Ethylene interpolymer products with unique melt flow, intrinsic viscosity (MFIVI), and low unsaturation.

Abstract

The present disclosure provides a melt flow-intrinsic viscosity index value MFIVI of 0.05 or greater and 0.80 or less; a first derivative of the melt flow distribution function at a load of 4000 g of greater than -1.51 and less than -1.15, Equation 1; a sum of unsaturations SUM of 0.005 or greater and less than 0.047 unsaturations per 100 carbon atoms; U and a residual catalytic metal of hafnium of 0.03 ppm to 5 ppm. The ethylene interpolymer product comprises at least two ethylene interpolymers. The ethylene interpolymer product is characterized by a melt index (I2) of 0.3 to 500 dg / min, a density of 0.855 to 0.975 g / cc, and 0 to 25 mole percent of one or more α-olefins. The ethylene interpolymer product has a polydispersity M of 1.7 to 25. w / M n and CDBI of 1% to 98% 50 These ethylene interpolymer products have utility in flexible and rigid applications.

Description

[Background technology]

[0001] Solution polymerization processes are typically carried out at temperatures above the melting point of the ethylene homopolymer or copolymer being produced. In a typical solution polymerization process, the catalyst, solvent, monomer, and hydrogen are supplied under pressure to one or more reactors.

[0002] In ethylene polymerization or ethylene copolymerization, the reactor temperature can range from 80°C to 300°C, while the pressure is generally in the range of 3 MPag to 45 MPag. The resulting ethylene homopolymer or copolymer remains dissolved in the solvent under reactor conditions. The residence time of the solvent in the reactor is relatively short, for example, 1 second to 20 minutes. The solution process can operate under a wide range of process conditions, enabling the production of a diverse variety of ethylene polymers. After the reactor, the polymerization reaction is quenched by adding a catalyst deactivator to prevent further polymerization. Optionally, the inactivated solution can be passivated by adding an acid scavenger. The inactivated solution, or optionally the passivated solution, is then sent to polymer recovery, where the ethylene homopolymer or copolymer is separated from the process solvent, unreacted residual ethylene, and unreacted optional α-olefins.

[0003] Solution polymerization requires improved processes that produce ethylene interpolymers at higher production rates, i.e., increased pounds of ethylene interpolymer produced per hour. Higher production rates increase the profitability of solution polymerization plants. The catalyst formulations and solution polymerization processes disclosed herein satisfy this need.

[0004] Solution polymerization also requires increasing the molecular weight of the ethylene interpolymer produced at a given reactor temperature. It is well known to those skilled in the art that, assuming a specific catalyst formulation, decreasing the reactor temperature increases the polymer molecular weight. However, decreasing the reactor temperature can be problematic if the solution viscosity becomes excessively high. Consequently, solution polymerization requires catalyst formulations that produce high molecular weight ethylene interpolymers at high reactor temperatures (or lower reactor viscosities). The catalyst formulations and solution polymerization processes disclosed herein satisfy this need.

[0005] Solution polymerization processes also require highly efficient catalyst formulations for incorporating one or more α-olefins into the growing polymer chain. In other words, catalyst formulations are needed that produce lower-density ethylene / α-olefin copolymers at a given [α-olefin / ethylene] weight ratio in the solution polymerization reactor. To put it another way, catalyst formulations are needed that produce ethylene / α-olefin copolymers with a specific density at a lower [α-olefin / ethylene] weight ratio in the reactor feed. Such catalyst formulations efficiently utilize available α-olefins and reduce the amount of α-olefins in the solution process recycling stream.

[0006] The catalyst formulations and solution processes disclosed herein produce unique ethylene interpolymer products having desired properties for various end-uses. One end-use, not limited to this specification, involves packaging films containing the disclosed ethylene interpolymer products. Examples of desired film properties, not limited to this specification, include improved optical properties, lower seal initiation temperatures, and improved hot tack performance. Films prepared from the ethylene interpolymer products disclosed herein have improved properties. [Overview of the Initiative] [Means for solving the problem]

[0007] This disclosure discloses an ethylene interpolymer product comprising at least two ethylene interpolymers, wherein the ethylene interpolymer product has a dimensionless melt flow-to-intrinsic viscosity index MFIVI in the range of 0.05 to 0.80; and the first derivative of the melt flow distribution function at a load of 4000 g in the range of -1.51 to -1.15.

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[0008] The embodiment includes the production of the ethylene interpolymer product using a continuous solution polymerization process with at least one homogeneous catalyst formulation. One embodiment of a preferred homogeneous catalyst formulation is formula (I): [ka] A crosslinked metallocene catalyst composition comprising component A as defined herein, wherein M is a metal selected from titanium, hafnium and zirconium; G is elemental carbon, silicon, germanium, tin or lead; X represents a halogen atom, and the R6 groups are independently a hydrogen atom, C 1~20 hydrocarbyl group, C 1~20 alkoxy group or C 6~10 aryloxide group, and these groups may be linear, branched or cyclic, or may be further substituted with a halogen atom, C 1~10 alkyl group, C 1~10 alkoxy group, C 6~10 aryl or aryloxide group; R1 is a hydrogen atom, C 1~20 hydrocarbyl group, C 1~20 alkoxy group, C 6~10 aryloxide group, or an alkylsilyl group containing at least one silicon atom and C 3~30 carbon atoms; R2 and R3 are independently a hydrogen atom, C 1~20 hydrocarbyl group, C 1~20 alkoxy group, C 6~10 aryloxide group, or an alkylsilyl group containing at least one silicon atom and C 3~30 carbon atoms; R4 and R5 are independently a hydrogen atom, C 1~20 hydrocarbyl group, C 1~20 alkoxy group, C 6~10 aryloxide group, or an alkylsilyl group containing at least one silicon atom and C 3~30 carbon atoms.

[0009] Embodiments include an improved continuous solution polymerization process, and the improved process uses a crosslinked metallocene catalyst to polymerize ethylene and optionally at least one α-olefin in a process solvent in one or more reactors to form an ethylene interpolymer product, and the improved process has an increased production rate PR defined by the following formula I and PR I = 100×(PR A - PRC ) / PR C ≥10% During the ceremony, PR A This refers to the improved process generation speed, PR C This represents the comparative production rate in a comparative continuous solution polymerization process where a crosslinked metallocene catalyst formulation was replaced with a non-crosslinked single-site catalyst formulation.

[0010] Additional embodiments include a crosslinked metallocene catalyst formulation comprising an almoxane co-catalyst (component M); a boron ionic activator (component B); and optionally a hindered phenol (component P). Examples of components M, B, and P, though not limited to these, include methyl almoxane (MMAO-7), trityltetrakis(pentafluorophenyl) borate, and 2,6-di-tert-butyl-4-ethylphenol, respectively.

[0011] Additional embodiments include one or more types of C5~C 12 The invention includes an improved process using a process solvent containing an alkane, and two or more reactors operating at temperatures of 80°C to 300°C and pressures of 3 MPag to 45 MPag. Embodiments may include reactor conditions such that the process solvent in one or more reactors has an average reactor residence time of 10 seconds to 720 seconds. Further embodiments may include reactor conditions such that the catalyst inlet temperature used in one or more reactors can vary between 20°C and 180°C.

[0012] Other embodiments include an improved continuous solution polymerization process in which the ethylene interpolymer product is formed by polymerizing ethylene and optionally at least one α-olefin in a process solvent in two or more reactors using a crosslinked metallocene catalyst formulation, the improved process being characterized by (a) and / or (b) below: (a) The ethylene interpolymer product has at least a 10% improvement (higher) in weight-average molecular weight M, as defined by the following formula. w It has, %improvementM w =100 × (M w A-M w C ) / M w C ≥10% In the formula, M w A M is the weight-average molecular weight of the ethylene interpolymer product produced using the improved process. w C This is the comparative weight-average molecular weight of the comparative ethylene interpolymer product; the comparative ethylene interpolymer product is generated in the comparative process by replacing the crosslinked metallocene catalyst formulation with a non-crosslinked single-site catalyst formulation; (b) The weight ratio of [α-olefin / ethylene] used in the improved process is reduced (improved) by at least 70%, as defined by the following formula:

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[0013] Embodiments of the ethylene interpolymer product include the first and second ethylene interpolymers. Other embodiments of the ethylene interpolymer product may include the first, second, and third ethylene interpolymers. Other embodiments of the ethylene interpolymer product may include the first and third ethylene interpolymers.

[0014] The first ethylene interpolymer has a melt index of 0.01 to 200 dg / min and a density of 0.855 g / cc to 0.975 g / cc; the first ethylene interpolymer may constitute 5 to 100 wt.% of the ethylene interpolymer product. The second ethylene interpolymer may constitute 0 to 95 wt.% of the ethylene interpolymer product and has a melt index of 0.3 to 1000 dg / min and a density of 0.855 g / cc to 0.975 g / cc. The third ethylene interpolymer may constitute 0 to 30 wt.% of the ethylene interpolymer product and has a melt index of 0.4 to 2000 dg / min and a density of 0.855 g / cc to 0.975 g / cc. Weight percent (wt.%) is obtained by dividing the individual weights of the first, second, or optionally selected third ethylene interpolymer by the total weight of the ethylene interpolymer product, the melt index is measured according to ASTM D1238 (load of 2.16 kg and 190°C), and the density is measured according to ASTM D792.

[0015] In further embodiments, CDBI of the first and second ethylene interpolymers 50 The upper limit may be 98%, 95% in other cases, and 90% in yet other cases; CDBI of the first and second ethylene interpolymers 50 The lower limit may be 70%, 75% in other cases, and 80% in yet other cases. CDBI of the third ethylene interpolymer 50 The upper limit may be 98%, 95% in other cases, and 90% in yet other cases; the CDBI of the third ethylene interpolymer 50 The lower limit may be 35%, 40% in other cases, and 45% in yet other cases.

[0016] In other embodiments, the first and second ethylene interpolymers w / M n The upper limit may be 2.4, 2.3 in other cases, and 2.2 in yet other cases; M of the first and second ethylene interpolymers w / M nThe lower limit may be 1.7, 1.8 in other cases, and 1.9 in yet other cases. M of the third ethylene interpolymer w / M n The upper limit may be 5.0, 4.8 in other cases, and 4.5 in yet other cases; M of an optional third ethylene interpolymer w / M n The lower limit may be 1.7, 1.8 in other cases, and 1.9 in yet other cases.

