights _Mn , _Mw , and _Mz , and polydispersity ( _Mw / _Mn ) of the ethylene interpolymer product were determined using ASTM D6474-12 (December 15, 2012). This method defines the molecular weight distribution of the ethylene interpolymer product by high temperature gel permeation chromatography (GPC). This method uses commercially available polystyrene standards for GPC calibration.

<Unsaturated content>
The amount of unsaturated groups, ie, double bonds, in the ethylene interpolymer product is determined by ASTM D3124-98 (vinylidene unsaturation, published March 2011) and ASTM D6248-98 (vinyl and trans unsaturated, 2012 July 7). Monthly issue). The ethylene interpolymer sample a) first undergoes carbon disulfide extraction to remove additives that may interfere with the analysis, and b) the sample (pellet, film or granular form) has a uniform thickness (0.1 mm). 5 mm) of the plaque and c) the plaque was analyzed by FTIR.

<Comonomer content>
The amount of comonomer in the ethylene interpolymer product was determined by FTIR (Fourier Transform Infrared Spectroscopy) according to ASTM D6645-01 (issued January 2010).

<Composition distribution branching index (CDBI)>
The "composition distribution branching index" or "CDBI" of the disclosed examples and comparative examples was determined using a crystal-TREF unit commercially available from Polymer Char (Valencia, Spain). The acronym "TREF" refers to elevated temperature elution fractionation. A sample of the ethylene interpolymer product (80 to 100 mg) was placed in the reactor of a Polymer Char crystal-TREF unit, and the reactor was charged with 35 ml of 1,2,4-trichlorobenzene (TCB) and heated to 150 ° C. Then, the sample was kept at this temperature for 2 hours to dissolve the sample. An aliquot (1.5 mL) of the TCB solution was then loaded onto a Polymer Char TREF column packed with stainless steel beads, and the column was equilibrated at 110 ° C. for 45 minutes. The ethylene interpolymer product was then crystallized from the TCB solution in the column by gradually cooling the TREF column from 110 ° C to 30 ° C using a cooling rate of 0.09 ° C per minute. The TREF column was then equilibrated at 30 ° C. for 30 minutes. Next, the crystal was crystallized by passing the pure TCB solution through the column at a flow rate of 0.75 mL / min while gradually increasing the temperature of the column from 30 ° C. to 120 ° C. at a heating rate of 0.25 ° C. per minute. The ethylene interpolymer product eluted from the TREF column. Using the Polymer Char software, a TREF distribution curve was generated as the ethylene interpolymer product eluted from the TREF column, ie, the TREF distribution curve was calculated from the ethylene interpolymer eluted from the column as a function of the TREF elution temperature. 3 is a plot of the amount (or strength) of a polymer. CDBI ₅₀ was calculated from the TREF distribution curve for each ethylene interpolymer product analyzed. "CDBI ₅₀ " is defined as the percentage of ethylene interpolymers whose composition is within 50% of the central comonomer composition (25% on both sides of the central comonomer composition). This is calculated from the TREF composition distribution curve and the normalized integral of the TREF composition distribution curve. One skilled in the art will understand that a calibration curve is required to convert the TREF elution temperature to comonomer content, ie, the amount of comonomer in the ethylene interpolymer fraction eluting at a particular temperature. Generation of such calibration curves has been described in the prior art, for example, in Wild et al. , J. et al. Polym. Sci. , Part B, Polym. Phys. , Vol. 20 (3), pages 441-455, which is fully incorporated herein by reference.

<Heat deflection temperature>
The heat deflection temperature of the ethylene interpolymer product was determined using ASTM D648-07 (approved March 1, 2007). The heat deflection temperature is determined by a bending tool that applies 0.455 MPa (66 PSI) of stress to the center of the formed ethylene interpolymer plaque (0.125 inch thick), allowing the plaque to pass through the medium at a constant rate. At a temperature of 0.25 mm (0.010 inches) when heated.

<Vicat softening point (temperature)>
The Vicat softening point of the ethylene interpolymer product was determined according to ASTM D1525-07 (issued December 2009). In this test, the designated needle penetrates when the sample is subjected to ASTM D1525-07 test conditions, heating rate B (120 ± 10 ° C./hour and 938 gram load (10 ± 0.2 N load)). Determine the temperature.

