CN110753708A

CN110753708A - Cover and cover

Info

Publication number: CN110753708A
Application number: CN201880024674.1A
Authority: CN
Inventors: X.王; T.李; F.西坦; C.多宾; K.泰勒; H.哈达曼; B.莫罗伊
Original assignee: Nova Chemicals International SA
Current assignee: Nova Chemicals International SA
Priority date: 2017-02-13
Filing date: 2018-02-12
Publication date: 2020-02-04
Anticipated expiration: 2038-02-12
Also published as: BR112019016671B1; JP2020510583A; KR20190116367A; CL2019002282A1; CN110753708B; PE20191366A1; CA2957706C; JP6828177B2; CA2957706A1; MX2019009550A; BR112019016671A2; AU2018217985A1; KR102259579B1; EP3580246A1; WO2018146649A1

Abstract

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

Description

Cover and cover

Technical Field

The present disclosure relates to caps and covers comprising at least one ethylene interpolymer (interpolymer) product made in a continuous solution polymerization process utilizing at least two reactors with at least one single site catalyst formulation and at least one heterogeneous catalyst formulation to produce fabricated caps and covers having improved properties.

Background

The ethylene interpolymer products are used in cap and closure applications to produce a variety of articles of manufacture, such as caps for carbonated or non-carbonated fluids, and closures including dispensing closures having a living hinge function. Such caps and covers are typically produced using conventional injection or compression molding processes.

In some embodiments, the ethylene interpolymers disclosed herein have a melt index from ≧ 0.3dg/min to ≦ 5.0dg/min, with G '[ @ G "═ 500Pa ] advantageous in compression molding processes, i.e., G' @ G" ═ 500Pa ] from ≧ 40Pa to ≦ 70 Pa. In some embodiments, the ethylene interpolymers disclosed herein have a melt index > 5.0dg/min to ≦ 20dg/min, have a G '[ @ G "═ 500Pa ] advantageous in injection molding processes, i.e., G' [ @ G" ═ 500Pa ] from ≧ 1Pa to ≦ 35 Pa. Additionally, the ethylene interpolymers disclosed herein have a melt index > 0.3dg/min to ≦ 8dg/min, have a G '[ @ G "═ 500Pa ] advantageous in continuous compression molding, i.e., G' @ G" ═ 500Pa ] from ≥ 80Pa to ≦ 120 Pa.

In the cap and closure market, there is a continuing need to develop new ethylene interpolymers with improved properties. Non-limiting examples of requirements include: stiffer covers and covers (higher modulus), which allows the manufacture of thinner and lighter covers and covers, i.e. improved sustainability (reduced resources); higher Heat Distortion Temperature (HDT), which extends the maximum service temperature of the lid and cover and is advantageous in hot fill applications; a faster crystallization rate, which allows the lid and cover to be manufactured at a higher production rate, i.e. more parts per hour; and improved Environmental Stress Cracking Resistance (ESCR), particularly for caps and caps used in chemically aggressive environments.

In some embodiments, the disclosed ethylene interpolymer products are produced in a solution polymerization process, wherein the catalyst components, solvent, monomers, and hydrogen are fed under pressure into more than one reactor for ethylene homopolymerization or ethylene copolymerization, the solution reactor temperature may be in the range of from about 80 ℃ to about 300 ℃, and the pressure is typically in the range of from about 3MPag to about 45MPag, and the resulting ethylene interpolymer remains dissolved in the solvent the residence time of the solvent in the reactor is relatively short, such as from about 1 second to about 20 minutes.

Disclosure of Invention

The present disclosure relates to caps and covers comprising at least one ethylene interpolymer product made in a continuous solution polymerization process utilizing at least two reactors with at least one single-site catalyst formulation and at least one heterogeneous catalyst formulation to produce fabricated caps and covers having improved properties.

Embodiments of the present disclosure include caps and covers having at least one layer comprising an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; wherein saidDilution index Y of ethylene interpolymer product_dGreater than 0.

Another embodiment of the present disclosure includes a cap and cover having at least one layer comprising 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 dilution index Y_dLess than 0.

Disclosed herein are covers or enclosures comprising at least one layer comprising an ethylene interpolymer product comprising:

a first ethylene interpolymer;

a second ethylene interpolymer; and

an optional third ethylene interpolymer;

wherein the first ethylene interpolymer is produced using a single-site catalyst formulation comprising component (i) defined by the formula:

(L^A)_aM(PI)_b(Q)_n

wherein

L^ASelected from the group consisting of unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl, and substituted fluorenyl;

m is a metal selected from titanium, hafnium and zirconium;

pl is a phosphinimine ligand;

q is independently selected from a hydrogen atom, a halogen atom, C_1-10Hydrocarbyl radical, C_1-10Alkoxy and C_5-10(ii) an aryloxide group; wherein each of said hydrocarbyl, alkoxy and aryloxy groups may be unsubstituted or further substituted by a halogen atom, C_1-18Alkyl radical, C_1-8Alkoxy radical, C_6-10Aryl or aryloxy, unsubstituted or substituted by up to two C_1-8Alkyl-substituted amido radical being unsubstituted or substituted by up to two C_1-8Alkyl substituted phosphido (phosphido) substitution;

wherein

a is 1; b is 1; n is 1 or 2; and (a + b + n) is equal to the valence of the metal M;

wherein the second ethylene interpolymer is produced using a first in-line Ziegler-Natta catalyst formulation;

wherein the third ethylene interpolymer is produced using the first or second in-line Ziegler-Natta catalyst formulation; wherein the ethylene interpolymer product has a dilution index Y_dLess than 0;

wherein the ethylene interpolymer product has a melt index from about 0.3dg/min to about 7dg/min, wherein the melt index is measured in accordance with ASTM D1238(2.16kg load and 190 ℃); and is

Wherein the ethylene interpolymer product has a G' [ @ G "═ 500Pa ] from 80Pa to 120 Pa.

Embodiments include a cap and a jacket having at least one layer comprising an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; wherein the terminal vinyl unsaturation/100 carbon atoms of the ethylene interpolymer is greater than or equal to 0.03.

Embodiments of the present disclosure include caps and covers having at least one layer comprising 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 total catalytic metal of 3 parts per million (ppm) or more.

Additional embodiments include covers and enclosures having at least one layer comprising an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; wherein the ethylene interpolymer product has a dilution index Y_dGreater than 0 and terminal vinyl unsaturation/100 carbon atoms of greater than or equal to 0.03, or total catalytic metals of greater than or equal to 3 parts per million (ppm), or dimensionless modulus X_d＞0。

Additional embodiments include covers and enclosures having at least one layer comprising an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and(iii) an optional third ethylene interpolymer; wherein the ethylene interpolymer product has a dilution index Y_dLess than 0 and terminal vinyl unsaturation/100 carbon atoms of greater than or equal to 0.03, or total catalytic metals of greater than or equal to 3 parts per million (ppm), or dimensionless modulus X_d＜0。

Additional embodiments include covers and enclosures having at least one layer comprising 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 terminal vinyl unsaturation/100 carbon atoms of greater than or equal to 0.03 and a total catalytic metal of greater than or equal to 3 parts per million (ppm) or a dimensionless modulus X_d＞0。

Embodiments include covers and enclosures having at least one layer comprising 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 total catalytic metal of 3 parts per million (ppm) or more and a dimensionless modulus X_d＞0。

Additional embodiments include covers and enclosures having at least one layer comprising 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 dilution index Y_dGreater than 0, terminal vinyl unsaturation/100 carbon atoms of greater than or equal to 0.03, and a total catalytic metal of greater than or equal to 3 parts per million (ppm) or a dimensionless modulus X_d＞0。

Additional embodiments include covers and enclosures having at least one layer comprising 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 dilution index Y_dLess than 0, terminal vinyl unsaturation/100 carbon atoms of greater than or equal to 0.03, and a total catalytic metal of greater than or equal to 3 parts per million (ppm) or a dimensionless modulus X_d＜0。

Additional embodiments include having at least one ethylene-containing polymerA cap and a cap of a layer of an interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; wherein the dimensionless modulus X of the ethylene interpolymer product_dGreater than 0, and total catalytic metal greater than or equal to 3 parts per million (ppm), and dilution index Y_dGreater than 0 or terminal vinyl unsaturation/100 carbon atoms of greater than or equal to 0.03.

Additional embodiments include covers and enclosures having at least one layer comprising an ethylene interpolymer product comprising: (i) a first ethylene interpolymer; (ii) a second ethylene interpolymer; and (iii) optionally a third ethylene interpolymer; wherein the dimensionless modulus X of the ethylene interpolymer product_dLess than 0, and total catalytic metal is greater than or equal to 3 parts per million (ppm), and the dilution index Y_dLess than 0 or terminal vinyl unsaturation/100 carbon atoms of 0.03 or more.

Embodiments also include a cap and a jacket having at least one layer comprising 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 dilution index Y_dGreater than 0, dimensionless modulus X_dGreater than 0, total catalytic metals greater than or equal to 3 parts per million (ppm), and terminal vinyl unsaturation per 100 carbon atoms greater than or equal to 0.03.

Embodiments also include a cap and a jacket having at least one layer comprising 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 dilution index Y_dLess than 0, dimensionless modulus X_dLess than 0, total catalytic metals greater than or equal to 3 parts per million (ppm), and terminal vinyl unsaturation per 100 carbon atoms greater than or equal to 0.03.

The ethylene interpolymer products disclosed herein have a melt index from about 0.3dg/min to about 20dg/min, about 0.948g/cm³To about 0.968g/cm³A density of from about 2 to about 25M_w/M_nAnd a CDBI of from about 54% to about 98%₅₀(ii) a Wherein the melt index is according to ASTM D1238 (2.16)kg load and 190 ℃) and the density is measured according to astm d 792.

Additionally, disclosed ethylene interpolymer products comprise: (i) about 15 to about 60 weight percent of a first ethylene interpolymer having a melt index from about 0.01dg/min to about 200dg/min and a density from about 0.855g/cm³To about 0.975g/cm³(ii) a (ii) About 30 to about 85 weight percent of a second ethylene interpolymer having a melt index of about 0.3 to about 1000dg/min and a density of about 0.89g/cm³To about 0.975g/cm³(ii) a And (iii) optionally, from about 0 wt% to about 30 wt% of a third ethylene interpolymer having a melt index from about 0.5dg/min to about 2000dg/min and a density from about 0.89g/cm³To about 0.975g/cm³(ii) a Wherein the weight percent 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 caps and caps comprising one or more ethylene interpolymer products synthesized in a solution polymerization process, wherein the ethylene interpolymer product may contain from 0 wt% to about 1.0 wt% of one or more α -olefins.

Additionally, the first ethylene interpolymer was synthesized using a single-site catalyst formulation, and the second ethylene interpolymer was synthesized using a first heterogeneous catalyst formulation. Embodiments of the caps and covers can comprise an ethylene interpolymer product wherein a third ethylene interpolymer is synthesized using either the first heterogeneous catalyst formulation or the second heterogeneous catalyst formulation.

The second ethylene interpolymer may be synthesized using the first in-line ziegler-natta catalyst formulation or the first batch ziegler-natta catalyst formulation. Optionally, the third ethylene interpolymer is synthesized using the first in-line ziegler-natta catalyst formulation or the first batch ziegler-natta catalyst formulation. The optional third ethylene interpolymer may be synthesized using a second in-line ziegler-natta catalyst formulation or a second batch ziegler-natta catalyst formulation.

Embodiments of the present disclosure include caps and covers comprising an ethylene interpolymer product, wherein the ethylene interpolymer product has 1 parts per million (ppm) or less of metal a; and wherein metal a is derived from a single site catalyst formulation; non-limiting examples of metal a include titanium, zirconium, or hafnium.

Additional embodiments include caps and caps comprising an ethylene interpolymer product having metal B and optionally metal C; wherein the total amount of metal B and metal C is from about 3 to about 11 parts per million (ppm); wherein metal B is derived from a first heterogeneous catalyst formulation and metal C is derived from an optional second heterogeneous catalyst. Metals B and C are independently selected from the following non-limiting examples: 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 contain an ethylene interpolymer product wherein the first ethylene interpolymer has a first M_w/M_nThe second ethylene interpolymer having a second M_w/M_nAnd the optional third ethylene has a third M_w/M_n(ii) a Wherein the first M_w/M_nLower than the second M_w/M_nAnd optionally a third M_w/M_n. Embodiments also include ethylene interpolymer products wherein the second ethylene interpolymer and the third ethylene interpolymer are blended to have a fourth M_w/M_nThe ethylene interpolymer blend of (a); wherein the fourth M_w/M_nUnlike the second M_w/M_nAnd (4) wide. Additional ethylene interpolymer product embodiments are characterized by a second M_w/M_nAnd a third M_w/M_nAre each less than about 4.0.

In addition, embodiments of the cap and cover include an ethylene interpolymer product wherein the first ethylene interpolymer has a first CDBI from about 70% to about 98%₅₀The second ethylene interpolymer has a second CDBI of about 45% to about 98%₅₀And the optional third ethylene interpolymer has a third CDBI of from about 35% to about 98%₅₀. Other embodiments include ethylene interpolymer products wherein the first CDBI is₅₀Higher than second CDBI₅₀(ii) a Optionally, the first CDBI₅₀Higher than third CDBI₅₀。

Embodiments also include covers and covers having a melt index of 0.4dg/min to 5.0dg/min and a G' [ @ G "═ 500Pa ] > 40Pa to 70 Pa. Further embodiments include caps and covers having a melt index > 5.0dg/min to ≦ 20dg/min and G' [ @ G "═ 500Pa ] > 1Pa to ≦ 35 Pa. Further embodiments include caps and covers having a melt index > 0.3dg/min to ≦ 7dg/min and G' [ @ G "═ 500Pa ] > 80Pa to ≦ 120 Pa.

Finally, a method of manufacturing any of the above lid and cover embodiments is disclosed, wherein the method comprises at least one compression molding step or one injection molding step.