[0017] In this disclosure, the amount of branched long chains in the ethylene interpolymer is characterized by the melt-flow-intrinsic viscosity index (MFIVI) ​​defined by Formula 1 (below) of this disclosure. The ethylene interpolymer product is characterized by an MFIVI value in the range of 0.05 to 0.80. The upper limit of the MFIVI for the first, second, and third ethylene interpolymers may be 0.8 or less, otherwise 0.7 or less, and still otherwise 0.6 or less. The lower limit of the MFIVI for the first and second ethylene interpolymers may be 0.05 or more. The lower limit of the MFIVI for the third ethylene interpolymer may be -0.05 or more, otherwise -0.025 or more, and still otherwise 0.0, i.e., an undetectable level of long-chain branching.

[0018] The ethylene interpolymer product has a first derivative of the melt flow distribution function at a load of 4000g with a value in the range of greater than -1.51 and less than or equal to -1.15.

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[0019] In this disclosure, in order to characterize the unsaturated properties in ethylene interpolymer products, the sum of unsaturated atoms has an unsaturated value of 0.005 or more and less than 0.047 per 100 carbon atoms. U SUM was used. U The formula is as follows: SUM U = 2 × I U +SC U +T U It is calculated according to the formula, where I U This is the internal unsaturation per 100 carbon atoms (100C) in the ethylene interpolymer product, SC U It is side-chain unsaturated, T U It is terminally unsaturated. SUM of ethylene interpolymer products U The upper limit may be less than 0.047, less than 0.046 in other cases, and less than 0.045 in yet other cases. SUM of ethylene interpolymer products U The lower limit may be 0.005 or higher, 0.007 or higher in other cases, and 0.010 or higher in yet other cases.

[0020] In this disclosure, the amount of residual catalyst metal in ethylene interpolymers was characterized by neutron activation analysis (NAA). Metal A in the first ethylene interpolymer R1 The upper limit of ppm may be 5.0 ppm, 4.0 ppm in other cases, and 3.0 ppm in yet other cases, and metal A in the first ethylene interpolymer R1The lower limit of ppm may be 0.03 ppm, 0.09 ppm in other cases, and 0.15 ppm in yet other cases. Metal A in the second ethylene interpolymer R2 The upper limit of ppm may be 5.0 ppm, 4.0 ppm in other cases, and 3.0 ppm in yet other cases; on the other hand, metal A in the second ethylene interpolymer R2 The lower limit of ppm may be 0.03 ppm, 0.09 ppm in other cases, and 0.15 ppm in yet other cases. The catalyst residue in the third ethylene interpolymer reflected the catalyst used in its production. When a crosslinked metallocene catalyst formulation was used, metal A in the third ethylene interpolymer R3 The upper limit of ppm may be 5.0 ppm, 4.0 ppm in other cases, and 3.0 ppm in yet other cases; metal A in the third ethylene interpolymer R3 The lower limit of ppm may be 0.03 ppm, 0.09 ppm in other cases, and 0.15 ppm in yet other cases. When a non-crosslinked single-site catalyst formulation is used, metal C in the third ethylene interpolymer. R3 The upper limit of ppm may be 3.0 ppm, 2.0 ppm in other cases, and 1.5 ppm in yet other cases, and the metal C in the third ethylene interpolymer. R3 The lower limit of ppm may be 0.03 ppm, 0.09 ppm in other cases, and 0.15 ppm in yet other cases. In the case of a homogeneous catalyst formulation containing bulky ligand-metal complexes that are not members of the type defined by formula (I) or (II), metal B in the third ethylene interpolymer. R3 The upper limit of ppm may be 5.0 ppm, 4.0 ppm in other cases, and 3.0 ppm in yet other cases, and metal B in the third ethylene interpolymer. R3 The lower limit of ppm may be 0.03 ppm, 0.09 ppm in other cases, and 0.15 ppm in yet other cases. When heterogeneous catalyst formulations are used, metal Z in the third ethylene interpolymer R3The upper limit of ppm may be 12 ppm, 10 ppm in other cases, or even 8 ppm in further other cases; the metal Z in the third ethylene interpolymer R3 The lower limit of ppm may be 0.5 ppm, 1 ppm in other cases, or even 3 ppm in further other cases.

[0021] Non-limiting embodiments of the articles produced include films comprising at least one layer comprising an ethylene interpolymer product comprising at least two ethylene interpolymers, wherein the ethylene interpolymer product has a dimensionless melt flow-intrinsic viscosity index MFIVI in the range of 0.05 or more and 0.80 or less; a first derivative of the melt flow distribution function at a load of 4000 g in the range of more than -1.51 and less than or equal to -1.15, [Number] a total unsaturation SUM of 0.005 or more and 0.047 or less per 100 carbon atoms U and a residual catalyst metal in the range of 0.03 ppm or more and 5 ppm or less of hafnium. Embodiments of these films have a film gloss at 45° that is 10% to 30% higher than that of a comparative film, and / or the film has a film haze that is 30% to 50% lower than that of a comparative film, where the comparative film has the same composition except that the ethylene interpolymer product synthesized using a crosslinked metallocene catalyst formulation is replaced with a comparative ethylene interpolymer product synthesized using a non-crosslinked single-site catalyst formulation.

[0022] Additional film embodiments include films in which at least one layer further comprises at least one second polymer, and the second polymer may be one or more ethylene polymers, one or more propylene polymers, or a mixture of ethylene polymers and propylene polymers. Further embodiments include films having a total thickness of 0.5 mils to 10 mils. Other embodiments include multilayer films having 2 to 11 layers, with at least one layer comprising at least one ethylene interpolymer product.

[0023] The following figures are shown for the purpose of illustrating selected embodiments of the present disclosure. It is understood that the embodiments in the present disclosure are not limited by these figures. For example, the exact number of tanks shown in FIGS. 3 and 4, or the arrangement of the tanks, is not limited. One aspect of the present invention is shown below, but the present invention is not limited thereto. [Invention 1] Ethylene interpolymer products comprising at least two types of ethylene interpolymers, the following ethylene interpolymer products comprising a to d: a) Dimensionless melt flow intrinsic viscosity index (MFIVI) ​​between 0.05 and 0.80, as defined by Equation 1. [Mathematics 1] JPEG0007873637000009.jpg22166 (In the formula, f 二峰性 It is defined by equation 2, [Math 2] JPEG0007873637000010.jpg12166 The polydisperse Pd (in Equation 2) of the ethylene interpolymer product was determined by size exclusion chromatography (SEC), where Pd = M w / M n And M w and M n These are the weight-average and number-average molecular weights, respectively; Correction factor C f (In Equation 2) is determined according to the following two steps (i) and (ii): (i) Melt flow distribution function of the ethylene interpolymer product defined by Equation 3 [Math 3] JPEG0007873637000011.jpg10166 However, Log(1 / I n It is determined by plotting ) versus Log(load), I n These are the measured melt indices of the ethylene interpolymer product at loads of 21600, 10000, 6000, and 2160 grams, measured at 190°C according to ASTM D1238. (ii) The first derivative of the melt flow distribution function is defined by Equation 4, [Math 4] JPEG0007873637000012.jpg14166 The correction coefficient C f (Equation 2) is the value of the first derivative (Equation 4) at a load of 4000g; The comonomer weight percentage, comonomer Wt% (Equation 1), is the weight percentage of comonomers in the ethylene interpolymer product, measured by FTIR according to ASTM D6645, and when the comonomer Wt% is greater than 14.95%, the comonomer coefficient f コモノマー (Equation 1) is defined by Equation 5, and when the comonomer Wt% is 14.95% or less, the comonomer coefficient is defined by Equation 6. [Number 5] JPEG0007873637000013.jpg18166 The fitted melt index I of the ethylene interpolymer product f Equation (1) is determined by the value of the melt flow distribution function (Equation 3) at a load of 4000g; IV and M v (Equation 1) represents the intrinsic viscosity and viscosity-average molar mass of the ethylene interpolymer product as determined by 3D-SEC, respectively. b) The first derivative (Equation 4) at a load of 4000g having a value greater than -1.51 and less than or equal to -1.15; [Number 6] JPEG0007873637000014.jpg13147 c) Sum of unsaturated carbon atoms defined by Equation 7, which is between 0.005 and 0.047 per 100 carbon atoms. U [Number 7] JPEG0007873637000015.jpg11166 In the formula, I U SC U and T U These are the amounts of internal, side-chain, and terminal unsaturation per 100 carbon atoms in the ethylene interpolymer product, as determined by ASTM D3124-98 and ASTM D6248-98, respectively; and d) A residual catalyst metal of hafnium in a concentration of 0.03 ppm or more and 5 ppm or less, which is measured using neutron activation. [Invention 2] The ethylene interpolymer product according to Invention 1, comprising a first ethylene interpolymer, a second ethylene interpolymer, and optionally a third ethylene interpolymer. [Invention 3] The ethylene interpolymer product according to Invention 1, wherein the ethylene interpolymer product has a melt index of 0.3 to 500 dg / min and a density of 0.855 to 0.975 g / cc, the melt index being measured according to ASTM D1238 (with a load of 2.16 kg and at 190°C), and the density being measured according to ASTM D792. [Invention 4] The ethylene interpolymer product according to Invention 1, further comprising 0 to 25 mole percent of one or more types of α-olefins. [Invention 5] One or more types of α-olefins are C 3 ~C 10 An ethylene interpolymer product according to Invention 5, comprising an α-olefin. [Invention 6] The ethylene interpolymer product according to Invention 5, wherein one or more α-olefins are 1-hexene, 1-octene, or a mixture of 1-hexene and 1-octene. [Invention 7] The ethylene interpolymer product has a polydisperse M of 1.7 to 25. w / M n It has a weight-average molecular weight M w and number-average molecular weight M n The ethylene interpolymer product according to Invention 1, wherein the size is measured using conventional size exclusion chromatography. [Invention 8] CDBI with 1% to 98% ethylene interpolymer products50 It has CDBI 50 The ethylene interpolymer product according to Invention 1, wherein the coefficient is measured using CTREF. [Invention 9] An ethylene interpolymer product according to Invention 1, produced by a solution polymerization process. [Invention 10] The ethylene interpolymer product according to Invention 2, wherein the first and second ethylene interpolymers, or the first and third ethylene interpolymers, are synthesized using a crosslinked metallocene catalyst formulation. [Invention 11] The ethylene interpolymer product according to Invention 10, wherein the crosslinked metallocene catalyst formulation contains component A defined by formula (I): [C1] JPEG0007873637000016.jpg79151 During the ceremony, M is Ti, Hf, or Zr; G is C, Si, Ge, Sn, or Pb; X is a halogen atom; R 6 Each time they appear, H and C appear independently. 1~20 Hydrocarbyl group, C 1~20 Alkoxy group, or C 6~10 Selected from aryloxide groups, these groups may be linear, branched, or cyclic, or they may be halogen atoms, C 1~10 Alkyl alkyl group, C 1~10 Alkoxy group, C 6~10 It may also be further substituted with an aryl or aryloxy group; R 1 H, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy group, C 6~10 An aryl oxide group, or at least one silicon atom and C 3~30 It is an alkylsilyl group containing a carbon atom; R 2 and R 3 H and C are independent of each other. 1~20 Hydrocarbyl group, C 1~20 Alkoxy group, C 6~10 An aryl oxide group, or at least one silicon atom and C 3~30 Selected from alkylsilyl groups containing carbon atoms; R 4 and R 5 H and C are independent of each other. 1~20 Hydrocarbyl group, C 1~20 Alkoxy group, C 6~10 An aryl oxide group, or at least one silicon atom and C 3~30 Selected from alkylsilyl groups containing carbon atoms, Ethylene interpolymer products. [Brief explanation of the drawing]