<Neutron Activation Analysis (NAA)>
The catalyst residue in the ethylene interpolymer was measured using neutron activation analysis, hereinafter referred to as NAA, and performed as follows. A radiating vial (consisting of ultra-high purity polyethylene, 7 mL internal volume) was filled with an ethylene interpolymer product sample and the sample weight was recorded. Using a pneumatic transfer system, the sample is placed in a SLOWPOKE ™ nuclear reactor (Atomic Energy of Canada Limited, Ottawa, Ontario, Canada) and a short half-life element (eg, Ti, V, Al, Mg, And Cl) for 30-600 seconds, or for long half-life elements (eg, Zr, Hf, Cr, Fe, and Ni) for 3-5 hours. The average thermal neutron flux in the reactor was 5 × 10 ¹¹ / cm ² / sec. After irradiation, the sample was removed from the reactor and aged to destroy the radioactivity, but the short half-life element was aged for 300 seconds or the long half-life element was aged for several days. After aging, the gamma ray spectrum of the sample is measured using a germanium semiconductor gamma ray detector (ORTEC® model GEM55185, Advanced Measurement Technology Inc., Oak Ridge, TN, USA) and a multi-channel analyzer (ORTEC model DSPEC Pro). Was recorded. The amount of each element in the sample was calculated from the gamma spectrum and recorded in parts per million relative to the total weight of the ethylene interpolymer sample. The NAA system was calibrated using Specpure standards (1000 ppm solution of the desired element (> 99% purity)). 1 mL of the solution (target element) was dropped on a 15 mm × 800 mm rectangular filter paper with a pipette, and air-dried. The filter paper was then placed in a 1.4 mL polyethylene irradiation vial and analyzed by the NAA system. Measure the sensitivity of the NAA procedure using standards (counts / μg).

<Color index>
The whiteness index (WI) and yellowness index (YI) of the ethylene interpolymer product were measured using a BYK Gardner Color-View colorimeter according to ASTM E313-10 (approved in 2010).

<Dilution index (Y _d ) measurement>
A series of small amplitude frequency sweep tests were performed on each sample using an Anton Paar MCR501 rotary rheometer equipped with a "TruGap (TM) Parallel Plate Measurement System". A 1.5 mm gap and 10% strain amplitude were used throughout the test. The frequency sweep was 0.05-100 rad / sec at intervals of 7 points per decade. Test temperatures were 170 °, 190 °, 210 °, and 230 ° C. A master curve at 190 ° C. was constructed for each sample using the Rheoplus / 32 V3.40 software through the Standard TTS (Time-Temperature Superposition) procedure, which allows both horizontal and vertical shifts.

The _Yd and _Xd data generated are summarized in Table 4. The flow properties of the ethylene interpolymer product, such as melt strength and melt flow ratio (MFR), are well characterized by a dilution index (Y _d ) and a dimensionless coefficient (X _d ), as detailed below. You. In both cases, the flow properties are a strong function of Y _d and X _d and additionally depend on the zero shear viscosity. For example, the melt strength (hereinafter MS) values of the disclosed examples and comparative examples were found to follow the same equation, and the characteristic VGP points

And the derived rearranged coordinates (X _d , Y _d ) were confirmed to be sufficiently representative of the structure.

Where:
a ₀₀ = −33.33; a ₁₀ = 9.529; a ₂₀ = 0.03517; a ₃₀ = 0.894; a ₄₀ = 0.02969;
r ² = 0.984, and the average relative standard deviation was 0.85%. Further, this relationship can be expressed in terms of a dilution index (Y _d ) and a dimensionless coefficient (X _d ).

Where:
a ₀ = 33.34; a ₁ = 9.794; a ₂ = 0.02589; a ₃ = 0.1126; a ₄ = 0.03307;
r ² = 0.989, and the average relative standard deviation was 0.89%.

The MFR of the disclosed examples and comparative samples were found to follow a similar equation, indicating that the dilution parameters Y _d and X _d indicate that the flow properties of the disclosed examples are different from the reference and comparative examples. Further confirmation.

Where:
b ₀ = 53.27; b ₁ = 6.107; b ₂ = 1.384; b ₃ = 20.34;
a r ² = 0.889, average relative standard deviation and 3.3%.