Brief Description of Drawings

For the purpose of illustrating selected embodiments of the present disclosure, the following drawings are provided; it should be understood that the illustrated embodiments do not limit the disclosure.

Figure 1 plots G' [ @ G ═ 500Pa for ethylene interpolymer products examples 1001 and 1002, examples 81 and 91, and comparative examples Q, V, R, Y and X]Plot against melt index. Examples 1001 and 1002 and examples 81 and 91 (filled symbols) are examples of the ethylene interpolymer products disclosed herein. Comparative examples Q and R are comparative lid and cap HDPE resins available from NOVA Chemicals inc; CCs153(0.9530 g/cm), respectively³1.4dg/min) and CCs757(0.9589 g/cm)³6.7dg/min), prepared in a two reactor solution process using a single site catalyst. Comparative example V is a commercial cap and lid HDPE resin available from the Dow chemical company, ContinuumDMDA-1250NT 7(0.957 g/cm)³1.5dg/min) was prepared in a two reactor gas phase process using a ziegler-natta catalyst. Comparative examples X and Y are from INEOS Olefins&Commercial cap and cap HDPE resins available from Polymers USA; respectively INEOS HDPE J50-1000-³11dg/min) and INEOS HDPE J60-800-³，7.9dg/min)。

FIG. 2 is the following dilution index (Y)_d) (dimension is degrees (°)) and dimensionless modulus (X)_d) The following drawings:

comparative example S (open triangle, Y)_d＝X_d0) is an ethylene interpolymer comprising an ethylene interpolymer (rheological) synthesized in a solution process using an in-line ziegler-natta catalystStudy reference);

examples 6, 101, 102, 103, 110, 115, 200, 201 (filled circles, Y)_d> 0 and X_d< 0) is an ethylene interpolymer product as described in the present disclosure comprising a first ethylene interpolymer synthesized using a single site catalyst formulation and a second ethylene interpolymer synthesized in a solution process using an in-line ziegler-natta catalyst formulation;

examples 120, 130 and 131 (solid squares, Y)_d＞0，X_d> 0) is an ethylene interpolymer product as described in this disclosure;

comparative examples D and E (open diamond, Y)_d＜0，X_d> 0) is an ethylene interpolymer comprising a first ethylene interpolymer synthesized using a single-site catalyst form (formation) and a second ethylene interpolymer synthesized in a solution process using a batch ziegler-natta catalyst formulation; and

comparative example A (open square, Y)_d> 0 and X_d< 0) is an ethylene interpolymer comprising first and second ethylene interpolymers synthesized in a solution process using a single site catalyst format.

FIG. 3 shows a typical Van Gurp Palmen (VGP) plot of phase angle [ ° ] versus complex modulus [ kPa ].

FIG. 4 plots the storage modulus (G ') and loss modulus (G') vs. frequency ω showing crossover_xAnd the phase angle reaches omega_cTwo decimal shifts (ω)_c＝0.01ω_x)。

Fig. 5 compares the amount of terminal vinyl unsaturation per 100 carbon atoms (terminal vinyl groups/100C) in the ethylene interpolymer products of the present disclosure (filled circles) with comparative examples B, C, E, E2, G, H, H2, I, and J (open triangles).

Figure 6 compares the total amount of catalytic metal (ppm) in the ethylene interpolymer products of the present disclosure (filled circles) with comparative examples B, C, E, E2, G, H, H2, I, and J (open triangles).

Best mode for carrying out the invention

Definition of terms

Other than in the examples, or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, extrusion conditions, and the like used in the specification and claims are to be understood as modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the various embodiments. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. The numerical values set forth in the specific examples should be reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

It should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10; i.e. having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10. Because the disclosed numerical ranges are continuous, they include every value between the minimum and maximum values. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations.

In practice, all compositional ranges expressed herein are limited as a whole and do not exceed 100% (volume percent or weight percent). Where multiple components may be present in the composition, the sum of the maximum amounts of each component may exceed 100%, and it is understood and as will be readily appreciated by those skilled in the art that the amounts of components actually used will correspond to a maximum of 100%.

For a more complete understanding of this disclosure, the following terms are defined and should be used in conjunction with the figures and the description of the various embodiments.

The term "dilution index (Y)_d) "and" dimensionless modulus (X)_d) "baseIn rheological measurements and are fully described in this disclosure.

The term "G '[ @ G" ═ 500Pa ] "(Pa) is a rheological measurement, i.e. the value of the storage modulus G' (Pa) in the case 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 and chemically bond thereto to form a polymer.

As used herein, the term "α -olefin" is used to describe a monomer having a straight hydrocarbon chain containing 3 to 20 carbon atoms and having a double bond at one end of the chain.

As used herein, the term "ethylene polymer" refers to macromolecules produced from ethylene monomers and optionally one or more additional monomers, regardless of the particular catalyst or particular method used to prepare the ethylene polymer.

The term "ethylene interpolymer" refers to a subset of polymers within the group of "ethylene polymers," excluding polymers produced in high pressure polymerization processes; non-limiting examples of polymers produced in high pressure processes 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 in the ethylene interpolymer group produced using a heterogeneous catalyst formulation; non-limiting examples thereof include Ziegler-Natta or chromium catalysts.

The term "homogeneous ethylene interpolymer" refers to a subset of the polymers in the group of ethylene interpolymers produced using metallocene or single site catalysts. In general, homogeneous ethylene interpolymers have a narrow molecular weight distribution, such as Gel Permeation Chromatography (GPC) M_w/M_nA value of less than 2.8; m_wAnd M_nRespectively, the weight average molecular weight and the number average molecular weight. In contrast, M of heterogeneous ethylene interpolymers_w/M_nGenerally greater than M of a homogeneous ethylene interpolymer_w/M_n. In general, homogeneous ethylene interpolymers also have a narrow comonomer distribution, i.e., each macromolecule within the molecular weight distribution has a similar comonomer content. In general, the composition distribution breadth index "CDBI" is used to quantify how the comonomer is distributed within the ethylene interpolymer, as well as to distinguish ethylene interpolymers produced with different catalysts or processes. "CDBI₅₀"is defined as the percentage of ethylene interpolymer whose composition is within 50% of the median comonomer composition; this definition is consistent with that described in U.S. patent 5,206,075 assigned to Exxon Chemical Patents inc. CDBI of ethylene interpolymers₅₀Can be calculated from the TREF curve (temperature rising elution fractionation); the TREF method is described in Wild et al, J.Polym.Sci., PartB, Polym.Phys., Vol.20 (3), p.441-455. In general, CDBI of homogeneous ethylene interpolymers₅₀Greater than about 70%. in contrast, CDBI of a heterogeneous ethylene interpolymer containing α -olefin₅₀CDBI generally lower than homogeneous ethylene interpolymers₅₀。

As is well known to those skilled in the art, homogeneous ethylene interpolymers are often further subdivided into "linear homogeneous ethylene interpolymers" and "substantially linear homogeneous ethylene interpolymers". The number of long chain branches of these two subgroups differs: more specifically, the linear homogeneous ethylene interpolymers have less than about 0.01 long chain branches per 1000 carbon atoms; while substantially linear ethylene interpolymers have greater than about 0.01 to about 3.0 long chain branches per 1000 carbon atoms. The long chain branches are macromolecules in nature, i.e., they are similar in length to the macromolecules to which they are attached. Hereinafter, in the present disclosure, the term "homogeneous ethylene interpolymer" refers to both linear homogeneous ethylene interpolymers and substantially linear homogeneous ethylene interpolymers.

Herein, the term "polyolefin" includes ethylene polymers and propylene polymers; non-limiting examples of propylene polymers include isotactic, syndiotactic and atactic propylene homopolymers, random propylene copolymers containing at least one comonomer and impact polypropylene copolymers or heterophasic polypropylene copolymers.

The term "thermoplastic" refers to a polymer that becomes liquid when heated, will flow under pressure, and solidifies upon cooling. Thermoplastic polymers include ethylene polymers and other polymers commonly used in the plastics industry; non-limiting examples of other polymers commonly used include barrier resins (EVOH), tie resins, polyethylene terephthalate (PET), polyamides, and the like.

As used herein, the term "monolayer" refers to a cover or enclosure wherein the wall structure comprises a monolayer.

As used herein, the term "hydrocarbyl" or "hydrocarbyl group" refers to straight or cyclic, aliphatic, olefinic, acetylenic, and aryl (aromatic) groups containing hydrogen and carbon, lacking one hydrogen.

As used herein, "alkyl" includes straight, branched, and cyclic alkane groups lacking one hydrogen group; non-limiting examples include methyl (-CH)₃) And ethyl (-CH)₂CH₃). The term "alkenyl" refers to straight, branched, and cyclic hydrocarbons containing at least one carbon-carbon double bond lacking one hydrogen group.

Herein, the term "R1" and superscript forms thereof "^R1"refers to the first reactor in a continuous solution polymerization process; it is to be understood that R1 is the same as the symbol R¹Are significantly different; the latter are used in the formulae, for example representing hydrocarbon radicals. Similarly, the term "R2" and superscript forms thereof "^R2"refers to the second reactor; and the term "R3" and superscript forms thereof "^R3"refers to the third reactor.

Catalyst and process for preparing same

Organometallic catalyst formulations that efficiently polymerize olefins are well known in the art. In 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 the first ethylene interpolymer. Another catalyst formulation is a heterogeneous catalyst formulation that produces a second ethylene interpolymer. Optionally, a heterogeneous catalyst formulation used to produce the second ethylene interpolymer is used to produce the third ethylene interpolymer, or a different heterogeneous catalyst formulation can be used to produce the third ethylene interpolymer. In a continuous solution process, the at least one homogeneous ethylene interpolymer and the at least one heterogeneous ethylene interpolymer solution are blended and an ethylene interpolymer product is produced.

Single site catalyst formulation

The catalyst component constituting the single-site catalyst formulation is not particularly limited, i.e., a plurality of catalyst components may be used. One non-limiting embodiment of a single-site catalyst formulation includes the following three or four components: bulky ligand-metal complexes; an aluminoxane cocatalyst; an ionic activator and optionally a hindered phenol. In table 2A of the present disclosure: "(i)" means "component (i)", i.e., the amount of bulky ligand-metal complex added to R1; "(ii)" means "component (ii)", i.e., the aluminoxane cocatalyst; "(iii)" means "component (iii)", i.e., an ionic activator; and "(iv)" means "component (iv)", i.e. the optional hindered phenol.

Non-limiting examples of component (I) are represented by formula (I):

(L^A)_aM(Pl)_b(Q)_n(I)

wherein (L)^A) Ligands representing large volumes; m represents a metal atom; pl represents a phosphinimine ligand; q represents a leaving group; a is 0 or 1; b is 1 or 2; (a + b) ═ 2; n is 1 or 2; and the sum of (a + b + n) is equal to the valence of the metal M.

Bulky ligands L of the formula (I)^ANon-limiting examples of (a) include unsubstituted or substituted ringsPentadienyl ligands or cyclopentadienyl-type ligands, heteroatom-substituted and/or heteroatom-containing cyclopentadienyl-type ligands. Additional non-limiting examples include cyclopentaphenanthreneyl ligands, unsubstituted or substituted indenyl ligands, benzindenyl ligands, unsubstituted or substituted fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraenediyl ligands, cyclopentacyclododecene ligands, azenyl (azenyl) ligands, azulene ligands, pentalene ligands, phosphoryl ligands, phosphinimine ligands, pyrrolyl ligands, pyrazolyl ligands, carbazolyl ligands, borabenzene ligands, and the like, including hydrogenated versions thereof, e.g., tetrahydroindenyl ligands. In other embodiments, L^AMay be any other ligand structure capable of bonding to metal M η, such embodiments including η with metal M³Bond sum η⁵And (4) bonding. In other embodiments, L^AMay contain one or more heteroatoms such as nitrogen, silicon, boron, germanium, sulfur and phosphorus which combine with carbon atoms to form open, acyclic or fused rings or ring systems, e.g. heterocyclopentadienyl ancillary ligands. L is^AOther non-limiting embodiments of (a) include bulky amides, phosphides, alkoxides, aryl oxides, imides, carbides, borides, porphyrins, phthalocyanines, corrins, and other polyazamacrocycles.

Non-limiting examples of metals M in formula (I) include the group 4 metals-titanium, zirconium and hafnium.

The phosphinimine ligand Pl is defined by the formula (II):

(R^p)₃P＝N- (II)

wherein R is^pThe groups are independently selected from: a hydrogen atom; a halogen atom; c unsubstituted or substituted by one or more halogen atoms_1-20A hydrocarbyl group; c_1-8An alkoxy group; c_6-10An aryl group; c_6-10An aryloxy group; an amide group; formula-Si (R)^s)₃In which R is^sThe groups are independently selected from hydrogen atom, C_1-8Alkyl or alkoxy, C_6-10Aryl radical, C_6-10An aryloxy group; or formula-Ge (R)^G)₃Germyl of (a), wherein R^GRadical definitions are as defined for R in this paragraph^s。

The leaving group Q is any ligand which can be "abstracted" from formula (I), forming a catalyst species capable of polymerizing one or more olefins. Equivalent terms for Q are "activatable ligand", i.e., equivalent terms for "leaving group". In some embodiments, Q is a monoanionic labile ligand with a sigma bond to M. Depending on the oxidation state of the metal, the value of n is 1 or 2, so that formula (I) represents a neutral bulky ligand-metal complex. Non-limiting examples of Q ligands include hydrogen, halogen, C_1-20Hydrocarbyl radical, C_1-20Alkoxy radical, C_5-10(ii) an aryloxide group; these radicals may be linear, branched or cyclic or further substituted by halogen atoms, C_1-10Alkyl radical, C_1-10Alkoxy radical, C_6-10Aryl or aryloxy substituted. Further non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl groups having 1 to 20 carbon atoms. In another embodiment, two Q ligands may form part of a fused ring or ring system.

Additional embodiments of component (I) of the single-site catalyst formulation include the structures, optical or enantiomers (meso and racemic isomers), and mixtures thereof, of the bulky ligand-metal complexes described in formula (I) above.