[0024] [Figure 1] This figure shows the melt flow distribution function, its first derivative, If (white circle), and Cf (white square). [Figure 2] This figure shows the calculation of the melt flow-intrinsic viscosity index (MFIVI). Ethylene interpolymers without long-chain branching (LCBs) or in which LCBs are undetectable lie on the reference line. Deviations from the reference line indicate the presence of LCBs. [Figure 3] This figure shows an embodiment of a continuous solution polymerization process using one CSTR reactor (tank 11a) and one tubular reactor (tank 17). [Figure 4] This figure shows an embodiment of a continuous solution polymerization process using two CSTR reactors (tanks 111a and 112a) and one tubular reactor (tank 117). The two CSTRs can operate in series or parallel mode. [Figure 5] This figure shows the molecular weight distribution determined by SEC and the branching content (BrF, C6 / 1000C) determined by GPCFTIR in Example 14 and Comparison 14. [Figure 6] This figure shows the deconvolution of ethylene interpolymer product example 4 into the first, second, and third ethylene interpolymers. [Figure 7] This figure shows the cold seal force (Newtons, N) of a multilayer film as a function of the sealing temperature. [Figure 8] This figure shows the hot tack force (Newtons, N) of a multilayer film as a function of sealing temperature. [Figure 9] This figure shows a comparison of the first derivatives of the unsaturated sum and melt flow distribution functions of ethylene interpolymer product examples 43-47 with respect to comparisons Q1-Q4, W1 and W2, and previously disclosed examples 1 and 2. [Modes for carrying out the invention]

[0025] Definition of Terms Unless otherwise indicated in the examples, all numbers or expressions used in the specification and claims to refer to quantities of ingredients, extrusion conditions, etc., should be understood in all cases as being modified by the term “approximately.” Therefore, unless otherwise specified, the numerical parameters shown in the following specification and appended claims are approximate and may vary depending on the desired properties that various embodiments seek to achieve. While there is no intention to limit the application of the doctrine of equivalents in the claims, each numerical parameter should be interpreted at least in light of the reported number of significant figures and by applying common rounding techniques. Numerical values ​​described in specific examples are reported as accurately as possible. However, any numerical value inherently contains a certain degree of error, which inevitably arises from the standard deviation observed in its respective test measurements.

[0026] It should be understood that any numerical range enumerated herein is intended to include all subranges contained therein. For example, the range "1 to 10" is intended to include all subranges between the enumerated minimum value of 1 and the enumerated maximum value of 10 (including those values), i.e., all subranges having a minimum value greater than or equal to 1 and a maximum value less than or equal to 10. Since the disclosed numerical ranges are continuous, they include all values ​​between the minimum and maximum values. Unless otherwise illustrated, the various numerical ranges specified herein are approximate.

[0027] All compositional ranges expressed herein are in practice limited to and not exceeding 100 percent (volume or weight percentage) in total. Where multiple components may be present in a composition, the sum of the maximum amounts of each component cannot exceed 100 percent, and the amounts of components actually used will conform to a maximum of 100 percent, as is understood and readily apparent to those skilled in the art.

[0028] To establish a more complete understanding of this disclosure, the following terms are defined and should be used in conjunction with the accompanying figures and the overall description of the various embodiments.

[0029] As used herein, the term “monomer” refers to a small molecule that can chemically react with itself or with other monomers to form polymers.

[0030] As used herein, the term "α-olefin" is used to describe monomers having a straight hydrocarbon chain containing 3 to 20 carbon atoms with a double bond at one end of the chain, and the equivalent term is "straight-chain α-olefin".

[0031] As used herein, the term “ethylene polymer” refers to a polymer produced from ethylene and optionally one or more additional monomers, and is not related to any specific catalyst or process used to produce the ethylene polymer. In the art of polyethylene, one or more additional monomers are often called “comonomers,” and frequently include α-olefins. The term “homopolymer” refers to a polymer containing only one monomer. Common ethylene polymers include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), ultra-low-density polyethylene (ULDPE), plastomers, and elastomers. The term ethylene polymer also includes polymers produced in high-pressure polymerization processes, and lesser than examples include low-density polyethylene (LDPE), ethylene vinyl acetate copolymer (EVA), ethylene alkyl acrylate copolymer, ethylene acrylic acid copolymer, and metal salts of ethylene acrylic acid (commonly called ionomers). The term ethylene polymer also includes block copolymers, which may contain two to four comonomers. The term ethylene polymer also includes combinations or blends of the ethylene polymers described above.

[0032] The term "ethylene interpolymer" refers to a subset of polymers within the "ethylene polymer" group, excluding polymers produced in high-pressure polymerization processes. Examples of polymers produced in high-pressure processes, not limited to these, include LDPE and EVA (the latter being copolymers of ethylene and vinyl acetate).

[0033] The term "heterogeneous ethylene interpolymer" refers to a subset of polymers within the group of ethylene interpolymers produced using heterogeneous catalyst formulations, including, but not limited to, Ziegler-Natta or chromium catalysts.

[0034] The term "homogeneous ethylene interpolymer" refers to a subset of polymers within the group of ethylene interpolymers produced using a homogeneous catalyst formulation. Typically, homogeneous ethylene interpolymers have a narrow molecular weight distribution, e.g., size exclusion chromatography (SEC) M2.8. w / M n It has a value, M w and M n These refer to weight and number-average molecular weight, respectively. On the other hand, the M of heterogeneous ethylene interpolymers w / M n M is typically a homogeneous ethylene interpolymer. w / M n Larger. Generally, homogeneous ethylene interpolymers also have a narrow comonomer distribution, i.e., each polymer within the molecular weight distribution has a similar comonomer content. Often, the Composition Distribution Width Index (CDBI) is used to quantify how comonomers are distributed in ethylene interpolymers and to distinguish ethylene interpolymers produced by different catalysts or processes. 50 "CDI" is defined as the percentage of ethylene interpolymer whose composition is within 50% of the central comonomer composition, and this definition is consistent with that described in U.S. Patent No. 5,206,075, assigned to Exxon Chemical Patents Inc. CDBI of Ethylene Interpolymer 50CDBI can be calculated from the TREF curve (temperature-induced elution fractionation), and the TREF method is described by Wild et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20(3), pp. 441-455. Typically, CDBI of homogeneous ethylene interpolymers. 50 This is over 70%. On the other hand, CDBI of α-olefins containing heterogeneous ethylene interpolymers 50 Generally, CDBI is a homogeneous ethylene interpolymer. 50 Lower. Blends of two or more homogeneous ethylene interpolymers (with different comonomer content) have a CDBI of less than 70%. 50 Such a blend may have a homogeneous blend or homogeneous composition. Similarly, two or more homogeneous ethylene interpolymers (weight-average molecular weight (M) w A blend of (different) is 2.8 or higher M w / M n Such a blend may have the properties of a homogeneous blend or homogeneous composition, and in this disclosure, such a blend may be referred to as a homogeneous blend or homogeneous composition.

[0035] In this disclosure, the term “homogeneous ethylene interpolymer” refers to both linear homogeneous ethylene interpolymers and substantially linear homogeneous ethylene interpolymers. In the art, linear homogeneous ethylene interpolymers are generally assumed to have no long-chain branching or an undetectable amount of long-chain branching, while substantially linear ethylene interpolymers are generally assumed to have more than about 0.01 to about 3.0 long-chain branchings per 1000 carbon atoms. Long-chain branchings are essentially polymers, i.e., their length is similar to the polymer to which the long-chain branchings are bonded.

[0036] In this disclosure, the term “homogeneous catalyst” is defined by the properties of the polymer produced by the homogeneous catalyst. More specifically, the catalyst has a narrow molecular weight distribution (SEC M less than 2.8). w / M n Value) and narrow comonomer distribution (CDBI 50A homogeneous catalyst is used to produce a homogeneous ethylene interpolymer having >70%. Homogeneous catalysts are well known in the art. Two subsets of homogeneous catalyst species include non-crosslinked metallocene catalysts and crosslinked metallocene catalysts. Non-crosslinked metallocene catalysts are characterized by two bulky ligands bonded to the catalyst metal, and an example thereof, not limited to, is bis(isopropyl-cyclopentadienyl)hafnium dichloride. In crosslinked metallocene catalysts, the two bulky ligands are covalently bonded (crosslinked) together, and an example thereof, not limited to, is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl(fuorenyl))hafnium dichloride, where the diphenylmethylene group is bonded together or crosslinked to the cyclopentadienyl and fluorenyl ligands. Two additional subsets of homogeneous catalyst species include non-crosslinked and crosslinked single-site catalysts. In this disclosure, single-site catalysts are characterized as having only one bulky ligand bonded to the catalytic metal. An example of a non-crosslinked single-site catalyst, not limited to this, is cyclopentadienyltri(tert-butyl)phosphineimine titanium dichloride. An example of a crosslinked single-site catalyst, not limited to this, is [C5(CH3)4-Si(CH3)2-N(tBu)] titanium dichloride, where the -Si(CH3)2 group functions as a crosslinking group.

[0037] In this specification, the term “polyolefin” includes ethylene polymers and propylene polymers; examples of propylene polymers that are not limited include isotactic, syndiotactic and atactic propylene homopolymers, random propylene copolymers comprising at least one comonomer (e.g., α-olefin), and impact polypropylene copolymers or heterophase polypropylene copolymers.

[0038] The term "thermoplastic" refers to polymers that become liquid when heated, flow under pressure, and solidify when cooled. Thermoplastic polymers include ethylene polymers and other polymers used in the plastics industry. Other polymers commonly used in film applications include, but are not limited to, barrier resins (EVOH), tie resins, polyethylene terephthalate (PET), and polyamides.

[0039] As used herein, the term "single-layer film" refers to a film comprising a single layer of one or more thermoplastic materials.

[0040] As used herein, the terms "hydrocarbyl," "hydrocarbyl group (radical)," or "hydrocarbyl group (group)" refer to linear, branched, or cyclic aliphatic, olefinic, acetylene, and aryl (aromatic) groups containing one hydrogen and one carbon.