  In addition, the polymerization processes and catalyst formulations disclosed herein provide a desired physical property balance (i.e., some final properties are through multidimensional optimization) compared to competing polyethylenes having comparable density and melt index. It allows the production of an ethylene interpolymer product that can be converted to a flexible article of manufacture (if desired) that can be balanced.

<G '[＠G''= 500 Pa] parameter>
The G ′ [＠ G ″ = 500 Pa] parameter was generated using conventional rheological equipment and data processing techniques well known to those skilled in the art. The rheological data was generated on a Rheometrics RDS-II (Rheometrics Dynamic Spectrometer II), a strain-controlled rotational rheometer. The analyzed ethylene interpolymer sample is in the form of a compression molded sample disk; the sample disk is placed between two parallel plate test fixtures in a heated chamber of the RDS-II; One is attached to the actuator and the other is attached to the transducer. The test is performed at a constant strain and a constant temperature of 190 ° C., in various frequency ranges, typically 0.05-100 radians / second. This test produces the following data characterizing the elastic and viscous attributes of the polymer melt: real, elastic or storage modulus (G ′), viscosity or loss modulus (G ″), complex viscosity η ^* and tan δ. (As a function of frequency (dynamic vibration)). The G ′ [＠ G ″ = 500 Pa] parameter was determined as follows: G ′ was plotted as a function of G ″ (a skilled artisan commonly calls this plot a Cole-Cole plot) and G ′ [＠G ″ = 500 Pa] is simply the G ′ value (Pa), and G ″ is equal to 500 Pa. Sample plaques were prepared as follows: (a) For samples having a melt index of less than 1.0 dg / min, about 5.5 g of ethylene interpolymer was compressed at 190 ° C. into 1.8 mm thick circular plaques. A 2.5 cm diameter sample disk was punched out of a circular plaque using a circular punch and molded and loaded on an RDS-II; or (b) for a sample having a melt index of 1.0 dg / min or more; Approximately 2.8 g of the ethylene interpolymer was compression molded at 190 ° C. into a 0.9 mm thick circular plaque, and a 2.8 cm diameter sample disk was punched out of the circular plaque using a circular punch and loaded into the RDS-II. . The finished plaque must be free of bubbles and impurities and have a smooth surface without defects.

<Tensile properties>
The following tensile properties were determined using ASTM D882-12 (August 1, 2012): tensile strength at break (MPa), elongation at yield (%), yield strength (MPa), ultimate elongation (%), Ultimate strength (MPa) and 1% and 2% secant modulus (MPa).

<Bending characteristics>
Flexural properties, ie, 2% flexural secant modulus, were determined using ASTM D790-10 (published April 2010).

<IZOD impact strength>
IZOD impact strength (ft-lbs / inch) was determined using an Izod impact pendulum-like tester using ASTM D256-05 (issued January 2005).

<Hexane extract>
The hexane extract was determined according to Federal Regulations 21 CFR § 177.1520 paragraphs (c) 3.1 and 3.2. Here, the amount of the hexane extract in the sample is determined by a gravimetric method.

<Polymerization>
The following examples are presented for the purpose of illustrating selected embodiments of the present disclosure, and it is understood that the examples shown do not limit the scope of the claims.

  Embodiments of the ethylene interpolymer product disclosed herein were produced in a continuous solution polymerization pilot plant with reactors arranged in a series configuration. Methylpentane (a commercially available blend of methylpentane isomers) was used as the process solvent. 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), and the tubular reactor (R3) Had a volume of 4.8 gallons (18 L). An example of an ethylene interpolymer product was produced using an R1 pressure of about 14 MPa to about 18 MPa, but R2 was operated at a lower pressure to promote continuous flow from R1 to R2. R1 and R2 were operated in serial mode, with the first output stream from R1 flowing directly into R2. Both CSTRs were agitated to provide conditions for the reactor contents to mix well. The process was operated continuously by feeding fresh process solvent, ethylene, 1-octene and hydrogen to the reactor.