The second single-site catalyst component, component (ii), is an aluminoxane cocatalyst which activates component (i) to a cationic complex. An equivalent term for "aluminoxane" is "aluminoxane"; although the exact structure of the cocatalyst is not yet known, the expert of the present subject matter generally considers this to be an oligomeric species containing recurring units of the general formula (III):

(R)₂AlO-(Al(R)-O)_n-Al(R)₂(III)

wherein the R groups may be the same or different straight, branched or cyclic hydrocarbon groups containing from 1 to 20 carbon atoms and n is from 0 to about 50. A non-limiting example of an aluminoxane is methylaluminoxane (or MAO), wherein each R group in formula (III) is a methyl group.

The third catalyst component (iii) in the form of a single site catalyst is an ionic activator. Typically, ionic activators are comprised of a cation and a bulky anion; wherein the latter is substantially non-coordinating. A non-limiting example of an ionic activator is a four coordinate boron ionic activator with four ligands bonded to the boron atom. Non-limiting examples of boron ion activators include the following formulas (IV) and (V) shown below:

[R⁵]⁺[B(R⁷)₄]^-(IV)

wherein B represents a boron atom, R⁵Is an aromatic hydrocarbon radical (e.g., triphenylmethyl cation), and each R⁷Independently selected from phenyl unsubstituted or substituted with 3 to 5 substituents selected from: fluorine atom, C_1-4Alkyl or alkoxy (which is unsubstituted or substituted by fluorine atoms); and formula-Si (R)⁹)₃Silyl group of (wherein each R is⁹Independently selected from hydrogen atom and C_1-4Alkyl groups); and a compound of formula (V):

[(R⁸)_tZH]⁺[B(R⁷)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, and R is⁸Is selected from C_1-8Alkyl, unsubstituted or substituted by up to three C_1-4Alkyl-substituted phenyl, or one R⁸Together with the nitrogen atom may form an anilino radical, and R⁷As defined above in formula (IV).

In both formulae (IV) and (V), R⁷A non-limiting example of (a) is pentafluorophenyl. In general, boron ion activators may be described as salts of tetrakis (perfluorophenyl) boron; non-limiting examples include anilinium, carbenium, oxonium, phosphonium and sulfonium salts of tetrakis (perfluorophenyl) boron with anilinium and trityl (or triphenylmethylium) salts. Additional non-limiting examples of ionic activators include: triethylammonium tetra (phenyl) boron; triphenylammonium tetrakis (phenyl) boron; tri (n-butyl) ammonium tetra (phenyl) boron; trimethylammonium tetrakis (p-tolyl) boron; trimethylammonium tetrakis (o-tolyl) boron; tributylammonium tetrakis (pentafluorophenyl) boron; tripropylammonium tetrakis (o, p-dimethylphenyl) boron; tributylammonium tetrakis (m, m-dimethylphenyl) boron; tributylammonium salt(p-trifluoromethylphenyl) boron; tributylammonium tetrakis (pentafluorophenyl) boron; tri (n-butyl) ammonium tetra (o-tolyl) boron; n, N-dimethylanilinium tetrakis (phenyl) boron; n, N-diethylanilinium tetrakis (phenyl) boron; n, N-diethylanilinium tetra (phenyl) N-butylboron; n, N-2,4, 6-pentamethylanilinium tetrakis (phenyl) boron; di (isopropyl) ammonium tetrakis (pentafluorophenyl) boron; dicyclohexylammonium tetra (phenyl) boron, triphenylphosphonium tetra (phenyl) boron; tris (methylphenyl) phosphonium tetrakis (phenyl) boron; tris (dimethylphenyl) phosphonium tetrakis (phenyl) boron;

onium (tropillium) tetrakis (pentafluorophenyl) borate; triphenylmethylonium tetrakis (pentafluorophenyl) borate; benzene (diazonium) tetrakis (pentafluorophenyl) borate;

onium tetrakis (2,3,5, 6-tetrafluorophenyl) borate; triphenylmethylonium tetrakis (2,3,5, 6-tetrafluorophenyl) borate; benzene (diazonium) tetrakis (3,4, 5-trifluorophenyl) borate;

onium tetrakis (3,4, 5-trifluorophenyl) borate; benzene (diazonium) tetrakis (3,4, 5-trifluorophenyl) borate;

onium tetrakis (1,2, 2-trifluorovinyl) borate; triphenylmethylonium tetrakis (1,2, 2-trifluorovinyl) borate; benzene (diazonium) tetrakis (1,2, 2-trifluorovinyl) borate;

onium tetrakis (2,3,4, 5-tetrafluorophenyl) borate; triphenylmethylonium tetrakis (2,3,4, 5-tetrafluorophenyl) borate; and benzene (diazonium) tetrakis (2,3,4, 5-tetrafluorophenyl) borate. Readily available commercial ionic activators include N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and triphenylmethyl onium tetrakis (pentafluorophenyl) borate.

An optional fourth catalyst component in the form of a single site catalyst is a hindered phenol, component (iv). Non-limiting examples of hindered phenols include butylated phenolic antioxidants, butylated hydroxytoluene, 2, 4-di-tert-butyl (tertiarybutyl) -6-ethylphenol, 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 formulations

Many heterogeneous catalyst formulations are well known to those skilled in the art, including but not limited to Ziegler-Natta and chromium catalyst formulations.

The term "batch Ziegler-Natta catalyst formulation" or "batch Ziegler-Natta procatalyst" refers to a catalyst or procatalyst synthesized in a much larger amount in one or more mixing vessels external to or separate from a continuously operated solution polymerization process.

A variety of compounds can be used to synthesize active ziegler-natta catalyst formulations. Various compounds that can be combined to produce an active ziegler-natta catalyst formulation are described below. One skilled in the art will appreciate that embodiments in the present disclosure are not limited to the particular compounds disclosed.

The active Ziegler-Natta catalyst formulation may be formed from a magnesium compound, a chloride, a metal compound, an aluminum alkyl co-catalyst, and an aluminum alkyl. In table 2A of the present disclosure: "(v)" means "component (v)" a magnesium compound; the term "(vi)" means "component (vi)" chloride; "(vii)" means "component (vii)" a metal compound; "(viii)" means "component (viii)" alkylaluminum cocatalyst; and "(ix)" means component (ix) aluminum alkyl. As will be appreciated by those skilled in the art, the ziegler-natta catalyst formulation may contain additional components; non-limiting examples of additional components are electron donors, such as amines or ethers.

Non-limiting examples of active in-line Ziegler-Natta catalyst formulations can be prepared as follows. In the first step, a solution of a magnesium compound (component (v)) is reacted with a solution of a chloride (component (vi)) to form a magnesium chloride support suspended in the solution. Non-limiting examples of magnesium compounds include Mg (R)¹)₂(ii) a Wherein R is¹The groups may be the same or different straight, branched or cyclic hydrocarbon groups containing from 1 to 10 carbon atoms. Non-limiting examples of chlorides include R²Cl; wherein R is²Represents a hydrogen atom or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms. In the first step, the solution of the magnesium compound may further contain an aluminum alkyl (component (ix)). Non-limiting examples of aluminum alkyls include Al (R)³)₃Wherein R is³The groups may be the same or different straight, branched or cyclic hydrocarbon groups containing from 1 to 10 carbon atoms. 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)_nOr MO (X)_n(ii) a Wherein M represents a metal selected from groups 4 to 8 of the periodic Table of the elements, or a mixture of metals selected from groups 4 to 8; o represents oxygen; and X represents chlorine or bromine; n is an integer from 3 to 6, which satisfies the oxidation state of the metal. Gold (II) as a suitable materialAdditional non-limiting examples of generic compounds include group 4 to group 8 metal alkyls, metal alkoxides, which can be prepared by reacting a metal alkyl with an alcohol, and mixed ligand metal compounds containing a mixture of halide, alkyl and alkoxide ligands. In a third step, a solution of an aluminum alkyl cocatalyst, component (viii), is added to the metal compound supported on magnesium chloride. A variety of aluminum alkyl cocatalysts are suitable, as represented by formula (VI):

Al(R⁴)_p(OR⁵)_q(X)_r(VI)

wherein R is⁴The groups may be the same or different hydrocarbyl groups having 1 to 10 carbon atoms; OR (OR)⁵The radicals may be identical or different alkoxy or aryloxy radicals, in which R⁵Is an oxygen-bonded hydrocarbon group having 1 to 10 carbon atoms; x is chlorine or bromine; and (p + q + r) ═ 3, provided that 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.

The process for synthesizing the active in-line Ziegler-Natta catalyst formulation described in the preceding paragraph may be carried out in a variety of solvents; non-limiting examples of the solvent include straight-chain or branched C₅To C₁₂Alkanes 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 wherein the "metal compound" is a chromium compound; non-limiting examples include silyl chromates, chromium oxides, 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 further comprise a cocatalyst; non-limiting examples of the cocatalyst include trialkylaluminum, alkylaluminoxane, dialkoxyalkylaluminum compound and the like.

The solution polymerization process comprises the following steps: in-line heterogeneous catalyst formulation

The ethylene interpolymer products disclosed herein that are useful for making flexible and rigid articles are produced in a continuous solution polymerization process. The Solution process has been fully described in Canadian patent application No. 2,868,640 entitled "Solution polymerization Process" filed on 21/10/2014, which is incorporated by reference herein in its entirety.

An embodiment of the process comprises at least two continuously stirred reactors R1 and R2 and optionally a tubular reactor R3. the feed (solvent, ethylene, at least two catalyst formulations, optionally hydrogen and optionally α -olefin) is continuously fed to the at least two reactors, a single-site catalyst formulation is injected into R1 and a 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 separately an ionic activator (component (iii)), a bulky ligand-metal complex (component (i)), an alumoxane cocatalyst (component (ii)) and optionally a hindered phenol (component (iv)).

R1 and R2 can operate in series or parallel modes of operation. More specifically, in series mode, 100% of the effluent of R1 flows directly into R2. In parallel mode, R1 and R2 operate independently, and the effluents of R1 and R2 are combined downstream of the reactor.

The heterogeneous catalyst formulation is injected into R2. in one embodiment, a first in-line Ziegler-Natta catalyst formulation is injected into R2. by optimizing the molar ratio of (aluminum alkyl)/(magnesium compound) or (ix)/(v), (chloride)/(magnesium compound) or (vi)/(v), (aluminum alkyl cocatalyst)/(metal compound) or (viii)/(vii) formed within the first heterogeneous catalyst assembly and the time at which these compounds must react and equilibrate, in the first heterogeneous catalyst assembly, the time between the chloride addition and the addition of the metal compound (component (vii)) is controlled, hereinafter denoted as HUT-1 (first hold time), and the time between the addition of component (vii) and the addition of the aluminum alkyl cocatalyst component (viii) is also controlled, hereinafter denoted as HUT-2 (second hold time), further, the time between the addition of the aluminum alkyl cocatalyst component (viii) is controlled, hereinafter denoted as HUT-2 (second hold time), further, the time between the addition and the addition of the aluminum alkyl cocatalyst component (vii) is controlled, and the time between the addition of the second heterogeneous catalyst assembly is optionally calculated as the molar ratio of the second heterogeneous catalyst injection into the first heterogeneous catalyst assembly, the second catalyst assembly is optionally, the catalyst assembly is maintained, the same, the molar ratio of the second heterogeneous catalyst assembly (R2) is calculated as the time, the second heterogeneous catalyst assembly, the second catalyst assembly is calculated as the catalyst assembly, the catalyst assembly is calculated as the ratio is calculated as the catalyst assembly, the time is calculated as the time, the time is calculated as the time, the time is calculated as the time, the time is calculated as the time, the time of the time is calculated as the time of the catalyst assembly, the catalyst.

In reactor R3, a third ethylene interpolymer may or may not be formed if a catalyst deactivator is added upstream of reactor R3, a third ethylene interpolymer may not be formed if a catalyst deactivator is added downstream of R3, a plurality of operating modes may be used to form the optional third ethylene interpolymer (provided that no catalyst deactivator is added upstream.) non-limiting examples of operating modes include (a) reaction of residual ethylene, residual optional α -olefin, and residual active catalyst into R3 to form the third ethylene interpolymer, or (b) addition of fresh process solvent, fresh ethylene, and optional fresh α -olefin to R3, and residual active catalyst into R3 to form the third ethylene interpolymer, or (c) addition of a second in-line catalyst formulation to R3 to polymerize residual ethylene and residual optional α -olefin to form the third ethylene interpolymer, or (d) addition of fresh catalyst to R585 to form the second ethylene interpolymer, or (c) addition of the second in-line catalyst formulation to the R3 to polymerize the residual ethylene and the residual optional olefin, to form the third ethylene interpolymer, or the third ethylene interpolymer, optionally the second in-line catalyst formulation.

In the series mode, R3 produces a third outlet stream (stream exiting R3) containing the first ethylene interpolymer, the second ethylene interpolymer, and optionally the third ethylene interpolymer. Catalyst deactivator may be added to the third outlet stream, producing a deactivated solution, provided that if a catalyst deactivator is added upstream of R3, then no catalyst deactivator is added.

The deactivated solution is passed through a pressure reduction device, a heat exchanger, and a passivating agent is added to form a passivated solution. The passivated solution was passed through a series of gas-liquid separators and the final ethylene interpolymer product was passed to polymer recovery. Non-limiting examples of polymer recovery operations include one or more gear pumps, single screw extruders or twin screw extruders that force the molten ethylene interpolymer product through a pelletizer.

Embodiments of the articles of manufacture disclosed herein may also be formed from ethylene interpolymer products synthesized using batch ziegler-natta catalysts. Typically, the first batch ziegler-natta procatalyst is injected into R2 and the procatalyst is activated within R2 by injection of an aluminum alkyl cocatalyst to form the first batch ziegler-natta catalyst. Optionally, a second batch of ziegler-natta procatalyst is injected into R3.