[0041] As used herein, “alkyl group” includes linear, branched, and cyclic paraffinic groups lacking one hydrogen group, including, but not limited to, methyl (-CH3) and ethyl (-CH2CH3) groups. The term “alkenyl group” refers to linear, branched, and cyclic hydrocarbons containing at least one carbon-carbon double bond lacking one hydrogen group.

[0042] As used herein, the term “aryl” group includes phenyl, naphthyl, pyridyl, and other groups whose molecules have an aromatic ring structure, and most not limited to naphthylene, phenanthrene, and anthracene. An “arylalkyl” group is an alkyl group having an aryl group attached thereto, and most not limited to benzyl, phenethyl, and tolylmethyl. An “alkylaryl” group is an aryl group having one or more alkyl groups attached thereto, and most not limited to tolyl, xylyl, mesityl, and cumyl.

[0043] As used herein, the term “heteroatom” includes any atom other than carbon and hydrogen that can bond to carbon. A “heteroatom-containing group” is a hydrocarbon group containing a heteroatom, which may contain one or more of the same or different heteroatoms. In one embodiment, a heteroatom-containing group is a hydrocarbyl group containing one to three atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen, and sulfur. Not limited examples of heteroatom-containing groups include imines, amines, oxides, phosphines, ethers, ketones, oxoazoline heterocycles, oxazolines, thioethers, and the like. The term “heterocycle” refers to a ring system having a carbon skeleton containing one to three atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen, and sulfur.

[0044] As used herein, the term “unsubstituted” means that a hydrogen group is bonded to the group of molecules following the term “unsubstituted.” The term “substituted” means that the group following the term has one or more parts in which one or more hydrogen groups are replaced at any position within the group, and examples of such parts, not limited to, include halogen groups (F, Cl, Br), hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, C1-C 10 Alkyl alkyl groups, C2-C 10 This includes alkenyl groups and combinations thereof. Not limited examples of substituted alkyl and aryl groups include acyl groups, alkylamino groups, alkoxy groups, aryloxy groups, alkylthio groups, dialkylamino groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, alkyl- and dialkyl-carbamoyl groups, acyloxy groups, acylamino groups, arylamino groups and combinations thereof.

[0045] In this specification, the term "R1" and its superscript form " R1 " refers to the first reactor in a continuous solution polymerization process, and R1 is symbol R 1It is understood that these are different, and the latter is used in chemical formulas, for example, to represent a hydrocarbyl group. Similarly, the term "R2" and its superscript form " R2 " refers to the second reactor, and the term "R3" and its superscript form " R3 " refers to the third reactor.

[0046] As used herein, the term “oligomer” refers to low molecular weight ethylene polymers, for example, ethylene polymers having a weight-average molecular weight (Mw) of about 2000 to 3000 Daltons. Other commonly used terms for oligomer include “wax” or “grease.” As used herein, the term “light fraction impurities” refers to relatively low boiling point compounds that may be present in various tanks and process streams within a continuous solution polymerization process, including, but not limited to, methane, ethane, propane, butane, nitrogen, CO2, chloroethane, HCl, etc.

[0047] Description of the Embodiment There is a need to improve the continuous solution polymerization process. For example, it is necessary to increase the molecular weight of the ethylene interpolymer produced at a given reactor temperature. Furthermore, solution polymerization requires highly efficient catalyst formulations for incorporating one or more α-olefins into the increasing polymer chain. In other words, catalyst formulations are needed to produce ethylene / α-olefin copolymers with a specific density at lower (α-olefin / ethylene) ratios in the reactor feed. In addition, ethylene interpolymer products with improved properties after conversion to the finished product are required.

[0048] In the embodiments disclosed herein, a "crosslinked metallocene catalyst formulation" was used in at least two solution polymerization reactors. This catalyst formulation contained "component A," which is a bulky ligand-metal complex defined by formula (I). [ka]

[0049] In formula (I): Examples of M include Group 4 metals, namely titanium, zirconium, and hafnium; Examples of G include Group 14 elements, carbon, silicon, germanium, tin, and lead; X represents a halogen atom, fluorine, chlorine, bromine, or iodine; R6 groups are independently hydrogen atoms, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy group or C 6~10 Aryl oxide groups (these groups may be linear, branched or cyclic, or they may contain a halogen atom, C) 1~10 Alkyl alkyl group, C 1~10 Alkoxy group, C 6~10 Selected from (which may be further substituted with an aryl or aryloxy group); R1 is a hydrogen atom, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy group, C 6~10 An aryl oxide group, or at least one silicon atom and C 3~30 Represents an alkylsilyl group containing a carbon atom; R2 and R3 independently represent a hydrogen atom, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy group, C 6~10 An aryl oxide group, or at least one silicon atom and C 3~30 Selected from alkylsilyl groups containing carbon atoms; R4 and R5 are independently hydrogen atoms, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy group, C 6~10 An aryl oxide group, or at least one silicon atom and C 3~30 Selected from alkylsilyl groups containing carbon atoms.

[0050] In the art, the term commonly used for the X(R6) group in formula (I) is "leaving group," i.e., any ligand that can be removed from formula (I) to form a catalytic species capable of polymerizing one or more olefins. The equivalent term for the X(R6) group is "activatable ligand." Further, non-limiting examples of the X(R6) group in formula (I) include amines, phosphines, ethers, carboxylates, and weak bases such as dienes. In another embodiment, two R6 groups may form part of a fused ring or ring system.

[0051] Further embodiments of component A include structural isomers, optical isomers, or enantiomers (meso and racemic isomers) of the structure shown in formula (I), as well as mixtures thereof. Although not to be construed as limiting, two species of component A include diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dichloride having the molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfCl2] and diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethyl having the molecular formula [(2,7-tBu2Flu)Ph2C(Cp)HfMe2].

[0052] Embodiments of ethylene interpolymer products include (i) ethylene interpolymer products comprising first and second ethylene interpolymers produced using a crosslinked metallocene catalyst; or (ii) ethylene interpolymer products comprising first and third ethylene interpolymers produced using a crosslinked metallocene catalyst formulation; or (iii) ethylene interpolymer products comprising first and second ethylene interpolymers produced using a crosslinked metallocene catalyst, and a third ethylene interpolymer produced using a homogeneous or heterogeneous catalyst formulation. Embodiments include the production of first, second, and third ethylene interpolymers in first, second, and third reactors, respectively. The first and second reactors may operate in series or parallel mode. In series mode, effluent from the first reactor flows directly into the second reactor. In parallel mode, effluent from the first reactor bypasses the second reactor, and effluents from the first and second reactors are combined downstream of the second reactor. A wide variety of catalyst formulations may be used in an optional third reactor. Examples of catalyst formulations used in the third reactor include, but are not limited to, the crosslinked metallocene catalyst formulations described above, the non-crosslinked single-site catalyst formulations described below, homogeneous catalyst formulations containing bulky ligand-metal complexes that are not members of the types defined by formula (I) (above) or formula (II) (below), or heterogeneous catalyst formulations. Examples of heterogeneous catalyst formulations include Ziegler-Natta or chromium catalyst formulations.

[0053] In the comparative 1 samples disclosed herein, for example, comparatives 1a and 1b, a “non-crosslinked single-site catalyst formulation” was used in two solution polymerization reactors. This catalyst formulation contained a bulky ligand-metal complex defined by formula (II), hereafter referred to as “component C”. (L A ) a M(PI) b (Q) n (II)

[0054] In formula (II): (L A) represents a bulky ligand; M represents a metal atom; PI represents a phosphine imine ligand; Q represents a leaving group; a is 0 or 1; b is 1 or 2; (a+b)=2; n is 1 or 2; the sum of (a+b+n) is equal to the valence of the metal M. Examples of M in formula (II) that are not limited include Group 4 metals, titanium, zirconium, and hafnium.

[0055] The bulky ligand L in equation (II) A Examples of which are not limited include unsubstituted or substituted cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom-substituted and / or heteroatom-containing cyclopentadienyl-type ligands. Additional examples of which are not limited include cyclopentaphenanthreneyl ligands, unsubstituted or substituted indenyl ligands, benzindenyl ligands, unsubstituted or substituted fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands, phosphineimines, pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands, etc., including their hydrogenated forms, such as tetrahydroindenyl ligands. In other embodiments, L A This may be any other ligand structure that can η-bond to metal M, and such embodiments include η to metal M. 3 -Bonds and η 5 -Includes both types of bonding. In other embodiments, L A This may include one or more heteroatoms, such as nitrogen, silicon, boron, germanium, sulfur, and phosphorus, which combine with carbon atoms to form ring-opening, acyclic, or fused rings or ring systems, such as heterocyclopentadienyl auxiliary ligands. A Other, less limited embodiments include bulky amides, phosphides, alkoxides, aryl oxides, imides, carbolides, borollides, porphyrins, phthalocyanines, choline, and other polyazomacrocycles.

[0056] The phosphine imine ligand PI is defined by equation (III). (R p )3P=N- (III) In the formula, R p The group is independently a hydrogen atom; a halogen atom; or unsubstituted or substituted with one or more halogen atoms. 1~20 Hydrocarbyl group; C 1~8 Alkoxy group; C 6~10 Aryl group; C 6~10 Aryloxy group; amide group; formula -Si(R s ) Selected from the silyl groups of 3, R s The group consists of a hydrogen atom and a carbon atom. 1~8 Alkyl or alkoxy group, C 6~10 Aryl group, C 6~10 Aryloxy group, or formula -Ge(R G ) Selected from the germanyl groups of 3, R G The basis is R in this paragraph s It is defined in such a way as it is defined.

[0057] The leaving group Q is any ligand that can be removed from formula (II) to form a catalytic species capable of polymerizing one or more olefins. In some embodiments, Q is a monoanionic unstable ligand having a sigma bond to M. Depending on the oxidation state of the metal, the value of n is 1 or 2, such that formula (II) represents a neutral bulky ligand-metal complex. Not limited examples of Q ligands include hydrogen atoms, halogens, and C 1~20 Hydrocarbyl group, C 1~20 Alkoxy group, C 5~10 It contains aryl oxide groups, which may be linear, branched, or cyclic, or a halogen atom, C 1~10 Alkyl alkyl group, C 1~10 Alkoxy group, C 6~10The Q ligand may be further substituted with an aryl or aryloxy group. Further, non-limiting examples of Q ligands include amines, phosphines, ethers, carboxylates, dienes, and weak bases such as hydrocarbyl groups having 1 to 20 carbon atoms. In another embodiment, the two Q ligands may form part of a fused ring or ring system.

[0058] Further embodiments of component C include structural isomers, optical isomers, or enantiomers (meso and racemic isomers) of the bulky ligand-metal complex represented by formula (II), as well as mixtures thereof.