The single-site catalyst component used was component (i) cyclopentadienyl tri (tert-butyl) phosphinimine titanium dichloride (Cp [(t-Bu) ₃ PN] TiCl ₂ ) (hereinafter referred to as PIC-1), Component (ii) methylaluminoxane (MAO-07), component (iii) trityltetrakis (pentafluoro-phenyl) borate, and component (iv) 2,6-di-tert-butyl-4-ethylphenol. The single site catalyst component solvent used was methylpentane for components (ii) and (iv) and xylene for components (i) and (iii). The amount 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 Component (i), PIC-1, was included. The molar ratio of the single-site catalyst components used to produce Example 81 was R1 (ii) / (i) molar ratio = 100, ie [(MAO-07) / (PIC-1)]; (Iv) / (ii) molar ratio = 0.0, ie [(2,6-di-tert-butyl-4-ethylphenol) / (MAO-07)]; R1 (iii) / (i) The molar ratio was 1.1, that is, [(trityltetrakis (pentafluoro-phenyl) borate) / (PIC-1)].

The in-line Ziegler-Natta catalyst formulation comprises component (v), butylethyl magnesium; component (vi), tert-butyl chloride; component (vii), titanium tetrachloride; component (viii), diethylaluminum ethoxide; (Ix), prepared from a component group of triethylaluminum. Methylpentane was used as a catalyst component solvent. An in-line Ziegler-Natta catalyst formulation was prepared using the following steps. In Step 1, triethylaluminum and dibutylmagnesium ((triethylaluminum) / (dibutylmagnesium) molar ratio is 20) are combined with a solution of tert-butyl chloride and reacted for about 30 seconds (HUT-1); A solution of titanium chloride is added to the mixture formed in step 1 and allowed to react for about 14 seconds (HUT-2); in step 3, the mixture formed in step 2 is allowed to react for another 3 seconds (HUT-3). And then injected into R2. The in-line Ziegler-Natta precatalyst formulation was injected into R2 using the process solvent and the flow rate of the catalyst-containing solvent was about 49 kg / hr. An in-line Ziegler-Natta catalyst formulation was formed in R2 by injecting a solution of diethylaluminum ethoxide into R2. The amount of titanium tetrachloride added to reactor 2 (R2), "R2 (vii) (ppm)", is shown in Table 2A. To be clear, in Example 81, the solution in R2 was 3.99 ppm. It contained TiCl ₄ . The molar ratio of the in-line Ziegler-Natta catalyst component, specifically, the R2 (vi) / (v) molar ratio, ie, [(tert-butyl chloride) / (butylethylmagnesium)]; R2 (viii) / (viii) ) Molar ratio, ie [(diethylaluminum ethoxide) / (titanium tetrachloride)]; and R2 (ix) / (vii) molar ratio, ie [(triethylaluminum) / (titanium tetrachloride)], are also shown in Table 2A. Is shown in Specifically, in Example 81, the R2 (vi) / (v) molar ratio = 1.83; the R2 (viii) / (vii) molar ratio = 1.35, and the R2 (ix) / (vii) molar ratio A molar ratio of = 0.35 was used to synthesize the in-line Ziegler-Natta catalyst. In all disclosed examples, 100% diethylaluminum ethoxide was injected directly into R2.

  In Example 81 (single site catalyst formulation in R1 + inline Ziegler-Natta catalyst in R2), the ethylene interpolymer product was produced at a production rate of 93.5 kg / hr, while Comparative Example 20 (both R1 and R2) The single-site catalyst formulation in Example 1) had a maximum production of 74 kg / hr of the comparative ethylene interpolymer product.

  The average residence time of the solvent in the reactor is mainly affected by the amount of solvent flowing through each reactor and the total amount of solvent flowing through the solution process, and the following are examples given in Tables 2A-2C The average reactor residence time was about 61 seconds for R1, about 73 seconds for R2, and about 50 seconds for R3 (the volume of R3 was about 4.8 gallons ( 18L).

  The polymerization in the continuous solution polymerization process was stopped by adding a catalyst deactivator to the third output stream leaving the tubular reactor (R3). The catalyst deactivator used was octanoic acid (caprylic acid), commercially available from P & G Chemicals (Cincinnati, OH, USA). The catalyst deactivator was added such that the moles of fatty acids added were 50% of the total moles of titanium and aluminum added to the polymerization process. Mol = 0.5 × (moles of titanium + moles of aluminum), and this molar ratio was used consistently in all examples.