Additional solution polymerization Process parameters

A variety of solvents may be used as process solvents; non-limiting examples include straight, branched or cyclic C₅To C₁₂Non-limiting examples of alkanes, α -alkenes include C₃To C₁₀α -olefins, general skill in the artIt is well known to the skilled artisan that the reactor feed stream (solvent, monomer, α -olefin, hydrogen, catalyst formulation, etc.) must be substantially free of catalyst deactivating poisons, non-limiting examples of which 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 practices, and non-limiting examples include molecular sieve beds, alumina beds, and oxygen scavenging catalysts for purifying solvents, ethylene, α -olefin, etc.

In operation of a continuous solution polymerization process, the total amount of ethylene supplied to the process may be divided or split among the three reactors R1, R2, and R3. This manipulated variable is called the Ethylene Split (ES), or "ES^R1”、“ES^R2"and" ES^R3"means the weight percent of ethylene injected into R1, R2, and R3, respectively, provided that ES^R1+ES^R2+ES ^R3100%. The ethylene concentration in each reactor was also controlled. R1 ethylene concentration is defined as the weight of ethylene in reactor 1 divided by the total weight of all materials added to reactor 1; the R2 ethylene concentration (wt%) and R3 ethylene concentration (wt%) are defined similarly. The total amount of ethylene converted in each reactor was monitored. The term "Q^R1"refers to the percentage of ethylene added to R1 that is converted to ethylene interpolymer by the catalyst formulation. Similarly, Q^R2And Q^R3Represents the percentage of ethylene added to R2 and R3 that is converted to ethylene interpolymer in the respective reactors. The term "Q^T"means the total or overall ethylene conversion throughout the continuous solution polymerization facility; namely, Q^T100 x [ weight of ethylene in interpolymer product]/([ weight of ethylene in interpolymer product)]Weight of unreacted ethylene]) Optionally, α -olefins may be added to the continuous solution polymerization process if added, α -olefins may be proportioned or split between R1, R2, and R3^R1”、“CS^R2"and" CS^R3"refers to the weight percent of α -olefin comonomer injected into R1, R2, and R3, respectively, with the proviso that CS is^R1+CS^R2+CS^R3＝100％。

In the continuous polymerization process, the polymerization is terminated by adding a catalyst deactivator. The catalyst deactivator substantially stops the polymerization reaction by turning the active catalyst species into an inert form. Suitable deactivators are well known in the art, non-limiting examples include: amines (e.g., U.S. Pat. No. 4,803,259 to Zboril et al); alkali or alkaline earth metal salts of carboxylic acids (e.g., U.S. Pat. No. 4,105,609 to Machan et al); water (e.g., U.S. Pat. No. 4,731,438 to Bernier et al); hydrotalcites, alcohols, and carboxylic acids (e.g., U.S. patent No. 4,379,882 to Miyata); or combinations thereof (U.S. patent No. 6,180,730 to Sibtain et al).

A passivating agent or acid scavenger is added to the deactivated solution before entering the gas/liquid separator. Suitable passivating agents are well known in the art, non-limiting examples include alkali or alkaline earth metal salts of carboxylic acids or hydrotalcites.

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

First ethylene interpolymer

The first ethylene interpolymer was produced with a single-site catalyst formulation if the optional α -olefin was not added to reactor 1(R1), the ethylene interpolymer produced in R1 was an ethylene homopolymer, if α -olefin was added, the following weight ratios are one parameter controlling the density of the first ethylene interpolymer: ((α -olefin)/(ethylene))^R1. Symbol sigma¹"refers to the density of the first ethylene interpolymer produced in R1. Sigma¹May be about 0.975g/cm³(ii) a In some cases about 0.965g/cm³(ii) a And in other cases about 0.955g/cm³。σ¹The lower limit of (B) may be about 0.855g/cm³(ii) a In some cases about 0.865g/cm³(ii) a And in other cases about 0.875g/cm³。

Determining CDBI of ethylene interpolymers₅₀(composition distribution branching index) method is well known to those skilled in the artIn (1). CDBI₅₀The CDBI relative to an α -olefin-containing ethylene interpolymer produced with a heterogeneous catalyst formulation is also well known to those skilled in the art₅₀CDBI of ethylene interpolymers produced with single site catalyst formulations₅₀And higher. CDBI of first ethylene interpolymer (produced with Single-site catalyst formulation)₅₀The upper limit of (c) may be about 98%, in other cases about 95%, and in other cases about 90%. CDBI of first ethylene interpolymer₅₀The lower limit of (c) 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, M of an ethylene interpolymer produced with a single site catalyst formulation relative to an ethylene interpolymer produced with a heterogeneous catalyst formulation_w/M_nAnd lower. Thus, in disclosed embodiments, the first ethylene interpolymer has a lower M relative to the second ethylene interpolymer_w/M_nWherein the second ethylene interpolymer is produced using a heterogeneous catalyst formulation. M of the first ethylene interpolymer_w/M_nThe upper limit of (d) may be about 2.8, in other cases about 2.5, and in other cases about 2.2. M of the first ethylene interpolymer_w/M_nThe lower limit of (c) 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. It will be understood by those skilled in the art that catalyst residues are typically quantified by parts per million of the metal in the first ethylene interpolymer, where metal refers to the metal in component (i), i.e., the metal in the "bulky ligand-metal complex," which will be referred to hereinafter (and in the claims) as "metal a. Non-limiting examples of metal a include the group 4 metals-titanium, zirconium, and hafnium, as previously described in this disclosure. The upper limit of the ppm of metal a in the first ethylene interpolymer can be about 1.0ppm, in other cases about 0.9ppm, and in other cases about 0.8 ppm. The lower limit of the ppm of metal a in the first ethylene interpolymer can be about 0.01ppm, in other cases about 0.1ppm, and in other cases about 0.2 ppm.

The amount of hydrogen added to R1 can vary over a wide range, allowing a continuous solution process to produce a first ethylene interpolymer with a wide variation in melt index, hereinafter I₂ ¹(melt index is measured at 190 ℃ using a 2.16kg 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 H₂ ^R1(ppm)。I₂ ¹The upper limit of (d) may be about 200dg/min, in some cases about 100dg/min, and in other cases about 50 dg/min; and in other cases about 1 dg/min. I is₂ ¹The lower limit of (B) may be about 0.01 dg/min; in some cases about 0.05 dg/min; in other cases about 0.1 dg/min; and in other cases about 0.5 dg/min.

The upper limit of the weight percent (wt%) of the first ethylene interpolymer in the ethylene interpolymer product can be about 60 wt%, in other cases about 55 wt%, and in other cases about 50 wt%. The lower limit of the weight percent of the first ethylene interpolymer in the ethylene interpolymer product can be about 15 weight percent, in other cases about 25 weight percent, and in other cases about 30 weight percent.

Second ethylene interpolymer

If the optional α -olefin was not added to reactor 2(R2) (by adding fresh α -olefin to R2 (or taking it from R1)), the ethylene interpolymer produced in R2 is an ethylene homopolymer if the optional α -olefin is present in R2, the following weight ratios are one parameter that controls the density of the second ethylene interpolymer produced in R2: ((α -olefin)/(ethylene))^R2. Hereinafter, the symbol "σ²"refers to the density of the ethylene interpolymer produced in R2. Sigma²May be about 0.975g/cm³(ii) a In some cases about 0.965g/cm³(ii) a And in other cases about 0.955g/cm³. Depending on the heterogeneous catalyst formulation used, σ²The lower limit of (B) may be about 0.89g/cm³(ii) a In some cases about 0.90g/cm³(ii) a And in other cases about 0.91g/cm³。

If the second ethylene interpolymer contains α -olefin, the CDBI relative to the first ethylene interpolymer produced with the single site catalyst formulation₅₀CDBI of a second ethylene interpolymer₅₀In one embodiment of the disclosure, the CDBI of the second ethylene interpolymer (containing α -olefin)₅₀Can be about 70%, in other cases about 65%, and in other cases about 60% in one embodiment of the disclosure, the CDBI of the second ethylene interpolymer (containing α -olefin)₅₀The lower limit of (B) can be about 45%, in other cases about 50%, and in other cases about 55%. if α -olefin is not added to the continuous solution polymerization process, the second ethylene interpolymer is an ethylene homopolymer, in the case of a homopolymer without α -olefin, the CDBI can still be measured using TREF₅₀. CDBI of the second ethylene interpolymer in the case of homopolymer₅₀The upper limit of (c) may be about 98%, in other cases about 96%, and in other cases about 95%. CDBI₅₀Can be about 88%, in other cases about 89%, and in other cases about 90% as is well known to those skilled in the art, the CDBI in the second ethylene interpolymer (containing α -olefin) can have a CDBI at a level where the level of α -olefin in the second ethylene interpolymer is near zero₅₀The CDBI of a second ethylene interpolymer that is a homopolymer of ethylene₅₀There is a smooth transition between the limits. Typically, the CDBI of the first ethylene interpolymer₅₀CDBI higher than second ethylene interpolymer₅₀。

M of a second ethylene interpolymer_w/M_nM higher than the first ethylene interpolymer_w/M_n. M of a second ethylene interpolymer_w/M_nMay be about 4.4, in other cases about 4.2, and in other casesThe lower is about 4.0. M of a second ethylene interpolymer_w/M_nThe lower limit of (c) may be about 2.2. When the melt index of the second ethylene interpolymer is high, or when the melt index of the ethylene interpolymer product is high, e.g., greater than 10 g/10min, M is observed_w/M_nIs 2.2. In other cases, M of the second ethylene interpolymer_w/M_nThe lower limit of (c) may be about 2.4, and in other cases about 2.6.

The second ethylene interpolymer contains catalyst residues reflecting the chemical composition of the heterogeneous catalyst formulation. Those skilled in the art will understand that heterogeneous catalyst residues are typically quantified by the parts per million of the metal in the second ethylene interpolymer, where metal refers to the metal derived from component (vii), i.e., the "metal compound," which metal will be referred to hereinafter (and in the claims) as "metal B. As previously stated in this disclosure, non-limiting examples of metal B include metals selected from groups 4 to 8 of the periodic table or mixtures of metals selected from groups 4 to 8. The upper limit of the ppm of metal B in the second ethylene interpolymer can be about 12ppm, in other cases about 10ppm, and in other cases about 8 ppm. The lower limit of the ppm of metal B in the second ethylene interpolymer can be about 0.5ppm, in other cases about 1ppm, and in other cases about 3 ppm. While not wishing to be bound by any particular theory, in the series mode of operation, it is believed that the chemical environment within the second reactor deactivates the single-site catalyst formulation, or; in the parallel mode of operation, the chemical environment within R2 deactivates the single-site catalyst formulation.

The amount of hydrogen added to R2 can vary over a wide range, allowing a continuous solution process to produce a second ethylene interpolymer with widely varying melt index, hereinafter designated as I₂ ². The amount of hydrogen added is expressed as parts per million (ppm) hydrogen in R2 relative to the total mass in reactor R2; hereinafter, it will be referred to as H₂ ^R2(ppm)。I₂ ²The upper limit of (d) may be about 1000 dg/min; in some cases about 750 dg/min; in other cases about 500 dg/min; and therein is provided withIn his case about 200 dg/min. I is₂ ²The lower limit of (B) can be about 0.3dg/min, in some cases about 0.4dg/min, in other cases about 0.5dg/min, and in other cases about 0.6 dg/min.

The upper limit of the weight percent (wt%) of the second ethylene interpolymer in the ethylene interpolymer product can be about 85 wt%, in other cases about 80 wt%, and in other cases about 70 wt%. The lower limit of the weight% of the second ethylene interpolymer in the ethylene interpolymer product can be about 30 weight%, in other cases about 40 weight%, and in other cases about 50 weight%.

A third ethylene interpolymer

If a catalyst deactivator is added upstream of R3, then no third ethylene interpolymer is produced in R3, if no catalyst deactivator is added and the optional α -olefin is not present, then the third ethylene interpolymer produced in R3 is an ethylene homopolymer, if no catalyst deactivator is added and the optional α -olefin is present in R3, the following weight ratios determine the density of the third ethylene interpolymer: ((α -olefin)/(ethylene))^R3In a continuous solution polymerization process, ((α -olefin)/(ethylene))^R3Is one of the control parameters for producing a third ethylene interpolymer having a desired density. Hereinafter, the symbol "σ³"refers to the density of the ethylene interpolymer produced in R3. Sigma³May be about 0.975g/cm³(ii) a In some cases about 0.965g/cm³(ii) a And in other cases about 0.955g/cm³. Depending on the heterogeneous catalyst formulation used, σ³The lower limit of (B) may be about 0.89g/cm³And in some cases about 0.90g/cm³And in other cases about 0.91g/cm³. Optionally, a second heterogeneous catalyst formulation may be added to R3.

Typically, the CDBI of the optional third ethylene interpolymer (comprising α -olefin)₅₀Can be about 65%, in other cases about 60%, and in other cases about 55%₅₀Will be lower than usingCDBI of first ethylene interpolymer resulting from Single-site catalyst formulation₅₀Typically, the optional third ethylene interpolymer (comprising α -olefin) is CDBI₅₀The lower limit of (b) can be about 35%, otherwise about 40%, and otherwise about 45%. if no α -olefin is added to the continuous solution polymerization process, the optional third ethylene interpolymer is an ethylene homopolymer₅₀The upper limit of (c) may be about 98%, in other cases about 96%, and in other cases about 95%. CDBI₅₀The lower limit of (c) may be about 88%, in other cases about 89%, and in other cases about 90%. Typically, the CDBI of the first ethylene interpolymer₅₀CDBI greater than third ethylene interpolymer and second ethylene interpolymer₅₀。

M of the optional third ethylene interpolymer_w/M_nThe upper limit of (d) may be about 5.0, in other cases about 4.8, and in other cases about 4.5. M of the optional third ethylene interpolymer_w/M_nThe lower limit of (c) may be about 2.2, in other cases about 2.4, and in other cases about 2.6. M of the optional third ethylene interpolymer_w/M_nM higher than the first ethylene interpolymer_w/M_n. When blended together, the second and third ethylene interpolymers have a fourth M_w/M_nSaid fourth M_w/M_nM less than that of the second ethylene interpolymer_w/M_nAnd (4) wide.