[0059] Although not to be interpreted as an limitation, the two species of component C include cyclopentadienyltri(tert-butyl)phosphineimine titanium dichloride having the molecular formula [Cp[(t-Bu)3PN]TiCl2] and cyclopentadienyltri(isopropyl)phosphineimine titanium dichloride having the molecular formula [Cp[(isopropyl)3PN]TiCl2].

[0060] The cross-linked metallocene catalyst formulation consists of component A (as defined above) and component M A , component B A and component P A Includes. Components M, B and P are defined below, with the superscript " A This indicates that each component was part of a catalyst formulation containing component A, i.e., a cross-linked metallocene catalyst formulation.

[0061] In this disclosure, comparative ethylene interpolymer products were prepared using a non-crosslinked single-site catalyst formulation. In these comparative samples, the crosslinked metallocene catalyst formulation was replaced by the non-crosslinked single-site catalyst formulation. The non-crosslinked single-site catalyst formulation consists of component C (as defined above) and component M C , component B C and component P C Includes. Components M, B and P are defined below, with the superscript " CThis indicates that each component was part of a catalyst formulation containing component C, i.e., a non-crosslinked single-site catalyst formulation.

[0062] Catalyst components M, B, and P are independently selected for each catalyst formulation. More specifically, component M A and M C This may or may not be the same compound, and component B A and B C This may or may not be the same compound, and component P A and P C This may or may not be the same compound. Furthermore, catalytic activity was optimized by independently adjusting the molar ratio of the components in each catalyst formulation.

[0063] Components M, B, and P are not particularly limited; that is, a wide variety of components can be used, as will be described later.

[0064] Component M functioned as a cocatalyst that activated component A or component C into a cationic complex that effectively polymerized ethylene or a mixture of ethylene and α-olefin to produce a high molecular weight ethylene interpolymer. In the crosslinked metallocene catalyst formulations and the non-crosslinked single-site catalyst formulations, component M was independently selected from a variety of compounds, but those skilled in the art will understand that the embodiments in this disclosure are not limited to the specific compounds disclosed. Suitable compounds for component M included almoxane cocatalysts (the equivalent term for almoxane is aluminoxane). The exact structure of the almoxane cocatalyst is uncertain, but experts in the field generally agree that it was an oligomeric species containing repeating units of general formula (IV). (R)2AlO-(Al(R)-O) n -Al(R)2(IV) In the formula, the R group may be the same or different linear, branched, or cyclic hydrocarbyl group containing 1 to 20 carbon atoms, and n is 0 to about 50. An unspecified example of an alumoxane was methylaluminoxane (or MMAO-7), where each R group in formula (IV) is a methyl group.

[0065] Component B was an ionic surfactant. Generally, ionic surfactants consist of a cation and a bulky anion, the latter of which is substantially non-coordinating.

[0066] In the crosslinked metallocene catalyst formulations and the non-crosslinked single-site catalyst formulations, component B was independently selected from a variety of compounds, but those skilled in the art will understand that the embodiments in this disclosure are not limited to the specific compounds disclosed. An example of component B that is not limited to this is a four-coordinate boron ionic surfactant in which four ligands are bonded to a boron atom. An example of a boron ionic surfactant that is not limited to this is the following formulas (V) and (VI) shown below. [R 5 ] + [B(R 7 )4] - (V) In the formula, B represents a boron atom, and R 5 is an aromatic hydrocarbyl (e.g., triphenylmethyl cation), and each R 7 These are, independently, unsubstituted or fluorine atoms, unsubstituted or substituted with fluorine atoms. 1~4 Phenyl groups substituted with 3 to 5 substituents selected from alkyl or alkoxy groups; and formula -Si(R 9 ) Selected from 3 silyl groups, each R 9 These are, independently, hydrogen atoms and C 1~4 Selected from alkyl groups; as well as compounds of formula (VI): [(R 8 ) t ZH] + [B(R 7 )4] - (VI) In the formula, B is a boron atom, H is a hydrogen atom, Z is a nitrogen or phosphorus atom, t is 2 or 3, and R 8 C 1~8 Alkyl alkyl groups, unsubstituted or with up to three Cs 1~4 Selected from phenyl groups substituted with alkyl groups, or one R 8R may combine with a nitrogen atom to form an anilinium group, 7 This was as defined above in equation (VI).

[0067] In both equations (V) and (VI), R 7An example of this, not limited to, was the pentafluorophenyl group. In general, boron ionic surfactants can be described as salts of tetra(perfluorophenyl)boron, and examples of this, not limited to, include anilinium, carbonium, oxonium, phosphonium, and sulfonium salts of tetra(perfluorophenyl)boron with anilinium and trityl (or triphenylmethylium). Additional, but not limited, examples of ionic surfactants include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N-diethyl Anilinium tetra(phenyl) n-butylboron, N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron, di-(isopropyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropylium tetrakisspentafluorophenyl borate, triphenylmethylium tetrakisspentafluorophenyl borate, benzene(diazonium) tetrakisspentafluorophenyl borate, tropylium tetrakis(2,3,5,6-tetrafluorophenyl) borate, triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl) borate, benzene(diazonium) tetrakis(3,4,The compounds included 5-trifluorophenyl) borate, tropylium tetrakis(3,4,5-trifluorophenyl) borate, benzene(diazonium) tetrakis(3,4,5-trifluorophenyl) borate, tropylium tetrakis(1,2,2-trifluoroethenyl) borate, triphenylmethylium tetrakis(1,2,2-trifluoroethenyl) borate, benzene(diazonium) tetrakis(1,2,2-trifluoroethenyl) borate, tropylium tetrakis(2,3,4,5-tetrafluorophenyl) borate, triphenylmethylium tetrakis(2,3,4,5-tetrafluorophenyl) borate, and benzene(diazonium) tetrakis(2,3,4,5-tetrafluorophenyl) borate. Easily available commercial ionic surfactants included N,N-dimethylanilinium tetrakispentafluorophenyl borate and triphenylmethylium tetrakispentafluorophenyl borate. ,

[0068] Component P is a hindered phenol and is an optional component in each catalyst formulation. In the crosslinked metallocene catalyst formulations and the non-crosslinked single-site catalyst formulations, component P was independently selected from a variety of compounds, but those skilled in the art will understand that the embodiments in this disclosure are not limited to the specific compounds disclosed. Examples of hindered phenols that are not limited to these include butylated phenolic antioxidants, butylated hydroxytoluene, 2,4-di-tert-butyl-6-ethylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate.

[0069] As will be fully explained below, the four components in the formulation are component A, component M A , component B A And optionally component P ABy optimizing the amount and molar ratio of the catalyst, an extremely active crosslinked metallocene catalyst formulation was generated. "Extremely active" means that a very large amount of ethylene interpolymer is generated from a very small amount of the catalyst formulation. Similarly, the four components in the formulation, namely component C, component M, C , component B C And optionally component P C By optimizing the amount and molar ratio of [comparative catalyst compound], an extremely active non-crosslinked single-site catalyst formulation (comparative catalyst formulation) was generated.

[0070] In this disclosure, heterogeneous catalyst formulations may be used in an optional third reactor to synthesize a third ethylene interpolymer. Examples of heterogeneous catalyst formulations include Ziegler-Natta and chromium catalyst formulations. Examples of Ziegler-Natta catalyst formulations include "in-line Ziegler-Natta catalyst formulations" or "batch Ziegler-Natta catalyst formulations." The term "in-line" refers to the continuous synthesis of a small amount of activated Ziegler-Natta catalyst and its immediate injection into a third reactor, where ethylene and one or more optional α-olefins are polymerized to form an optional third ethylene interpolymer. The term "batch" refers to the synthesis of a much larger amount of catalyst or pro-catalyst in one or more mixing tanks outside of, or separated from, a continuous solution polymerization process. Once prepared, the batch Ziegler-Natta catalyst formulation, or batch Ziegler-Natta pro-catalyst, was transferred to a catalyst storage tank. The term "pro-catalyst" originally referred to an inert catalyst formulation (inert to ethylene polymerization), but the pro-catalyst was converted to an active catalyst by the addition of an alkylaluminum co-catalyst. If necessary, the pro-catalyst was pumped from a storage tank to at least one continuous-operation reactor, where the active catalyst polymerized ethylene with one or more optionally selected α-olefins to form an ethylene interpolymer. The pro-catalyst could be converted to an active catalyst either inside or outside the reactor.

[0071] A wide variety of compounds can be used to synthesize activated Ziegler-Natta catalyst formulations. The following describes various compounds that can be combined to produce activated Ziegler-Natta catalyst formulations. Those skilled in the art will understand that the embodiments in this disclosure are not limited to the specific compounds disclosed.

[0072] Activated Ziegler-Natta catalyst formulations may be formed from magnesium compounds, chloride compounds, metal compounds, alkylaluminum co-catalysts, and aluminum alkyls. In this disclosure, the term "component (v)" is equivalent to a magnesium compound, "component (vi)" is equivalent to a chloride compound, "component (vii)" is equivalent to a metal compound, "component (viii)" is equivalent to an alkylaluminum co-catalyst, and "component (ix)" is equivalent to an aluminum alkyl. As will be understood by those skilled in the art, Ziegler-Natta catalyst formulations may also contain additional components, the most recent examples of which are electron donors, such as amines or ethers.

[0073] Examples of active in-line Ziegler-Natta catalyst formulations, not limited to those described above, may be prepared as follows: In the first step, a solution of a magnesium compound (component (v)) is reacted with a solution of a chloride compound (component (vi)) to form a magnesium chloride support suspended in solution. Examples of magnesium compounds, not limited to those described above, include Mg(R 1 )2 is included, and in the formula, R 1 The group may be the same or different linear, branched, or cyclic hydrocarbyl groups containing 1 to 10 carbon atoms. Examples of chloride compounds, not limited to R, include: 2 Includes Cl, in the formula, R 2 represents a hydrogen atom or a linear, branched, or cyclic hydrocarbyl group containing 1 to 10 carbon atoms. In the first step, the solution of the magnesium compound may also contain an aluminum alkyl (component (ix)). Not limited examples of aluminum alkyls are Al(R 3 )3 is included, and in the formula, R 3The group may be the same or different linear, branched, or cyclic hydrocarbyl groups containing 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 to support the metal compound on the magnesium chloride. Suitable metal compounds, not limited to M(X) n or MO(X) n The formula includes, where M represents a metal selected from groups 4 to 8 of the periodic table, or a mixture of metals selected from groups 4 to 8; O represents oxygen; X represents a chloride or bromide; and n is an integer from 3 to 6 that satisfies the oxidation state of the metal. Additional, not limited, examples of suitable metal compounds include group 4 to 8 metal alkyls, metal alkoxides (which can be prepared by reacting a metal alkyl with an alcohol), and mixed ligand metal compounds including halides, alkyl and alkoxide ligands. In the third step, a solution of alkylaluminum cocatalyst (component (viii)) is added to the metal compound supported on magnesium chloride. A wide variety of alkylaluminum cocatalysts are preferred, as represented by formula (VII). Al(R 4 ) p (OR 5 ) q (X) r (VII) In the formula, R 4 The group may be the same or different hydrocarbyl groups having 1 to 10 carbon atoms; OR 5 The group may be the same or different alkoxy or aryloxy group, R 5is a hydrocarbyl group having 1 to 10 carbon atoms bonded to oxygen; X is a chloride or bromide; (p+q+r)=3, where p is greater than 0. Examples of commonly used alkylaluminum cocatalysts, not limited to these, 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.