  A two-stage devolatilization process is used to recover the ethylene interpolymer product from the process solvent, i.e., using two vapor / liquid separators and a second (from a second V / L separator) The bottom stream was passed through a gear pump / pelletizer combination. Kyowa Chemical Industry Co. DHT-4V® (hydrotalcite) supplied by LTD (Tokyo, Japan) was used as a passivator or acid remover in a continuous solution process. A slurry of DHT-4V in the process solvent was added before the first V / L separator. The molar amount of DHT-4V added was about 10 times higher than the molar amount of chloride added to the process, but the chlorides added were titanium tetrachloride and tert-butyl chloride.

  Prior to pelletizing, about 500 ppm of IRGANOX® 1076 (primary antioxidant) and about 500 ppm of IRGAFOS® 168 (secondary antioxidant), based on the weight of the ethylene interpolymer product, The addition stabilized the ethylene interpolymer product. The antioxidant was dissolved in the process solvent and added between the first and second V / L separator.

Tables 2B and 2C disclose additional solution process parameters such as the distribution of ethylene and 1-octene between reactors recorded during the production of Example 81 and Comparative Example 20, reactor temperature, and ethylene conversion. I do. In Comparative Example 20, the single site catalyst formulation was injected into both reactor R1 and reactor R2, and the ES ^R1 was 45%, the percent assigned to reactor 1. In Example 81, the single site catalyst formulation was injected into R1, the in-line Ziegler-Natta catalyst formulation was injected into R2, and the ES ^R1 was 35%.

  The present disclosure relates to caps and closures comprising at least one ethylene interpolymer product, wherein the at least one ethylene interpolymer product comprises at least one single-site catalyst formulation and at least one heterogeneous catalyst formulation. Manufactured in a continuous solution polymerization process utilizing at least two reactors to produce manufactured caps and closures having improved properties.

Claims (24)