The catalyst residue in the optional third ethylene interpolymer reflects the chemical composition of the heterogeneous catalyst formulation used, i.e., 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, a first component (vii) and a second component (vii) may be used to synthesize the first and second heterogeneous catalyst formulations. As described above, "metal B" refers to the metal derived from the first component (vii). Hereinafter, "metal C" means a metal derived from the second component (vii). The metal B and the optional metal C may be the same or different. Non-limiting examples of metal B and metal C include metals selected from groups 4 to 8 of the periodic table, or mixtures of metals selected from groups 4 to 8. The upper limit of ppm (metal B + metal C) in the optional third ethylene interpolymer can be about 12ppm, in other cases about 10ppm, and in other cases about 8 ppm. The lower limit of ppm (metal B + metal C) in the optional third ethylene interpolymer can be about 0.5ppm, in other cases about 1ppm, and in other cases about 3 ppm.

Optionally, hydrogen may be added to R3. The amount of hydrogen in R3 was adjusted and hereinafter referred to as H₂ ^R3(ppm) permitting a continuous solution process to be conducted to produce a third ethylene interpolymer having a substantially different melt index, hereinafter designated as I₂ ³。I₂ ³The upper limit of (D) may be about 2000 dg/min; in some cases about 1500 dg/min; in other cases about 1000 dg/min; and in other cases about 500 dg/min. I is₂ ³The lower limit of (B) can be about 0.5dg/min, in some cases about 0.6dg/min, in other cases about 0.7dg/min, and in other cases about 0.8 dg/min.

The upper limit of the weight percent (wt%) of the optional third ethylene interpolymer in the ethylene interpolymer product can be about 30 wt%, in other cases about 25 wt%, and in other cases about 20 wt%. The lower limit of the weight% of the optional third ethylene interpolymer in the ethylene interpolymer product can be about 0 weight%, in other cases about 5 weight%, and in other cases about 10 weight%.

Ethylene interpolymer products

The upper limit of the density of the ethylene interpolymer product suitable for use in a cap or hood is about 0.970g/cm³(ii) a In some cases about 0.969g/cm³(ii) a And in other cases about 0.968g/cm³. The lower limit of the density of the ethylene interpolymer product suitable for use in the cap or cage can be about 0.945g/cm³(ii) a In some cases about 0.947g/cm³(ii) a And in other cases about 0.948g/cm³。

CDBI of ethylene interpolymer product₅₀Upper part ofThe limit may be about 97%, in other cases about 90%, and in other cases about 85%₅₀97% ethylene interpolymer product; in this case, the ethylene interpolymer product is an ethylene homopolymer. CDBI of ethylene interpolymers₅₀The lower limit of (c) may be about 50%, in other cases about 55%, and in other cases about 60%.

M of ethylene interpolymer product_w/M_nThe upper limit of (d) may be about 6, in other cases about 5, and in other cases about 4. M of ethylene interpolymer product_w/M_nThe lower limit of (c) 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 reflects the following chemical composition: the single site catalyst formulation employed in R1; a first heterogeneous catalyst formulation employed in R2; and optionally first or optionally first and second heterogeneous catalyst formulations employed in R3. In the present disclosure, catalyst residues are quantified by measuring the parts per million of catalytic metals in the ethylene interpolymer product. In addition, the elemental contents (ppm) of magnesium, chlorine and aluminum were quantified. The catalytic metal is derived from two or optionally three sources, in particular: 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) optional "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 catalytic metal" is equal to the sum of catalytic metals a + B + C. Additionally, in the present disclosure, the terms "first total catalytic metal" and "second total catalytic metal" are used to distinguish the first ethylene interpolymer product of the present disclosure from a comparative "polyethylene composition" produced using different catalyst formulations.

The upper limit of the ppm of metal a in the ethylene interpolymer product can be about 0.6ppm, in other cases about 0.5ppm, and in other cases about 0.4 ppm. The lower limit of the ppm of metal a in the ethylene interpolymer product can be about 0.001ppm, in other cases about 0.01ppm, and in other cases about 0.03 ppm. The upper limit of ppm (metal B + metal C) in the ethylene interpolymer product can be about 11ppm, in other cases about 9ppm, and in other cases about 7 ppm. The lower limit of ppm (metal B + metal C) in the ethylene interpolymer product can be about 0.5ppm, in other cases about 1ppm, and in other cases about 3 ppm.

In some embodiments, ethylene interpolymers can be produced where the catalytic metals (metal a, metal B, and metal C) are the same metal; a non-limiting example would be titanium. In such embodiments, the ppm of (metal B + metal C) in the ethylene interpolymer product is calculated using equation (VII):

ppm^(B+C)＝((ppm^(A+B+C)–(f^Axppm^A))/(1-f^A) (VII)

wherein: ppm of^(B+C)Is the calculated ppm of (metal B + metal C) in the ethylene interpolymer product; ppm of^(A+B+C)Is the total ppm of catalyst residues in the ethylene interpolymer product as measured by experiment, i.e., (metal a ppm + metal B ppm + metal Cppm); f. of^ADenotes the weight fraction of the first ethylene interpolymer in the ethylene interpolymer product, f^AMay vary from about 0.15 to about 0.6; and ppm of^ARepresenting the ppm of metal a in the first ethylene interpolymer. In equation (VII), ppm is assumed^AIt was 0.35 ppm.

Embodiments of the ethylene interpolymer products disclosed herein have less catalyst residue relative to the polyethylene polymer described in US 6,277,931. In us patent 6,277,931, higher catalyst residues add to the complexity of the continuous solution polymerization process; one example of the increased complexity includes an additional purification step to remove catalyst residues from the polymer. In contrast, in the present disclosure, catalyst residues are not removed. In the present disclosure, the upper limit of "total catalytic metals," i.e., (metal a ppm + metal B ppm + optional metal C ppm) in the ethylene interpolymer product can be about 11ppm, in other cases about 9ppm, and in other cases about 7 ppm. The lower limit of the total ppm of catalyst residues (metal a + metal B + optional metal C) in the ethylene interpolymer product can be about 0.5ppm, in other cases about 1ppm, and in other cases about 3 ppm.

The upper limit of the melt index of the ethylene interpolymer product can be 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. The lower limit of the melt index of the ethylene interpolymer product can be about 0.5dg/min, in some cases about 0.6 dg/min; in other cases about 0.7 dg/min; and in other cases about 0.8 dg/min.

As shown in fig. 1, for the zone III ethylene interpolymer product, the upper limit of the melt index of the ethylene interpolymer product can be about 8dg/min, in some cases about 7 dg/min; in other cases about 5 dg/min; and in other cases about 3 dg/min. The lower limit of the melt index of the ethylene interpolymer product may be about 0.3, in some cases about 0.4dg/min, in some cases about 0.5dg/min, in other cases about 0.6dg/min, and in other cases about 0.7 dg/min.

Table 1 shows the computer-generated ethylene interpolymer products. The simulation is based on basic kinetic models (each catalyst formulation has specific kinetic constants) and feed and reactor conditions. The simulation was based on the configuration of a solution pilot plant described below for producing the examples of ethylene interpolymer products disclosed herein. Simulated example 13 was synthesized using a single site catalyst formulation in R1 (PIC-1) and an in-line Ziegler-Natta catalyst formulation in R2 and R3. Table 1 discloses non-limiting examples of the 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 were combined to produce simulated example 13 (ethylene polymer product). As shown in Table 1, the density of the product of simulated example 13 was 0.9169g/cm³Melt index of 1.0dg/min, branching frequency of 12.1 (C per 1000 carbon atoms)₆Number of branches (1-octene comonomer)) and M_w/M_nWas 3.11. Simulated example 13 contained: first, second and third ethylene interpolymers, first, second and third melts thereofThe indexes are respectively 0.31dg/min, 1.92dg/min and 4.7 dg/min; the first, second and third densities are 0.9087g/cm³、0.9206g/cm³And 0.9154g/cm³(ii) a First, second and third M_w/M_nAre respectively 2.03M_w/M_n、3.29M_w/M_nAnd 3.28M_w/M_n(ii) a And first, second and third CDBI₅₀Respectively 90% to 95%, 55% to 60% and 45% to 55%. The simulated production rate for simulated example 13 was 90.9kg/hr and the outlet temperature of R3 was 217.1 ℃.

Ethylene interpolymer products suitable for caps and caps

Tables 2A to 2C summarize solution pilot plant process conditions for making the following ethylene interpolymer products: the target density of example 81 and comparative example 20 was about 0.953g/cm³And a target melt index of about 1.5 dg/min; example 91 and comparative example 30 have a target density of about 0.958g/cm³And a target melt index of about 7.0 dg/min; and the target density for examples 1001 and 1002 was about 0.955g/cm³And a target melt index of about 0.6 dg/min. Examples 81, 91, 1001 and 1002 were made 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 made in both

reactors

1 and 2 using a single site catalyst formulation. The production rate of example 81 was 15% higher relative to comparative example 20. The production rate of example 91 was 26% higher relative to comparative example 30. Examples (81, 91, 1001 and 1002) and comparative examples (20 and 30) were all produced with

reactors

1 and 2 arranged in series, i.e. the effluent from reactor 1 flowed directly into reactor 2. In all examples, 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 commercial cap and cap ethylene interpolymer available from NOVA Chemicals Inc. under the designation CCs153-A (0.9530 g/cm)³And 1.4dg/min) which was produced in a two reactor solution process using a single site catalyst. Comparative example V is a commercial cap and cap ethylene interpolymer Continuum DMDA-1250NT 7(0.9550 g/cm) obtained from Dow Chemical Company³1.5dg/min) in a double reactionThe reactor gas phase process is produced using a ziegler-natta catalyst, which is produced in a two reactor gas phase process with a batch ziegler-natta catalyst formulation.

As shown in FIG. 1, the rectangle defined by region I defines a melt index region in the range of about 0.4dg/min to 5 dg/min. Within zone I, the disclosed ethylene interpolymer products,

example 81, having the desired value of G' [ @ G "═ 500Pa ] when the lid and cover were made using a compression molding process. Specifically, example 81 has a value of G' [ @ G "═ 500Pa ] of ≥ 40Pa to ≤ 70 Pa; and these values are between comparative example Q and comparative example V. In detail, the elasticity of the polymer melt as measured by the storage modulus G' affects the compression molding manufacturing process. Generally, the higher G', the higher the die swell of the polymer melt. Ethylene interpolymers having a melt index less than 5 can be used to produce caps and covers using a Continuous Compression Molding (CCM) process. CCM uses a nozzle with a specified diameter to extrude a specific amount of polymer melt, followed by high speed knife cutting to form molten pellets. The pellets are then placed in a mold and compression molded to form the cap. Example 81 has the appropriate die swell characteristics (controlled by appropriate choice of G' value) which is advantageous in terms of nozzle selection and control of die swell to improve CCM processing, for example to reduce or eliminate the undesirable phenomenon of pellet bounce.

Table 3 compares the physical properties of example 91 with comparative examples R, Y and X. Comparative example R is a commercial cap and cap ethylene interpolymer obtained from NOVA Chemicals Inc. under the designation CCs757(0.9530 gcm)³And 1.4dg/min) which was produced in a two reactor solution process using a single site catalyst. Comparative examples Y and X are from INEOS Olefins&Commercial cap and cap ethylene interpolymers obtained from Polymers USA as INEOS HDPE J50-1000-.

As shown in FIG. 1, the rectangle defined by region II defines a melt index region ranging from > 5dg/min to ≦ 20 dg/min. Within region II, the disclosed ethylene interpolymer product, example 91, has the desired value of G' [ @ G "═ 500Pa ] when the lid and cover are made using a compression molding process. Specifically, example 91 has a value of ≧ 1Pa to ≦ 35Pa for G' [ @ G "═ 500Pa ]; and these values are lower than those of comparative examples R, Y and X. In particular, higher melt indices (5 to 20dg/min) may be used for lid and closure manufacture in injection molding processes, i.e. higher melt indices reduce residual stresses (crystallizing into this part) that may cause surface warpage within the lid or closure. Lower melt elasticity, as indicated by lower G' values, increases the degree of relaxation of the polymer chains, thereby dissipating residual stresses and producing caps and covers of the desired shape and size. Of course, covers and shrouds having the desired dimensions or "design" dimensions are advantageous in downstream processing; for example in a downstream process of filling the bottle and applying a cap or closure to the bottle. No current commercial polyethylene material exists that combines the properties of homogeneous and heterogeneous ethylene interpolymers in the melt index range of 5 to 20.

Table 3 compares the physical properties of examples 1001 and 1002 with all other examples and comparative examples disclosed herein.

As shown in FIG. 1, the rectangle defined by region III defines a melt index region ranging from > 0.3dg/min to ≦ 8 dg/min. In region III, the disclosed ethylene interpolymer product, examples 1001 and 1002, has the desired value of G' [ @ G "═ 500Pa ] for continuous compression molding or injection molding. Specifically, examples 1001 and 102 and similar materials have G' [ @ G "═ 500Pa ] values of ≧ 80Pa to ≦ 120Pa, which is different from examples and comparative examples falling within the ranges of regions I and II.

_dDilution index (Y) of ethylene interpolymer product

In fig. 2, dilution indices (Y) are plotted for several embodiments of the ethylene interpolymer products disclosed herein (filled symbols) and a comparative ethylene interpolymer product, comparative examples A, D, E and S_dDimension ° (degrees)) and dimensionless modulus (X)_d). In addition, fig. 2 defines the following three quadrants:

type I: y is_d> 0 and X_d＜0；

Type II: y is_d> 0 and X_dIs greater than 0; and is

Type III: y is_d< 0 and X_d＞0。

Type IV polymers are not shown in fig. 2, but are confirmed by examples 1001 and 1002 shown in table 4; y of type IV ethylene interpolymer product_d< 0 and X_dIs less than 0. As shown in fig. 1, the type IV ethylene interpolymer product falls in zone III. The regioIII ethylene interpolymer product has advantages in continuous compression molding, giving melt index > 0.3dg/min to ≤ 8dg/min and G' [ @ G "═ 500Pa]More than or equal to 80Pa and less than or equal to 120 Pa.