[0074] The process described in the above paragraph for synthesizing the activated inline Ziegler-Natta catalyst formulation can be carried out in a variety of solvents, and examples of solvents that are not limited include linear or branched C5-C5 12 Contains alkanes or mixtures thereof.

[0075] To produce the activated inline Ziegler-Natta catalyst formulation, the amounts and molar ratios of the five components (v) to (ix) are optimized as described below.

[0076] Additional embodiments of heterogeneous catalyst formulations include formulations in which the “metal compound” is a chromium compound, including, but not limited to, silyl chromates, chromium oxide, and chromosene. In some embodiments, the chromium compound is supported on a metal oxide such as silica or alumina. Heterogeneous catalyst formulations containing chromium may also include co-catalysts, including, but not limited to, trialkylaluminum, alkylaluminoxane, and dialkoxyalkylaluminum compounds.

[0077] Long chain branching (LCB) is a structural feature in polyethylene well known to those skilled in the art. Conventionally, there are three methods for quantifying the amount of LCB: nuclear magnetic resonance (NMR) spectroscopy (see, e.g., JC Randall, J Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, 29, 201); triple-detection SEC with a DRI, viscometer, and low-angle laser light scattering detector (see, e.g., W.W. Yau and DR. Hill, Int. J. Polym. Anal. Charact. 1996; 2:151); and rheology (see, e.g., W.W. Graessley, Acc. Chem. Res. 1977, 10, 332-339). Long chain branching is essentially a polymer, and therefore long enough to be observed in NMR spectra, triple-detection SEC experiments, or rheological experiments.

[0078] A limitation of LCB analysis by NMR is that it cannot distinguish the branching length of branches with 6 or more carbon atoms (therefore, NMR cannot be used to characterize LCBs in ethylene / 1-octen copolymers having hexyl groups as side chain branches).

[0079] The triple detection SEC method measures the intrinsic viscosity ([η]) (see WW Yau, D. Gillespie, Analytical and Polymer Science, TAPPI Polymers, Laminations, and Coatings Conference Proceedings, Chicago 2000;2:699 or F. Beer, G. Capaccio, LJ Rose, J. Appl. Polym. Sci. 1999, 73:2807 or PM Wood-Adams, JM Dealy, AW deGroot, OD Redwine, Macromolecules 2000;33:7489). The intrinsic viscosity ([η]) of branched polymers. b ) and the intrinsic viscosity ([η]) of linear polymers of the same molecular weight. lBy referring to the following, the viscosity branching index factor (g'=[η]) can be used to evaluate branching characteristics. b / [η] l ) was used. However, both single-chain branching (SCB) and long-chain branching (LCB) contribute to the intrinsic viscosity ([η]), and efforts have been made to separate the contribution of SCB to ethylene / 1-butene and ethylene / 1-hexene copolymers rather than to ethylene / 1-octene copolymers (see Lue et al., U.S. Patent No. 6,870,010B1).

[0080] This disclosure describes the development of a novel method for quantifying the amount of long-chain branching in ethylene / α-olefin interpolymers. This novel method defines a new parameter called the melt-intrinsic viscosity index (MFIVI) ​​for quantifying the degree of LCB in a resin, which correlates with the melt-flow index (MI) and intrinsic viscosity (IV) of the resin in question. This novel method eliminates the influence of molar mass and molar mass distribution, bimodality in the molar mass distribution, and the type and content of comonomers, enabling the quantification of the amount of long-chain branching in different ethylene interpolymers.

[0081] The melt flow-intrinsic viscosity index (MFIVI) ​​is defined by the following equation, Equation 1.

number

[0082] The various parameters in Equation 1 are fully explained in the following paragraphs.

[0083] f in Equation 1 二峰性 The parameters are defined by equation (2).

number

[0084] In equation (2), the parameter Pd quantifies the polydispersity of the ethylene interpolymer under consideration, and Pd is the conventional polydispersity measured by size exclusion chromatography (SEC), i.e., Pd = M w / M n And M w and M n These are the weight and number-average molecular weight, respectively.

[0085] Parameter C in Equation 2 f This is the correction factor for the ethylene interpolymer in question, and is determined according to the following two-step procedure (steps (i) and (ii)). In step (i), the melt flow distribution function Log(1 / I) defined by equation (3) is determined. n The coefficient is determined for the target ethylene interpolymer.

number

[0086] The melt flow distribution function is Log(1 / I n It is determined by plotting ) versus Log(load), I n These are the measured melt indices of the target ethylene interpolymer at loads of 21600, 10000, 6000, and 2160 grams (measured at 190°C according to ASTM D1238). The dotted lines in Figure 1 show the melt flow distribution function of Example 1, which has β0, β1, and β2 values ​​of 0.84371, 0.93083, and -0.35128, respectively, and the least squares regression R 2 The value was 0.99983. Table 1 records the melt flow distribution functions of the ethylene interpolymer products (Examples 1, 2, and 44), as well as comparative Q1-Q4, W1, and W2. In step (ii), the first derivative of the melt flow distribution function was calculated according to Equation 4.

number

[0087] The solid line in Figure 1 shows the first derivative (Equation 4) of the melt flow distribution function in Example 1. Correction coefficient C f (In Equation 2) is the value of the first derivative (Equation 4) at a load of 4000g. In Example 1, C f The value was -1.600, as indicated by the white square symbol in Figure 1 (Log(4000) = 3.6021). Table 2B shows the values ​​for Examples 1, 2 and 44, as well as comparisons of Q1, Q3, Q4, W1 and W2. f This is a record of the values.

[0088] The ethylene interpolymer product of this disclosure has a first derivative of the melt flow distribution function at a load of 4000g having a value of -1.51 or more and -1.15 or less.

number

[0089] Returning to Equation 1, parameter I f This represents the fitted melt index. The white circle symbol in Figure 1 represents I in Example 1. f The value is shown. More generally, in any ethylene interpolymer in question, I f The value is determined by the value of the melt flow distribution function (Equation 3) at a load of 4000g. Table 2B shows the values ​​for Examples 1, 2 and 44, and comparisons of Q1, Q3, Q4, W1 and W2. f This is a record of the values.

[0090] In Equation 1, the parameter comonomer Wt% is the weight percentage of the comonomer in the ethylene interpolymer to be measured by FTIR according to ASTM D6645. Table 2B records the comonomer Wt% values ​​for Examples 1, 2, and 44, as well as comparative Q1, Q3, Q4, W1, and W2.

[0091] The parameter f that appears in Equation 1 コモノマー See the reference. f used in Equation 1 コモノマーThe value is determined by the comonomer Wt% value, specifically, if the comonomer Wt% is greater than 14.95%, the value used in formula 1 is f. コモノマー The value is determined by Equation 5, and if the comonomer Wt% is 14.95% or less, the value of f used in Equation 1 is used. コモノマー The value is determined by equation 6.

number

[0092] Finally, the parameters IV and M in Equation 1 v These represent the intrinsic viscosity and viscosity-average molar mass of the ethylene interpolymer to be determined by 3D-SEC, respectively. The 3D-SEC procedure is described in detail in this disclosure. Table 2B shows IV and M for Examples 1, 2 and 44, and comparative Q1, Q3 and Q4. v This is a record of the values.

[0093] Figure 2 shows the calculation of the melt flow-intrinsic viscosity index (MFIVI) ​​as described above in Equation 1. MFIVI allows for the quantification of the degree of long-chain branching (LCB) in ethylene interpolymers. In Figure 2, the terms defined above are shown.

number

number

[0094] In this disclosure, resins without LCB (or in which LCB is undetectable) are characterized by an MFIVI value less than 0.05, as is evident from Table 2A, and the reference resins had MFIVI values ​​in the range of -0.042 to 0.043. Two reference resins, Comparison 1a (black triangle), MFIVI = 0.037 (Table 2B) and Comparison T (black diamond), MFIVI = -0.005 (Table 2C), are plotted in Figure 2. Comparison 1a was an ethylene / 1-octene interpolymer produced using a non-crosslinked single-site catalyst formulation in a solution two-reactor process, commercially available as SURPASS® FPs117-C from NOVA Chemicals Corporation, Calgary, Alberta. Comparison T was EXCEED® 1018, available from ExxonMobil Chemical Company, Spring, Texas, which is an ethylene / 1-hexene interpolymer produced using a single-site catalyst formulation in a gas-phase process.

[0095] The ethylene interpolymer products of this disclosure are characterized by the presence of long-chain branching, as is evident from the MFIVI values ​​between 0.05 and 0.80. As shown in Table 2B, ethylene interpolymer product examples 44,1 and 44,2

[0096] As shown in Table 2B, comparisons Q1, Q3, and Q4 contained long-chain branching, as is evident from their MFIVI values ​​of 0.05 or greater and significant deviations from the reference line in Figure 2 (white squares). Comparison Q consisted of commercially available products from Borealis, Vienna, Austria; specifically, comparison Q1 was QUEO® 0201, comparison Q3 was QUEO 0203, and comparison Q4 was QUEO 1001. The MFIVI values ​​for comparisons W1 and W2 were not determined, but these samples contained long-chain branching (i.e., MFIVI value ≥ 0.05), and comparisons W1 and W2 were samples of EXACT® 201 and EXACT 201HS, commercially available from ExxonMobil Chemical Company, Spring, Texas, respectively. Additional comparison samples are shown in Table 2C. Comparison R1 contained LCB, had an MFIVI of 0.298, and showed significant deviations from the reference line in Figure 2 (white diamond). Comparison R1 was a commercially available product called AFFINITY® PL1880G, available from The Dow Chemical Company, Midland, Michigan. Comparisons S1 and S2 included LCBs and had MFIVI values ​​of 0.403 and 0.582, respectively, showing significant deviations from the reference line (Figure 2, black circles). Long-chain branched comparisons S1 and S2 were commercially available products called ENABLE®, available from ExxonMobil Chemical Company, Spring, Texas, specifically ENABLE 20-05HH and Enable 27-03, respectively. Comparison U included an LCB and had an MFIVI of 0.249, showing a significant deviation from the reference line in Figure 2. Comparison U was a commercially available product code ELITE® AT 6202, available from The Dow Chemical Company, Midland, Michigan. Comparative samples V2a and V2b contained LCBs, as is evident from their MFIVI values ​​of 0.102 and 0.099, respectively, and showed significant deviations from the reference line in Figure 2 (dash symbols). Comparative samples V2a and V2b were two samples of a commercially available product called ELITE 5100G, available from The Dow Chemical Company, Midland, Michigan.