(I) a first ethylene interpolymer;
(Ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer;
A cap and closure comprising at least one layer comprising an ethylene interpolymer product comprising:
The first ethylene interpolymer has the formula:
^{_{(L A) a M (Pl}} ) b (Q) n
(Wherein, L ^A is unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl, and is selected from the group consisting of substituted fluorenyl;
M is a metal selected from titanium, hafnium, and zirconium;
Pl is a phosphinimine ligand;
Q is independently selected from the group consisting of a hydrogen atom, a halogen atom, a _C1-10 hydrocarbyl radical, a _C1-10 alkoxy radical, and a _C5-10 aryloxide radical;
Each of the above hydrocarbyl, alkoxy, and aryl oxide radicals are unsubstituted or substituted by halogen atoms, C _1-18 alkyl radicals, C _1-8 alkoxy radicals, C _6-10 aryl or aryloxy radicals. no, or amide radical is substituted by C _1-8 alkyl radical of up to two, or not substituted, or be further substituted by phosphide radicals substituted by C _1-8 alkyl radical of up to two Often;
a is 1; b is 1; n is 1 or 2; (a + b + n) is equal to the valence of metal M)
Produced using a single-site catalyst formulation comprising component (i) defined by:
Said second ethylene interpolymer is produced using a first in-line Ziegler-Natta catalyst formulation;
The third ethylene interpolymer is produced using the first in-line Ziegler-Natta catalyst formulation or the second in-line Ziegler-Natta catalyst formulation;
The ethylene interpolymer products has a dilution index Y _d of less than 0;
The ethylene interpolymer product has a melt index of about 0.3 to about 7 dg / min, the melt index being measured according to ASTM D1238 (2.16 kg load and 190 ° C.)
The ethylene interpolymer product has a G ′ [＠G ″ = 500 Pa] of 80 Pa to 120 Pa;
Caps and closures.   The cap or closure of claim 1, wherein the single site catalyst formulation further comprises an alumoxane cocatalyst, a boron ionic activator, and optionally a hindered phenol.   The cap or closure according to claim 2, wherein the alumoxane cocatalyst is methylalumoxane (MAO) and the boron ionic activator is trityltetrakis (pentafluoro-phenyl) borate. Wherein the ethylene interpolymer product is
a) 0.03 or more terminal vinyl unsaturation per 100 carbon atoms;
b) 3 million parts per million (ppm) or more of total catalytic metal; or c) dimensionless coefficient X _{d of} less than 0;
The cap or closure of claim 1, further comprising one or more of the following.   The cap or closure of claim 1, wherein the ethylene interpolymer product has a melt index from about 0.3 to about 5 dg / min. The ethylene interpolymer products, a density measured according to ASTM D792, has a density of about 0.948～ about 0.968 g / cm ^3, a cap or closure as claimed in claim 1. The cap or closure of claim 1, wherein the ethylene interpolymer product has a M _w / M _n of about 2 to about 25. 2. The cap or closure of claim 1, wherein the ethylene interpolymer product has a CDBI ₅₀ of about 54% to about 98%. (I) wherein the first ethylene interpolymer comprises about 15 to about 60 weight percent of the ethylene interpolymer product, has a melt index of about 0.01 to about 200 dg / min and about 0.855 to about 0 Has a density of .975 g / cc;
(II) the second ethylene interpolymer comprises about 30 to about 85 weight percent of the ethylene interpolymer product, a melt index of about 0.3 to about 1000 dg / min and about 0.89 to about 0 Has a density of .975 g / cc;
(III) the third ethylene interpolymer comprises about 0 to about 30 weight percent of the ethylene interpolymer product, a melt index of about 0.5 to about 2000 dg / min and about 0.89 to about 0 Has a density of .975 g / cc;
The weight percentage is the weight of the first, second, or third ethylene interpolymer, individually divided by the weight of the ethylene interpolymer product;
The density is measured according to ASTM D792,
A cap or closure according to claim 1.   The cap or closure of claim 1, wherein the ethylene interpolymer product is synthesized using a solution polymerization process. The cap or closure of claim 1, wherein the ethylene interpolymer product further comprises 0 to about 1.0 mole percent of one or more C ₃ -C ₁₀ α-olefins.   The cap or closure of claim 11, wherein the one or more α-olefins is 1-hexene, 1-octene or a mixture of 1-hexene and 1-octene.   The cap or closure of claim 1, wherein the ethylene interpolymer product has less than 1 part per million (ppm) of metal A, wherein the metal A is derived from component (i).   Wherein the ethylene interpolymer product comprises metal B and optionally metal C, wherein the sum of metal B and metal C is from about 3 to about 11 parts per million; Wherein the metal C is derived from the second in-line Ziegler-Natta catalyst formulation; and optionally, the metal B and the metal C are: The cap or closure of claim 1, wherein the cap or closure is the same metal.   15. The metal of claim 14, wherein said metal B and said metal C are independently selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium or osmium. A cap or closure as described.   15. The cap or closure of claim 14, wherein said metal B and said metal C are independently selected from titanium, zirconium, hafnium, vanadium or chromium. (I) the first ethylene interpolymer has a first CDBI ₅₀ of about 70 to about 98%;
(II) the second ethylene interpolymer has a second CDBI ₅₀ of about 45 to about 98%;
(III) when present, the optional third ethylene interpolymer has a third CDBI ₅₀ of about 35 to about 98%;
A cap or closure according to claim 1. It said first CDBI ₅₀ is the higher than the second CDBI _50, wherein the first CDBI ₅₀ is higher than the third CDBI _50, cap or closure as claimed in claim 16. (I) wherein the first ethylene interpolymer has a first _M w / _{M n} of about 1.7 to about 2.8;
(II) the second ethylene interpolymer has a second _Mw / _Mn of about 2.2 to about 4.4;
(III) the third ethylene interpolymer has a third _Mw / _Mn of about 2.2 to about 5.0;
The first M _w / M _n is lower than the second M _w / M _n and the third M _w / M _n ;
A cap or closure according to claim 1. By blending the second ethylene interpolymer and the third ethylene interpolymer, a heterogeneous ethylene interpolymer blend having a fourth M _w / M _n is formed and the fourth M _w / M _n is formed. 20. The ethylene interpolymer product of claim 19, wherein is no more than the second _Mw / _Mn .   The cap or closure according to claim 1, having a G ′ [＠G ″ = 500 Pa] of 90 Pa to 120 Pa.   The cap or closure according to claim 1, having a G ′ [＠G ″ = 500 Pa] of 100 Pa to 120 Pa.   The cap or closure of claim 1, further comprising a nucleating agent or a mixture of nucleating agents.   The process of manufacturing a cap or closure according to claim 1, wherein the process comprises at least one compression molding step or one injection molding step.