Region III

Table 4 also lists the data plotted in fig. 2. In fig. 2, comparative example S (open triangle) was used as a rheological reference in the dilution index testing protocol. Comparative example S is an ethylene interpolymer product comprising an ethylene interpolymer synthesized in one solution reactor using an in-line Ziegler-Natta catalyst, i.e.

FP120-C, an ethylene/1-octene interpolymer commercially available from NOVAChemicals Corporation (Calgary, Alberta, Canada). Comparative examples D and E (open diamond, Y)_d＜0，X_d> 0) is an ethylene interpolymer product comprising a first ethylene interpolymer synthesized using a two reactor solution process using a single site catalyst form and a second ethylene interpolymer synthesized using a batch ziegler-natta catalyst formulation, i.e., each

5100G and ELITE 5400G, both ethylene/1-octene interpolymers obtained from the Dow Chemical Company (Midland, Michigan, USA). Comparative example A (open square, Y)_d> 0 and X_d< 0) is an ethylene interpolymer product comprising a first and a second ethylene interpolymer synthesized using a single site catalyst form in a two reactor solution process, namely SURPASS FPs117-C, which is an ethylene/1-octene interpolymer commercially available from NOVA Chemicals Corporation (Calgary, Alberta, Canada).

The dilution index (Y) is defined below_d) And dimensionless modulus (X)_d). In addition to having molecular weight, molecular weight distribution and branched structure, ethylene interpolymerizesBlends of the blends may also exhibit a layered structure in the melt phase. In other words, the ethylene interpolymer component may or may not be homogeneous at the molecular level, depending on the miscibility of the interpolymer and the physical history of the blend. Such a layered physical structure in the melt is expected to have a significant impact on flow and thus processing and conversion and end-use properties of the finished article. The nature of this layered physical structure between the interpolymers can be characterized.

The layered physical structure of the ethylene interpolymers can be characterized using melt rheology. A convenient method may be based on a small amplitude frequency sweep test. The rheological results are expressed as the phase angle delta and the complex modulus G^*The functional relationship of (a) is called a vanguard-Palmen diagram (as described in M.Van guard, J.Palmen, Rheol. Bull. (1998)67(1): 5-8; and Dealy J, Plazek D.Rheol. Bull. (2009)78(2): 16-31). For a typical ethylene interpolymer, the phase angle δ is dependent on G^*Becomes small enough to increase towards its upper limit of 90 deg.. A typical VGP graph is shown in fig. 3. The VGP map is a label of the resin architecture. The delta 90 ° rise is monotonic for an ideal linear monodisperse interpolymer. Delta (G) of branched interpolymers or blends containing branched interpolymers^*) Inflection points reflecting the topology of branched interpolymers can be shown (see S.Trinkle, P.Walter, C.Friedrich, Rheo. acta (2002)41: 103-. The deviation of the phase angle δ from a monotonic increase may indicate a deviation from an ideal linear interpolymer if the inflection point is low (e.g., δ ≦ 20 °) due to the presence of long chain branching, or if the inflection point is high (e.g., δ ≧ 70 °), due to the blend containing at least two interpolymers with dissimilar branching structures.

For commercial linear low density polyethylene, no inflection points were observed except for some commercial polyethylene containing a small amount of Long Chain Branching (LCB). In order to use the VGP map without considering the presence of LCBs, it is an option to use a point where the frequency ω is_cSpecific cross frequency omega_cLower two decimal places, i.e. omega_c＝0.01ω_x. The crossover point is referenced as it is known to be a characteristic point related to the Melt Index (MI), density, and other specifications of the ethylene interpolymer. For a given pointThe cross-modulus correlates with the plateau modulus (see S.Wu.J.Polym Sci, PolymPhys eds (1989)27: 723; M.R.Nobile, F.Cocchini.Rheol Acta (2001)40: 111). The two decimal shifts of the phase angle δ are to find comparable points at which the corresponding viscoelastic response of the component can be detected. The two decimal shifts are shown in fig. 4. The complex modulus of the spot

Relative to cross modulusStandardisation, i.e.

To minimize variations due to overall molecular weight, molecular weight distribution, and short chain branching. As a result, at ω_c＝0.01ω_xThe coordinates of the VGP map of the low frequency bins, i.e.

And delta_cThe effect due to mixing is characterized. Similar to the point of inflection, the corner point,

the closer the point is to the upper 90 ° limit, the more the blend behaves like an ideal single component.

As avoidance of ethylene delta_cAn alternative method of interfering with the molecular weight, molecular weight distribution and short chain branching of the interpolymer components is by coordinatingComparison with the target reference sample resulted in the following two parameters:

"dilution index (Y)_d)”

"dimensionless modulus (X)_d)”

Constant C₀、C₁And C₂Determined by fitting the VGP data for the reference sample to the following equation:

is that the reference sample is at delta thereof_c＝δ(0.01ω_x) Complex modulus of (a). The density of the product to be synthesized by using a solution reactor with an in-line Ziegler-Natta catalyst is 0.920g/cm³And melt index (MI or I)₂) With an ethylene interpolymer of 1.0dg/min as the reference sample, the constants are:

C₀＝93.43°

C₁＝1.316°

C₂＝0.2945

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

From

Of (a) are combined with the coordinates (X)_d,Y_d) Allowing for comparisons between the ethylene interpolymer products disclosed herein and comparative examples. Recombined G disclosed in Table 4_c*[kPa]The value is equivalent to the value used in the formula to calculate the dimensionless modulus (X)_d) Is/are as follows

An item.

Dilution index (Y)_d) Reflect the factWhether the blends behave like simple blends of linear ethylene interpolymers (lack of layered structure in the melt) or exhibit unique responses reflecting the layered physical structure in the melt. Y is_dThe lower, the more the sample shows an independent response from the ethylene interpolymer comprising the blend; y is_dThe higher the sample, the more like a single component or a single ethylene interpolymer.

Returning to FIG. 2: y of type I (upper left quadrant) ethylene interpolymer product (filled symbols) of this disclosure_dIs greater than 0; in contrast, Y for comparative ethylene interpolymers of type III (lower right quadrant) (comparative examples D and E)_dIs less than 0. In the case of the type I ethylene interpolymer product (solid circles), the first ethylene interpolymer (single site catalyst) and the second ethylene interpolymer (in-line ziegler natta catalyst) behave as a simple blend of the two ethylene interpolymers with no layered structure present in the melt. However, in the case of comparative examples D and E (open diamonds), the melt comprising the first ethylene interpolymer (single site catalyst) and the second ethylene interpolymer (batch ziegler natta catalyst) had a layered structure.

The ethylene interpolymer products of the present disclosure fall into one of two quadrants: form I, X_d< 0, or; type II, X_dIs greater than 0. Dimensionless modulus (X)_d) Reflects the total molecular weight and the molecular weight distribution (M)_w/M_n) Differences related to short chain branching (relative to reference samples). Without wishing to be bound by theory, conceptually, the dimensionless modulus (X)_d) M which can be considered as an interpolymer with ethylene in the melt_w/M_nAnd radius of gyration (< R)_g＞²) It is related. Conceptually, increasing X_dHaving and increasing M_w/M_nAnd/or < R_g＞²Similar effect without the risk of lowering the molecular weight fraction and sacrificing certain relevant properties.

The solution processes disclosed herein are capable of producing a copolymer having a higher X relative to comparative example a (recall that comparative example a includes first and second ethylene interpolymers synthesized with a single site catalyst)_dThe ethylene interpolymer product of (a). Without wishing to be bound by theory, with X_dIncrease inThe higher molecular weight fraction of the macromolecular coil will swell more (conceptually, < R)_g＞²Higher) and upon crystallization, the probability of tie chain formation also increases, resulting in higher toughness. The field of polyethylene is replete with disclosures relating higher toughness (e.g., improved ESCR and/or PENT in molded articles) to increased likelihood of tie chain formation.

In the dilution index test protocol, Y_dMay be about 20, in some cases about 15, and in other cases about 13. Y is_dThe lower limit of (c) may be about-30, in some cases-25, in other cases-20, and in other cases-15.

In the dilution index test protocol, X_dIs 1.0, in some cases is about 0.95, and in other cases is about 0.9. X_dThe lower limit of (B) is-2, in some cases-1.5, and in other cases-1.0.

Terminal vinyl unsaturation of ethylene interpolymer products

The ethylene interpolymer product of the present disclosure is further characterized by a terminal vinyl unsaturation of greater than or equal to 0.03 terminal vinyl groups/100 carbon atoms (≧ 0.03 terminal vinyl groups/100C); as determined by Fourier Transform Infrared (FTIR) spectroscopy according to ASTM D3124-98 and ASTM D6248-98.

Figure 5 compares the terminal vinyl/100C content of the ethylene interpolymers of the present disclosure with several comparative examples. The data shown in fig. 5 is also listed in tables 5A and 5B. FIG. 5 and all comparative examples in tables 5A and 5B are ELITE products available from the Dow chemical company (Midland, Michigan, USA); the Elite product is an ethylene interpolymer produced in a two reactor solution process and comprises an interpolymer synthesized using a single site catalyst and an interpolymer synthesized using a batch Ziegler-Natta catalyst: comparative example B was ELITE 5401G; comparative example C was ELITE 5400G; comparative examples E and E2 were ELITE 5500G; comparative example G was ELITE 5960; comparative examples H and H2 were ELITE 5100G; comparative example I was ELITE 5940G; and comparative example J was ELITE 5230G.

As shown in fig. 5, the average terminal ethylene in the ethylene interpolymers of the present disclosureThe radical content is 0.045 terminal vinyl groups/100C; and the terminal vinyl unsaturation of examples 81 and 91 approaches this average, i.e., 0.044 and 0.041 terminal vinyls/100C, respectively. The terminal vinyl unsaturation of examples 1001 and 1002 approaches this average value, i.e., 0.045 terminal vinyl groups/100C. In contrast, the average terminal vinyl content in the comparative sample was 0.023 terminal vinyl groups/100C. Similar to examples 81 and 91, the comparative example shown in fig. 5 also comprises a first ethylene interpolymer synthesized with a single-site catalyst formulation and a second ethylene interpolymer synthesized with a heterogeneous catalyst formulation. Statistically, at a confidence level of 99.999%, the ethylene interpolymers of the present disclosure are significantly different from the comparative examples of fig. 5; that is, the t-test assuming equal variance indicates that the mean of the two populations (0.045 and 0.023 terminal vinyl groups/100C) differs significantly at 99.999% confidence level (t (obs) ═ 12.891 > 3.510t (critical double tail); or p value ═ 4.84 × 10^-17< 0.001 α (with 99.999% confidence).

Catalyst residue (Total catalytic Metal)

The ethylene interpolymer product of the present disclosure is further characterized by a total catalytic metal (Ti) of 3 parts per million (ppm) or greater, wherein the amount of catalytic metal is determined by neutron activation analysis (n.a.a.) as described herein.

Figure 6 compares the total catalytic metal content of the disclosed ethylene interpolymers with several comparative examples. The data of FIG. 6 are also set forth in tables 6A and 6B. All comparative examples in FIG. 6 and tables 6A and 6B are ELITE products available from the Dow Chemical Company (Midland, Michigan, USA) for more details see section above.

As shown in fig. 6, the average total catalytic metal content in the ethylene interpolymers of the present disclosure is 7.02ppm of titanium. Although no elemental analysis (n.a.a.) was performed for examples 81 and 91, fig. 5 clearly shows that 7.02ppm titanium is a reasonable estimate for the residual titanium in examples 81 and 91 (as reported in table 3). In contrast, the average total catalytic metal in the comparative sample shown in FIG. 6 was 1.63ppm titanium. Statistically, at a confidence level of 99.999%, the ethylene interpolymers of the present disclosure are significantly different from the comparative examples; i.e. t-test assuming equal varianceMean values (7.02 and 1.63ppm titanium) for the two populations were shown to be significantly different at 99.999% confidence levels, i.e. (t (obs) > 12.71 > 3.520t (critical double tail) or p-value ═ 1.69 × 10^-16< 0.001 α (with 99.999% confidence).

Rigid finished product

There is a need for ethylene interpolymer products having optimized density, melt index and G' [ @ G "═ 500Pa ] for use in compression molding processes. In addition, there is a need for ethylene interpolymer products having optimized density, melt index and G' [ @ G "═ 500Pa ] for injection molding processes. There is also a need to improve the stiffness of the cap and closure articles while maintaining or increasing Environmental Stress Crack Resistance (ESCR). The various embodiments of the ethylene interpolymer products disclosed herein are well suited to meet some or all of these needs.

Additional non-limiting applications in which the disclosed ethylene interpolymer products may be used include: delicatessen containers, artificial butter drums, trays, cups, lids, bottles, bottle cap liners, pails, crates, cans, bumpers, industrial bulk containers, industrial containers, material handling containers, playground equipment, entertainment equipment, safety equipment, wire and cable applications (power cables, communication cables and conduits), pipes and hoses, pipe applications (pressure and non-pressure pipes, such as natural gas distribution, water mains, indoor plumbing, storm sewer, sanitary sewer, corrugated pipe and conduit), foam products (foam boards or foam blocks), military packaging (equipment and ready-to-eat food), personal care packaging (diapers and sanitary products), cosmetics, pharmaceutical and medical packaging, truck liners, pallets and automotive dunnage. The rigid finished articles outlined in this paragraph have improved Heat Distortion Temperature (HDT), faster crystallization rate (reduced t)_1/2) And higher melt strength ethylene interpolymer products. Such rigid finished products can be manufactured using conventional injection molding, compression molding and blow molding techniques.