[0097] Table 3 shows the internal volume per 100 carbon atoms (100C) (I U ), side chain (SC U ) and terminal (T U The amount of unsaturation and the SUMU defined by Equation 7 are disclosed.

number

[0098] Ethylene interpolymer product example 44 is SUM 0.036 unsaturated / 100C U Although it had a value (i.e., <0.047), previously disclosed ethylene interpolymer product examples 1 and 2 had SUM values ​​of 0.0360 and 0.0350 unsaturated / 100C, respectively. U It had a value. The comparison is with SUM 0.047 or higher. U The ethylene interpolymer product of this disclosure has an unsaturated total value (SUM) in the range of 0.005 or more and less than 0.047 per 100 carbon atoms. U Characterized by:

[0099] Solution polymerization process Embodiments of a continuous solution polymerization process are shown in Figures 3 and 4. Figures 3 and 4 should not be construed as limiting, and it should be understood that embodiments are not limited to the exact arrangement of the tanks shown, or can be broken down into a good number of tanks. Briefly, Figure 3 shows a tubular reactor following one continuous stirred tank reactor (CSTR), and Figure 4 shows an optional tubular reactor following two CSTRs. The dotted lines in Figures 3 and 4 indicate the optional function of the continuous polymerization process. In this disclosure, the equivalent terms for tubular reactor 17 (Figure 3) or 117 (Figure 4) were “third reactor” or “R3,” where the third ethylene interpolymer may or may not be produced in this reactor.

[0100] In Figure 3, process solvent 1, ethylene 2, and an optional α-olefin 3 are combined to produce reactor feed stream RF1, which flows into reactor 11a. The formation of the combined reactor feed stream RF1 is not particularly important; that is, the reactor feed stream can be combined in all possible combinations, including embodiments in which streams 1-3 are independently injected into reactor 11a. Optionally, hydrogen may be injected into reactor 11a via stream 4, which is generally added to control the molecular weight of the first ethylene interpolymer produced in reactor 11a. Reactor 11a is continuously stirred by a stirring assembly 11b, which includes a motor located outside the reactor and a stirrer located inside the reactor.

[0101] The crosslinked metallocene catalyst formulation is injected into reactor 11a via stream 5e. Catalyst component streams 5d, 5c, 5b, and optional 5a refer to an ionic activator (component B), a bulky ligand-metal complex (component A), an almoxane cocatalyst (component M), and an optional hindered phenol (component P), respectively. The catalyst component streams can be arranged in all possible configurations, including embodiments in which streams 5a-5d are injected independently into reactor 11a. Each catalyst component is dissolved in a catalyst component solvent. The catalyst component solvents for components A, B, M, and P may be the same or different. The catalyst component solvents are selected so as not to form precipitates in any process stream, for example, in stream 5e, where the catalyst component combination does not form precipitates. In this disclosure, the term “first homogeneous catalyst assembly” refers to a combination of streams 5a-5e, a flow controller, and a tank (not shown in Figure 3) that functions to deliver the crosslinked metallocene catalyst formulation to the first reactor 11a. The optimization of the cross-linked metallocene catalyst formulation is described below.

[0102] Reactor 11a generates stream 11c, which is a first outlet stream, containing a first ethylene interpolymer dissolved in a process solvent, as well as unreacted ethylene, unreacted α-olefin (if present), unreacted hydrogen (if present), active catalyst, deactivating catalyst, residual catalyst components, and other impurities (if present).

[0103] The first outlet stream, stream 11c, enters the tubular reactor 17. The term “tubular reactor” is intended to convey its conventional meaning, namely that it is a simple tube with a length / diameter (L / D) ratio of at least 10 / 1. The following reactor feed streams are injected into the tubular reactor 17: process solvent 13, ethylene 14, and α-olefin 15. As shown in Figure 3, streams 13, 14, and 15 may be combined to form reactor feed stream RF3, the latter of which is injected into reactor 17. The formation of stream RF3 is not particularly important, i.e., the reactor feed streams can be combined in all possible combinations. Optionally, hydrogen may be injected into reactor 17 via stream 16. The crosslinked metallocene catalyst formulation is injected into reactor 17 via stream 40. In Figure 3, stream 40 represents the output from the "second homogeneous catalyst assembly," and one embodiment of the second homogeneous catalyst assembly is similar to the first homogeneous catalyst assembly described above, i.e., it has the same stream, flow controller and tank.

[0104] In reactor 17, a third ethylene interpolymer is formed. The third ethylene interpolymer may be formed using various operating modes, including, but not limited to, (a) residual ethylene, residual optional α-olefin and residual active catalyst entering reactor 17 react to form the third ethylene interpolymer; (b) fresh process solvent 13, fresh ethylene 14 and optional fresh α-olefin 15 are added to reactor 17, and the residual active catalyst entering reactor 17 forms the third ethylene interpolymer; (c) a fresh catalyst formulation is added to reactor 17 to polymerize residual ethylene and residual optional α-olefin to form the third ethylene interpolymer; or (d) fresh process solvent 13, ethylene 14, optional α-olefin 15 and fresh catalyst formulation are added to reactor 17 to form the third ethylene interpolymer. The effluent from reactor 17 exits through outlet stream 17b. A catalyst deactivator from tank 18B is added to the reactor outlet stream 17b to form an inactivation solution stream 19. The inactivation solution passes through the vacuum device 20 and the heat exchanger 21. Optionally, a passivation agent may be added via tank 22 to form a passivation solution stream 23. Stream 23 passes through the vacuum device 24 and enters the first vapor / liquid separator 25. Hereafter, "V / L" is equivalent to vapor / liquid. Two streams are formed in the first V / L separator: a first bottom stream 27 containing a solution rich in ethylene interpolymer and also containing residual ethylene, residual optional α-olefins and catalyst residues; and a first gaseous top stream 26 containing ethylene, process solvent, optional α-olefins, optional hydrogen, oligomers and, if present, light fraction impurities.

[0105] The first bottom stream enters the second V / L separator 28. In the second V / L separator, two streams are formed: a second bottom stream 30 containing a solution richer in ethylene interpolymer products and less process solvent compared to the first bottom stream 27; and a second gaseous top stream 29 containing the process solvent, optional α-olefins, ethylene, oligomers, and light fraction impurities if present.

[0106] The second bottom stream 30 flows into the third V / L separator 31. In the third V / L separator, two streams are formed: a product stream 33 containing ethylene interpolymer products, inactivated catalyst residue, and less than 5% by weight of residual process solvent; and a third gaseous top stream 32 essentially containing process solvent, optional α-olefins, and light fraction impurities if present.

[0107] The embodiments also include embodiments that use one or more V / L separators that operate under reduced pressure, i.e., at an operating pressure lower than atmospheric pressure, and / or embodiments in which heat is applied during the devolitation process, i.e., one or more heat exchangers are used upstream of or within one or more V / L separators. Such embodiments facilitate the removal of residual process solvents and comonomers such that the residual volatile matter in the ethylene interpolymer product is less than 500 ppm.

[0108] The product stream 33 proceeds to a polymer recovery operation. Examples of polymer recovery operations, though not limited to these, include one or more gear pumps, a single-screw extruder, or a twin-screw extruder forcing the molten ethylene interpolymer product into a pelletizer. Other embodiments include the use of a defoliation extruder, which can remove residual process solvents and optional α-olefins so that the volatile matter in the ethylene interpolymer product is less than 500 ppm. Once pelletized, the solidified ethylene interpolymer product is typically transported to a product silo.

[0109] The first, second, and third gaseous top streams shown in Figure 3 (streams 26, 29, and 32, respectively) are sent to a distillation column where the solvent, ethylene, and an optional α-olefin are separated for recycling; or the first, second, and third gaseous top streams are recycled to a reactor; or a portion of the first, second, and third gaseous top streams are recycled to a reactor and the remainder is sent to a distillation column.

[0110] Figure 4 shows an embodiment of a continuous solution polymerization process using two CSTR reactors and an optional tubular reactor. Process solvent 101, ethylene 102, and an optional α-olefin 103 are combined to produce a reactor feed stream RF101, which flows into reactor 111a. Optionally, hydrogen may be injected into reactor 111a via stream 104. Reactor 111a is continuously stirred by a stirring assembly 111b.

[0111] The first crosslinked metallocene catalyst formulation is injected into reactor 111a via stream 105e. Catalyst component streams 105d, 105c, 105b, and an optional 105a each contain an ionic activator (component B 1 , superscript " 1 (This refers to the first reactor), bulky ligand-metal complex (component A 1 ), almoxane co-catalyst (component M 1 ) and optional hindered phenol (component P 1 ) contains. Each catalyst component is dissolved in the catalyst solvent. Component A 1 B 1 M 1 and P 1 The catalyst component solvents may be the same or different. In Figure 4, the first homogeneous catalyst assembly refers to a combination of streams 105a-105e, a flow controller, and a tank that functions to deliver the activated crosslinked metallocene catalyst formulation to reactor 111a.

[0112] Reactor 111a generates stream 111c, which is a first outlet stream containing a first ethylene interpolymer dissolved in a process solvent. Figure 4 includes two embodiments in which reactors 111a and 112a can operate in series or parallel mode. In series mode, 100% of stream 111c (the first outlet stream) passes through flow controller 111d to form stream 111e, which enters reactor 112a. In parallel mode, 100% of stream 111c passes through flow controller 111f to form stream 111g. Stream 111g bypasses reactor 112a and combines with stream 112c (the second outlet stream) to form stream 112d (the third outlet stream).

[0113] A fresh reactor feed stream is injected into reactor 112a; process solvent 106, ethylene 107, and an optional α-olefin 108 are combined to produce reactor feed stream RF102. The formation of stream RF102 is not critical, i.e., the reactor feed streams can be combined in all possible combinations, including injecting each stream independently into the reactor. Optionally, hydrogen may be injected into reactor 112a via stream 109 to control the molecular weight of the second ethylene interpolymer. Reactor 112a is continuously stirred by a stirring assembly 112b, which includes a motor located outside the reactor and a stirrer inside the reactor.