The desired physical properties of the rigid finished product depend on the application of interest. Non-limiting examples of desirable properties include: elasticity (G'), stiffness, flexural modulus (1% and 2% secant modulus), tensile toughness; environmental Stress Cracking Resistance (ESCR); slow crack growth resistance (PENT); wear resistance; shore hardness; heat Distortion Temperature (HDT); VICAT softening point; IZOD impact strength; the ARM has impact resistance; sharp impact strength; and color (whiteness and/or yellowness index).

Additives and auxiliaries

Depending on its intended use, the claimed ethylene interpolymer product and caps and covers may optionally comprise additives and adjuvants. Non-limiting examples of additives and adjuvants include antiblocking agents, antioxidants, heat stabilizers, slip agents, processing aids, antistatic additives, colorants, dyes, filler materials, light stabilizers, light absorbers, lubricants, pigments, plasticizers, nucleating agents, or mixtures of more than one nucleating agent, and combinations thereof.

Test method

Prior to testing, each sample was conditioned at 23 ± 2 ℃ and 50 ± 10% relative humidity for at least 24 hours, with subsequent tests performed at 23 ± 2 ℃ and 50 ± 10% relative humidity. As used herein, the term "ASTM conditions" refers to a laboratory maintained at 23. + -. 2 ℃ and 50. + -. 10% relative humidity. Prior to testing, the samples to be tested were conditioned in the laboratory for at least 24 hours. ASTM refers to the american society for testing and materials.

Density of

Ethylene interpolymer product density was determined using ASTM D792-13 (11 months 1 days 2013).

Melt index

The ethylene interpolymer product melt index was determined using ASTM D1238 (8 months 1 day 2013). Melt index I₂、I₆、I₁₀And I₂₁The weight measurements were carried out at 190 ℃ using 2.16kg, 6.48kg, 10kg and 21.6kg, respectively. Herein, the term "stress index" or its abbreviation "s.ex." is defined by the following relationship:

S.Ex.＝log(I₆/I₂)/log(6480/2160)

wherein I₆And I₂Melt flow rates were measured at 190 ℃ using 6.48kg and 2.16kg loads, respectively. In the present disclosure, the melt index is used in grams/10 minutes or g/10min ordg/min or dg/min. These units are equivalent.

Environmental Stress Cracking Resistance (ESCR)

ESCR was determined according to ASTM D1693-13 (11/1/2013). Using condition B, the sample thickness was in the range of 1.84mm to 1.97mm (0.0725 inches to 0.0775 inches) and the incision depth was in the range of 0.30mm to 0.40mm (0.012 inches to 0.015 inches). The Igepal concentration used was 10 vol%.

Gel Permeation Chromatography (GPC)

Ethylene interpolymer product molecular weight M_n、M_wAnd M_zAnd polydispersity (M)_w/M_n) Determined using ASTM D6474-12 (12 months and 15 days 2012). This method illustrates the molecular weight distribution of the ethylene interpolymer product by high temperature Gel Permeation Chromatography (GPC). The method uses commercially available polystyrene standards to calibrate GPC.

Unsaturated content

The number of unsaturated groups, i.e., double bonds, in the ethylene interpolymer product is determined according to ASTM D3124-98 (vinylidene unsaturation, published 3 months 2011) and ASTM D6248-98 (vinyl and trans unsaturation, published 7 months 2012). Ethylene interpolymer sample: a) first a carbon disulphide extraction is performed to remove additives that may interfere with the analysis; b) pressing the sample (pellets, film or granules) into a plate of uniform thickness (0.5 mm); and c) by FTIR analysis of the plate.

Comonomer content

The amount of comonomer in the ethylene interpolymer product was determined by FTIR (fourier transform infrared spectroscopy) according to ASTM D6645-01 (published 1 month 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 Temperature Rising Elution Fractionation (Temperature Rising Elution Fractionation). An ethylene interpolymer product sample (80mg to 100mg) was placed in the reactor of a Polymer Char Crystal-TREF Unit and the reaction was repeatedThe application was filled with 35ml of 1,2, 4-Trichlorobenzene (TCB), heated to 150 ℃ and kept at this temperature for 2 hours to dissolve the sample. An aliquot of the TCB solution (1.5mL) was then loaded into a Polymer Char TREF column packed with stainless steel beads and the column equilibrated at 110 ℃ for 45 minutes. The ethylene interpolymer product was then crystallized from the TCB solution in the column by slowly cooling the TREF column from 110 ℃ to 30 ℃ at a cooling rate of 0.09 ℃/minute. The TREF column was then equilibrated at 30 ℃ for 30 minutes. The crystallized ethylene interpolymer product is then eluted from the column by passing pure TCB solvent through the TREF column at a flow rate of 0.75 mL/min as the column temperature is slowly raised from 30 ℃ to 120 ℃ using a heating rate of 0.25 ℃/min. Using Polymer Char software, a TREF profile is generated as the ethylene interpolymer product is eluted from the TREF column, i.e., the TREF profile is a plot of the amount (or strength) of ethylene interpolymer eluted from the column as a function of TREF elution temperature. For each ethylene interpolymer product analyzed, the CDBI was calculated from the TREF distribution curve₅₀。“CDBI₅₀"is defined as the percentage of ethylene interpolymer whose composition is within 50% of the median comonomer composition (25% on each side of the median comonomer composition). It is calculated from the TREF composition distribution curve and the normalized cumulative integral of the TREF composition distribution curve. One skilled in the art will appreciate that a calibration curve is required to convert the TREF elution temperature to comonomer content, i.e., the amount of comonomer in the ethylene interpolymer fraction that elutes at a particular temperature. The generation of such calibration curves is described in the prior art, e.g. Wild et al, j.polym.sci., part B, polym.phys, volume 20 (3), page 441-; which is fully incorporated herein by reference.

Heat distortion temperature

The heat distortion temperature of the ethylene interpolymer product was determined using ASTM D648-07 (approved on 3/1/2007). The heat distortion temperature is the temperature at which a deformation tool applies a stress of 0.455MPa (66PSI) to the center of a formed ethylene interpolymer sheet (3.175mm (0.125 inch) thick) to deform it by 0.25mm (0.010 inch) as it is heated in media at a constant rate.

Vicat softening point (temperature)

The Vicat softening point of the ethylene interpolymer product was determined according to ASTM D1525-07 (published 12 months 2009). This test determines the temperature at which a specified degree of needling occurs when the sample is subjected to ASTM D1525-07 test conditions, namely heating rate B (120 + -10 deg.C/hour and 938 grams load (10 + -0.2N load).

Neutron Activation Analysis (NAA)

Neutron activation analysis, hereinafter NAA, was used to determine catalyst residues in ethylene interpolymers and was performed as follows. A radiation bottle (consisting of ultra-pure polyethylene, with an internal volume of 7mL) was filled with the ethylene interpolymer product sample and the sample weight was recorded. Using a pneumatic transport system, the samples were placed in a SLOWPOKE^TMInside a nuclear reactor (Atomic Energy of Canada limited, Ottawa, Ontario, Canada), elements having a short half-life (e.g., Ti, V, Al, Mg, and Cl) are irradiated for 30 to 600 seconds, or elements having a long half-life (e.g., Zr, Hf, Cr, Fe, and Ni) are irradiated for 3 to 5 hours. The average thermal neutron flux in the reactor is 5X 10¹¹/cm²And s. After irradiation, the sample is removed from the reactor and aged, thereby attenuating radioactivity; elements with short half-lives are aged for 300 seconds, or elements with long half-lives are aged for several days. After aging, germanium semiconductor gamma ray detectors are used (

Model GEM55185, Advanced Measurement Technology inc, oaklidge, TN, USA) and a multi-channel analyzer (model ORTEC DSPEC Pro) record the gamma-ray spectra of the samples. The amount of each element in the sample was calculated from gamma ray spectroscopy and reported in parts per million relative to the total weight of the ethylene interpolymer sample. N.a.a. system was calibrated with Specpure standard (1000ppm solution of the desired element (purity > 99%)). 1mL of the solution (element of interest) was pipetted onto a 15mm × 800mm rectangular filter paper and air dried. The filter paper was then placed into a 1.4mL polyethylene irradiation vial and analyzed by the n.a.a. system. The sensitivity (in counts/microgram) of the n.a.a. procedure was determined using standards.

Color index

The Whiteness Index (WI) and Yellowness Index (YI) of the ethylene interpolymer product were measured according to astm e313-10 (approved by 2010) using a BYK Gardner Color-View colorimeter.

_dMeasurement of dilution index (Y)

Using equipment "TruGap^TMThe Anton Paar MCR501 rotary rheometer of the parallel plate measurement system "performed a series of small amplitude frequency sweep tests on each sample. Throughout the test, a gap of 1.5mm and a strain amplitude of 10% were used. The frequency sweep is 0.05rad/s to 100rad/s, seven points apart every ten points. The test temperatures were 170 °, 190 °, 210 ° and 230 ℃. A master curve was established at 190 ℃ for each sample using Rheoplus/32V3.40 software by standard TTS (time-temperature superposition) procedure, achieving both horizontal and vertical displacements.

Table 4 summarizes the Y generated_dAnd X_dAnd (4) data. The flow properties of the ethylene interpolymer product, such as melt strength and Melt Flow Ratio (MFR), are determined by the dilution index (Y) as detailed below_d) And dimensionless modulus (X)_d) Well characterized. In both cases, the flow property is Y_dAnd X_dIs also dependent 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, confirming the characteristic VGP pointAnd derived recombined coordinates (X)_d，Y_d) The structure is well represented:

wherein

a₀₀＝-33.33；a₁₀＝9.529；a₂₀＝0.03517；a₃₀＝0.894；a₄₀＝0.02969

And is

r²0.984, and the average relative standard deviation is 0.85%. In addition, this relationship may dilute the index (Y)_d) And do not haveDimensional modulus (X)_d) Represents:

MS＝a₀+a₁logη₀+a₂Y_d+a₃X_d+a₄Y_dX_d

wherein

a₀＝33.34；a₁＝9.794；a₂＝0.02589；a₃＝0.1126；a₄＝0.03307

And is

r²0.989, and the average relative standard deviation is 0.89%.

Finding that the MFRs of the disclosed examples and comparative examples follow similar equations, further confirms the dilution parameter Y_dAnd X_dIndicating that the flow properties of the disclosed examples are different from the reference and comparative examples:

MFR＝b₀-b₁logη₀-b₂Y_d-b₃X_d

wherein

b₀＝53.27；b₁＝6.107；b₂＝1.384；b₃＝20.34

And is

r²0.889, and an average relative standard deviation of 3.3%.

In addition, the polymerization processes and catalyst formulations disclosed herein allow for the production of ethylene interpolymer products that can be converted into flexible finished articles having a desired balance of physical properties (i.e., several end-use properties can be balanced (as desired) by multi-dimensional optimization) relative to comparative polyethylenes having comparable densities and melt indices.

G′[@G″＝500Pa]Parameter(s)

The G ' [ @ G "@ 500Pa ] parameter is generated using conventional rheological equipment and data processing techniques well known to those of ordinary skill in the art rheological data is generated on a Rheometrics RDS-II (Rheometrics dynamic spectrometer II) which is a strain controlled rotary rheometer the ethylene interpolymer sample analyzed is in the form of a compression formed sample disc placed in a heating chamber of RDS-II between two parallel plate test fixtures, one fixture connected to an actuator and the other fixture connected to a converter, the test is conducted at a constant temperature of fixed strain and 190 ℃ in a frequency range of typically 0.05rad/s to 100rad/s, the test generates data characterizing elastic and viscous properties of the polymer melt, the true elastic or storage modulus (G '), viscosity or loss modulus (G"), complex viscosity η, and tan δ as a function of frequency (dynamic oscillation) ("G ' [ @ 500 @ G ] parameters are determined as a function of G ', a" for a real elastic or storage modulus (G '), a viscosity or loss modulus (G "), complex viscosity η @, and tan δ as a plot of the finished product diameter of the sample is equal to a 2.5G ℃. (a) when the sample is prepared from a round as a round shaped sample without a punch forming plate, the sample, the punch is no impurities, the sample is made as a round plate, and is equal to a round shaped as a round plate with a punch 2.5 mm, and no punch, no punch 2G-5 mm, no impurities is loaded, and is loaded from a round plate, the sample is loaded as a round plate, and no punch, no punch is loaded as a round as a punch, no punch is equal to a punch, no punch is equal to a punch 2.5 mm, no punch, no impurities in the sample is equal to a punch 2 mm, no punch is equal to a punch, no punch 2.

Tensile Properties

The following tensile properties were determined using ASTM D882-12 (8/1/2012): tensile break strength (MPa), elongation at yield (%), yield strength (MPa), ultimate elongation (%), ultimate strength (MPa), and 1% and 2% secant modulus (MPa).

Flexural Properties

Flexural properties, i.e., 2% flex secant modulus, were determined using ASTM D790-10 (published 4 months 2010).

IZOD impact strength

IZOD impact strength (ft-lbs/in) was determined using an IZOD impact pendulum tester using ASTM D256-05 (published 1 month 2005).

Hexane extractables

The hexane extractables were determined according to Federal registration code 21CFR § 177.1520 sections (c)3.1 and 3.2, wherein the amount of hexane extractables in the samples was determined gravimetrically.

Examples

Polymerisation

The following examples are provided for the purpose of illustrating selected embodiments of the present disclosure, and it is to be understood that the examples provided do not limit the claims provided.

Embodiments of the ethylene interpolymer products disclosed herein are produced in a continuous solution polymerization pilot plant comprising reactors arranged in a series configuration. Methylpentane was used as the process solvent (commercial blend of methylpentane isomers). The volume of the first CSTR reactor (R1) was 3.2 gallons (12L), the volume of the second CSTR reactor (R2) was 5.8 gallons (22L), and the volume of the tubular reactor (R3) was 4.8 gallons (18L). An example of an ethylene interpolymer product produced using an R1 pressure of about 14Mpa to about 18 Mpa; r2 was operated at lower pressure to promote continuous flow from R1 to R2. R1 and R2 were operated in series mode with the first outlet stream from R1 flowing directly into R2. The two CSTRs were stirred to provide conditions for thorough mixing of the reactor contents. The process is carried out continuously by feeding fresh process solvent, ethylene, 1-octene and hydrogen into the reactor.

The single-site catalyst components used were: component (i), cyclopentadienyl tris (tert-butyl) phosphinimine titanium dichloride (Cp [ (t-Bu)₃PN]TiCl₂) Hereinafter, denoted as PIC-1; component (ii), methylaluminoxane (MAO-07); component (iii), trityl tetrakis (pentafluorophenyl) borate; and component (iv), 2, 6-di-tert-butyl-4-ethylphenol. The single-site catalyst component solvents used are 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; it is evident that in example 81 in Table 2A, the solution in R1 contained 0.13ppm of component (i), i.e., PIC-1. The molar ratios used to produce the single site catalyst component of example 81 were: r1(ii)/(i) with a molar ratio of 100, i.e., [ (MAO-07)/(PIC-1)](ii) a R1(iv)/(ii) molar ratio 0.0, i.e., [ ((2, 6-di-tert-butyl-4-ethylphenol)/(MAO-07)]](ii) a And R1(iii)/(i)1.1, i.e., [ (trityl tetrakis (pentafluorophenyl) borate)/(PIC-1)]。

An in-line ziegler-natta catalyst formulation was prepared from the following components: component (v), butyl ethyl magnesium; component (vi), tert-butyl chloride; component (vii), titanium tetrachloride; component (viii), diethyl aluminum ethoxide; and component (ix), triethylaluminum. Methylpentane was used as the catalyst component solvent. An in-line ziegler-natta catalyst formulation was prepared using the following procedure. In step 1, a solution of triethylaluminum and dibutylmagnesium in a molar ratio ((triethylaluminum)/(dibutylmagnesium) of 20) is combined with a solution of tert-butylchloride and allowed to react for about 30 seconds (HUT-1); in step 2, a titanium tetrachloride solution was added to the mixture formed in step 1 and allowed to react for about 14 seconds (HUT-2); and in step 3, the mixture formed in step 2 was reacted for another 3 seconds (HUT-3) and then injected into R2. The in-line ziegler-natta procatalyst formulation was injected into R2 using the process solvent, with the catalyst-containing solvent flow rate being about 49 kg/hr. An in-line ziegler-natta catalyst formulation was formed in R2 by injecting a solution of diethylaluminum ethoxide into R2. Table 2A shows the amount of titanium tetrachloride "R2 (vii) (ppm)" added to reactor 2 (R2); as is apparent from example 81, the solution in R2 contained 3.99ppm of TiCl₄. Table 2A also shows the molar ratios of the on-line ziegler-natta catalyst components, in particular: r2(vi)/(v) molar ratio, i.e., [ (tert-butyl chloride)/(butyl ethyl magnesium)](ii) a R2(viii)/(vii) molar ratio, i.e., [ ((diethylaluminum ethoxide)/(titanium tetrachloride)](ii) a And R2(ix)/(vii) molar ratio, i.e., [ (triethylaluminum)/(titanium tetrachloride)]. It is apparent that in example 81, the following molar ratios were used to synthesize an in-line ziegler-natta catalyst: r2(vi)/(v) molar ratio of 1.83; r2(viii)/(vii) molar ratio of 1.35; and the R2(ix)/(vii) molar ratio was 0.35. In all examples disclosed, 100% diethylaluminumethoxide was injected directly into R2.

In example 81 (single site catalyst formulation in R1 + in-line Ziegler-Natta catalyst in R2), the production rate of ethylene interpolymer product was 93.5 kg/h; in contrast, in comparative example 20 (single site catalyst formulation in both R1 and R2), the maximum production rate of the comparative ethylene interpolymer product was 74 kg/h.

The average residence time of the solvent in the reactors is mainly influenced by the amount of solvent flowing through each reactor and the total amount of solvent flowing through the solution process, and the following are representative or typical values for the examples shown in tables 2A-2C: the average reactor residence time was: about 61 seconds in R1, about 73 seconds in R2, and about 50 seconds in R3 (volume of R3 is about 4.8 gallons (18L)).

The polymerization in the continuous solution polymerization process was terminated by adding a catalyst deactivator to the third outlet stream exiting the tubular reactor (R3). The catalyst deactivator used was octanoic acid (octanoic acid), commercially available from P & G Chemicals, Cincinnati, OH, u.s.a. Adding a catalyst deactivator such that the number of moles of fatty acid added is 50% of the total molar amount of titanium and aluminum added to the polymerization process; it is clear that the molar amount of octanoic acid added is 0.5 × (molar amount of titanium + molar amount of aluminum); this molar ratio was used throughout all examples.

The ethylene interpolymer product is recovered from the process solvent using a two stage devolatilization process, i.e., using two gas/liquid separators, and the second bottoms stream (from the second V/L separator) is passed through a gear pump/pelletizer combination. In a continuous solution process, the catalyst is prepared using a catalyst supplied by Kyowa Chemical Industry Co.LTD, Tokyo, Japan

(hydrotalcite) as a passivating or acid scavenger. A slurry of DHT-4V in process solvent was added before the first V/L separator. The molar amount of DHT-4V added is about 10 times the molar amount of chloride added to the process; the chlorides added are titanium tetrachloride and tert-butyl chloride.

Prior to pelletization, by adding about 500ppm based on the weight of the ethylene interpolymer product

1076 (primary antioxidant) and about 500ppm of

168 (auxiliary antioxidant)Agent) to stabilize the ethylene interpolymer product. The antioxidant is dissolved in the process solvent and added between the first V/L separator and the second V/L separator.

Tables 2B and 2C disclose additional solution process parameters such as split streams of ethylene and 1-octene between reactors, reactor temperature and ethylene conversion, etc. recorded during production of example 81 and comparative example 20. In comparative example 20, a single-site catalyst formulation was injected into both reactor R1 and reactor R2, and ES^R1I.e. the percentage of ethylene distributed to reactor 1 was 45%. In example 81, a single site catalyst formulation was injected into R1, an in-line Ziegler-Natta catalyst formulation was injected into R2, and ES^R1The content was 35%.

TABLE 1

Computer generated simulation example 13: single site catalyst formulation (PIC-1) in R1 and in R2 and R3 In-line ziegler-natta catalyst formulation

TABLE 2A

Ethylene interpolymer products continuous solutions of examples 81, 91, 1001, and 1002 and comparative examples 20 and 30 Polymerization Process parameters

TABLE 2B

Additional dissolution of ethylene interpolymer products examples 81, 91, 1001, and 1002 and comparative examples 20 and 30 Liquid process parameters

TABLE 2C

TABLE 3

Physical properties of ethylene interpolymer products examples 81, 91, 1001, and 1002 and comparative examples Q, V, R, Y and X

Table 3 (continuation)

^aAverage value: about

Database of Ti (ppm) in products (NOVA Chemicals),

¹as determined by ASTM D882-12,

²determined by ASTM D790-10

TABLE 4

Dilution index for selected embodiments of the ethylene interpolymers of the present disclosure relative to comparative examples S, A, D and E _d _d ₂₁ ₂(Y) and dimensionless modulus data (X) (MFR ═ melt flow rate (I/I); MS ═ melt strength)

TABLE 5A

Several embodiments of the disclosed ethylene interpolymers and the unsaturation of comparative examples B, C, E, E2, G, H, H2, I, and J Data; determined by ASTM D3124-98 and ASTM D6248-98

FIG. 5B

Additional unsaturation data for several embodiments of the disclosed ethylene interpolymers; by ASTM D3124-98 and ASTM D6248-98 determination

TABLE 6A

Disclosed ethylene interpolymers and neutrons in several embodiments of comparative examples G, I, J, B, C, E, E2, H, and H2 Activation Assay (NAA) catalyst residue

TABLE 6B

Additional Neutron Activation Analysis (NAA) catalyst residues in several embodiments of the disclosed ethylene interpolymers

INDUSTRIAL APPLICABILITY

The present disclosure relates to caps and caps comprising at least one ethylene interpolymer product made using at least one single site catalyst formulation and at least one heterogeneous catalyst formulation in a continuous solution polymerization process utilizing at least two reactors to produce fabricated caps and caps having improved properties.

Claims

1. A cover or shield comprising at least one layer comprising an ethylene interpolymer product comprising:

(I) a first ethylene interpolymer;

(II) a second ethylene interpolymer; and

(III) optionally a third ethylene interpolymer;

wherein

m is a metal selected from titanium, hafnium and zirconium;

pl is a phosphinimine ligand;

wherein a is 1; b is 1; n is 1 or 2; and (a + b + n) is equal to the valence of the metal M;

wherein the third ethylene interpolymer is produced using the first or second in-line Ziegler-Natta catalyst formulation;

wherein the ethylene interpolymer product has a dilution index Y_dLess than 0; and is

Wherein the ethylene interpolymer product has a G' [ @ G ═ 500Pa ] from 80Pa to 120 Pa.

2. The lid or cover of claim 1 wherein the single-site catalyst formulation further comprises an aluminoxane co-catalyst; a boron ion activator; and optionally a hindered phenol.

3. The lid or cover of claim 2 wherein the aluminoxane cocatalyst is Methylaluminoxane (MAO) and the boron ion activator is trityl tetrakis (pentafluorophenyl) borate.

4. The cap or cover of claim 1 wherein said ethylene interpolymer product is further characterized as having one or more of the following:

a) the terminal vinyl unsaturation/100 carbon atoms is more than or equal to 0.03;

b) the total catalytic metal is more than or equal to 3 parts per million (ppm); or

c) Dimensionless modulus X_dLess than 0.

5. The cap or cover of claim 1 wherein the ethylene interpolymer product has a melt index from about 0.3dg/min to about 5 dg/min.

6. The cap or cover of claim 1 wherein the ethylene interpolymer product has a density from about 0.948 g/cc to about 0.968g/cc, wherein the density is measured in accordance with ASTM D792.

7. The cap of claim 1 orA cap, wherein M of the ethylene interpolymer product_w/M_nFrom about 2 to about 25.

8. The cap or cover of claim 1 wherein the CDBI of the ethylene interpolymer product₅₀From about 54% to about 98%.

9. The lid or cover of claim 1, wherein

(I) The first ethylene interpolymer comprises from about 15 to about 60 weight percent of the ethylene interpolymer product and has a melt index from about 0.01dg/min to about 200dg/min and a density from about 0.855 g/cc to about 0.975 g/cc;

(II) the second ethylene interpolymer comprises from about 30 to about 85 weight percent of the ethylene interpolymer product and has a melt index from about 0.3dg/min to about 1000dg/min and a density from about 0.89 g/cc to about 0.975 g/cc;

(III) the third ethylene interpolymer comprises from about 0 wt% to about 30 wt% of the ethylene interpolymer product and has a melt index from about 0.5dg/min to about 2000dg/min and a density from about 0.89 g/cc to about 0.975 g/cc;

wherein weight percent is the weight of the first, the second, or the third ethylene interpolymer, respectively, divided by the weight of the ethylene interpolymer product; and is

Wherein the density is measured according to ASTM D792.

10. The cap or cover of claim 1 wherein the ethylene interpolymer product is synthesized using a solution polymerization process.

11. The cap or cover of claim 1 wherein the ethylene interpolymer product further comprises from 0 mole% to about 1.0 mole% of one or more C₃To C₁₀α -olefins.

12. The lid or cover of claim 11 wherein the one or more α -olefins is 1-hexene, 1-octene or a mixture of 1-hexene and 1-octene.

13. The cap or cover of claim 1, wherein said ethylene interpolymer product has 1 parts per million (ppm) or less of metal A, wherein said metal A is derived from said component (i).

14. The cap or cover of claim 1 wherein said ethylene interpolymer product contains metal B and optionally metal C, and the total amount of said metal B + said metal C is from about 3ppm to about 11 ppm; wherein the metal B is derived from the first online Ziegler-Natta catalyst formulation and the metal C is derived from the second online Ziegler-Natta catalyst formulation; optionally, the metal B and the metal C are the same metal.

15. A lid or cover as claimed in 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.

16. The lid or cover of claim 14 wherein said metal B and said metal C are independently selected from titanium, zirconium, hafnium, vanadium or chromium.

17. The lid or cover of claim 1, wherein

(I) A first CDBI of the first ethylene interpolymer₅₀From about 70% to about 98%;

(II) a second CDBI of the second ethylene interpolymer₅₀From about 45% to about 98%; and is

(III) a third CDBI of the third ethylene interpolymer, if present₅₀From about 35% to about 98%.

18. The lid or cover of claim 16, wherein the first CDBI₅₀Higher than the second CDBI₅₀And the first CDBI₅₀Higher than the third CDBI₅₀。

19. The lid or cover of claim 1, wherein

(I) First M of the first ethylene interpolymer_w/M_nFrom about 1.7 to about 2.8;

(II) a second M of said second ethylene interpolymer_w/M_nFrom about 2.2 to about 4.4; and is

(III) a third M of said third ethylene interpolymer_w/M_nFrom about 2.2 to about 5.0;

wherein the first M_w/M_nIs lower than the second M_w/M_nAnd the third M_w/M_n。

20. The ethylene interpolymer product of claim 19, wherein said second ethylene interpolymer and said third ethylene interpolymer are blended to form a copolymer having a fourth M_w/M_nThe heterogeneous ethylene interpolymer blend of (a); wherein the fourth M_w/M_nIs less than the second M_w/M_nAnd (4) wide.

21. The lid or cover of claim 1 having a G' [ @ G "═ 500Pa ] from 90 Pa to 120 Pa.

22. The lid or cover of claim 1 having a G' [ @ G "═ 500Pa ] from 100 Pa to 120 Pa.

23. The cap or cover of claim 1 further comprising a nucleating agent or a mixture of more than one nucleating agent.

24. A method of manufacturing a lid or cover as claimed in claim 1, wherein the method comprises at least one compression moulding step or one injection moulding step.