[0114] As shown in Figure 4, the second crosslinked metallocene catalyst formulation is injected into reactor 112a via stream 110e, and the second ethylene interpolymer is formed in reactor 112a. Catalyst component streams 110d, 110c, 110b, and 110a each contain ionic activator component B 2 (Superscript " 2 (This refers to the second reactor), bulky ligand-metal complex (component A 2 ), almoxane co-catalyst (component M 2 ) and optional hindered phenol (component P 2The catalyst component streams may be arranged in all possible configurations, including embodiments in which streams 110a to 110d are independently injected into reactor 111a. Each catalyst component is dissolved in the catalyst component solvent.

[0115] Equation (I) defines the types of catalyst component A, but component A used in reactor 112a 2 This is catalyst component A used in reactor 111a. 1 It may be the same as or different from the same. Similarly, catalyst component B 2 and B 1 , catalyst component M 2 and M 1 and catalyst component P 2 and P 1 The chemical compositions may be the same or different. In this disclosure, the term “second homogeneous catalyst assembly” refers to a combination of streams 110a-110e, a flow controller, and a tank that functions to deliver the second crosslinked metallocene catalyst formulation to the second reactor, reactor 112a in Figure 4. The optimization of the first and second crosslinked metallocene catalyst formulations is described below.

[0116] Although not shown in Figure 4, an additional embodiment includes splitting stream 105a into two streams such that a portion of stream 105a is injected into reactor 111a and the remaining portion of stream 105a is injected into reactor 112a. In other words, the first crosslinked metallocene catalyst formulation is injected into both reactors.

[0117] When reactors 111a and 112a operate in series mode, the second outlet stream 112c contains the second ethylene interpolymer and the first ethylene interpolymer dissolved in the process solvent; as well as unreacted ethylene, unreacted α-olefin (if present), unreacted hydrogen (if present), active catalyst, deactivating catalyst, catalyst components, and other impurities (if present). Optionally, the second outlet stream 112c is deactivated by adding catalyst deactivator A from catalyst deactivator tank 118A to form deactivated solution A stream 112e, in which case Figure 4 shows the two-reactor solution process as the default. If the second outlet stream 112c is not deactivated, the second outlet stream enters tubular reactor 117.

[0118] When reactors 111a and 112a operate in parallel mode, the second outlet stream 112c contains the second ethylene interpolymer dissolved in the process solvent. The second outlet stream 112c combines with stream 111g to form a third outlet stream 112d, the latter containing the second ethylene interpolymer and the first ethylene interpolymer dissolved in the process solvent. Optionally, the third outlet stream 112d is deactivated by adding catalyst deactivator A from catalyst deactivator tank 118A to form deactivated solution A stream 112e. If the third outlet stream 112d is not deactivated, it enters the tubular reactor 117.

[0119] Optionally, one or more of the following reactor feed streams may be injected into the tubular reactor 117: process solvent 113, ethylene 114, and α-olefin 115. As shown in Figure 4, streams 113, 114, and 115 may be combined to form reactor feed stream RF103, which is injected into reactor 117. The formation of stream RF103 is not particularly important, i.e., the reactor feed streams can be combined in all possible combinations. Optionally, hydrogen may be injected into reactor 117 via stream 116.

[0120] Optionally, homogeneous or heterogeneous catalyst formulations may be injected into reactor 117. Examples of homogeneous catalyst formulations, though not limited to them, include crosslinked metallocene catalyst formulations, non-crosslinked single-site catalyst formulations, or homogeneous catalyst formulations in which the bulky ligand-metal complex is not a member of the type defined by formula (I) or formula (II). Stream 140 in Figure 4 represents the output from the “third homogeneous catalyst assembly.” One embodiment of the third homogeneous catalyst assembly is similar to the first homogeneous catalyst assembly described above, i.e., it has similar streams, flow controllers, and tanks.

[0121] In Figure 4, streams 134a to 134h represent a "heterogeneous catalyst assembly." In one embodiment, the inline Ziegler-Natta catalyst compound is generated within the heterogeneous catalyst assembly. Components containing the inline Ziegler-Natta catalyst compound are introduced via streams 134a, 134b, 134c, and 134d. Stream 134a contains a blend of aluminum alkyl and magnesium compounds, stream 134b contains a chloride compound, stream 134c contains a metal compound, and stream 134d contains an alkylaluminum co-catalyst. Optimization of the inline Ziegler-Natta catalyst compound is described above. Efficient in-line Ziegler-Natta catalyst formulations are formed by optimizing the following molar ratios: (aluminum alkyl) / (magnesium compound) or (ix) / (v); (chloride compound) / (magnesium compound) or (vi) / (v); (alkylaluminum co-catalyst) / (metal compound) or (viii) / (vii); and (aluminum alkyl) / (metal compound) or (ix) / (vii); as well as the time required for these compounds to react and equilibrate.

[0122] The upper limit of the (aluminum alkyl) / (magnesium compound) molar ratio in stream 134a may be 70, in some cases 50, and in other cases 30. The lower limit of the (aluminum alkyl) / (magnesium compound) molar ratio may be 3.0, in some cases 5.0, and in other cases 10. Stream 134b contains a solution of the chloride compound, component (vi), in the process solvent. Stream 134b is combined with stream 134a, and a magnesium chloride catalyst support is produced by mixing streams 134a and 134b. The (chloride compound) / (magnesium compound) molar ratio is optimized to produce an efficient in-line Ziegler-Natta catalyst (efficient in olefin polymerization). The upper limit of the (chloride compound) / (magnesium compound) molar ratio may be 4, in some cases 3.5, and in other cases 3.0. The lower limit of the (chloride compound) / (magnesium compound) molar ratio may be 1.0, in some cases 1.5, and in other cases 1.9. The time between the addition of the chloride compound and the addition of the metal compound (component (vii)) via stream 134c is controlled and hereafter referred to as HUT-1 (first hold-up time). HUT-1 is the time it takes for streams 134a and 134b to equilibrate and form the magnesium chloride support. The upper limit of HUT-1 may be 70 seconds, 60 seconds in some cases, and 50 seconds in others. The lower limit of HUT-1 may be 5 seconds, 10 seconds in some cases, and 20 seconds in others. HUT-1 is controlled by adjusting the length of the conduit between the injection port of stream 134b and the injection port of stream 134c, and by controlling the flow rates of streams 134a and 134b. The time between the addition of component (vii) and the addition of the alkylaluminum cocatalyst and component (viii) via stream 134d is controlled and hereafter referred to as HUT-2 (second hold-up time). HUT-2 is the time it takes for the magnesium chloride support and stream 134c to react and equilibrate. The upper limit for HUT-2 may be 50 seconds, 35 seconds in some cases, and 25 seconds in others. The lower limit for HUT-2 may be 2 seconds, 6 seconds in some cases, and 10 seconds in others.HUT-2 is controlled by adjusting the length of the conduit between the injection port of stream 134c and the injection port of stream 134d, and by controlling the flow rates of streams 134a, 134b, and 134c. The amount of alkylaluminum cocatalyst added is optimized to produce an efficient catalyst, which is achieved by adjusting the (alkylaluminum cocatalyst) / (metal compound) molar ratio, or the (viii) / (vii) molar ratio. The upper limit of the (alkylaluminum cocatalyst) / (metal compound) molar ratio may be 10, in some cases 7.5, and in other cases 6.0. The lower limit of the (alkylaluminum cocatalyst) / (metal compound) molar ratio may be 0, in some cases 1.0, and in other cases 2.0. Furthermore, the time between the addition of the alkylaluminum cocatalyst and the injection of the inline Ziegler-Natta catalyst mixture into reactor 117 is controlled and hereafter referred to as HUT-3 (third hold-up time). HUT-3 is the time it takes for stream 134d to mix and equilibrate to form the inline Ziegler-Natta catalyst mixture. The upper limit of HUT-3 may be 15 seconds, 10 seconds in some cases, and 8 seconds in others. The lower limit of HUT-3 may be 0.5 seconds, 1 second in some cases, and 2 seconds in others. HUT-3 is controlled by adjusting the length of the conduit between the injection port of stream 134d and the catalyst injection port in reactor 117, and by controlling the flow rates of streams 134a-134d. As shown in Figure 4, optionally, 100% of the alkylaluminum cocatalyst in stream 134d may be injected directly into reactor 117 via stream 134h. Optionally, a portion of stream 134d may be injected directly into reactor 117 via stream 134h, and the remainder of stream 134d may be injected into reactor 117 via stream 134e.

[0123] The amount of in-line heterogeneous catalyst compound added to reactor 17 is expressed as parts per million (ppm) of the metal compound (component (vii)) in the reactor solution, and is hereafter referred to as "R3(vii)(ppm)". The upper limit of R3(vii)(ppm) may be 10 ppm, 8 ppm in some cases, and 6 ppm in others. The lower limit of R3(vii)(ppm) may be 0.5 ppm in some cases, 1 ppm in others, and 2 ppm in yet other cases. The (aluminum alkyl) / (metal compound) molar ratio, or (ix) / (vii) molar ratio in reactor 17, is also controlled. The upper limit of the (aluminum alkyl) / (metal compound) molar ratio in the reactor may be 2, 1.5 in some cases, and 1.0 in others. The lower limit of the (aluminum alkyl) / (metal compound) molar ratio may be 0.05, 0.075 in some cases, and 0.1 in others.

[0124] Any combination of streams 134a to 134h, used to prepare and deliver the inline Ziegler-Natta catalyst formulation to reactor 117, may be heated or cooled. In some cases, the upper temperature limit for streams 134a to 134h may be 90°C, in other cases 80°C, and in yet other cases 70°C. In some cases, the lower temperature limit may be 20°C, in other cases 35°C, and in yet other cases 50°C.

[0125] A third ethylene interpolymer may or may not be formed in reactor 117. The third ethylene interpolymer is not formed when catalyst deactivator A is added upstream of reactor 117 via catalyst deactivator tank 118A. The third ethylene interpolymer is formed when catalyst deactivator B is added downstream of reactor 117 via catalyst deactivator tank 118B. The optional third ethylene interpolymer produced in reactor 117 can be formed using various operating modes as described above, except that catalyst deactivator A is not added upstream of reactor 117.

[0126] In series mode, reactor 117 produces a third outlet stream 117b containing a first ethylene interpolymer, a second ethylene interpolymer, and optionally a third ethylene interpolymer. As shown in Figure 4, catalyst deactivator B can be added to the third outlet stream 117b via catalyst deactivator tank 118B to produce an inactivation solution B stream 119, however, catalyst deactivator B is not added if catalyst deactivator A is added upstream of reactor 117. As described above, when catalyst deactivator A is added, the inactivation solution A (stream 112e) is equivalent to stream 117b exiting tubular reactor 117.

[0127] In parallel mode, reactor 117 produces a fourth outlet stream 117b containing a first ethylene interpolymer, a second ethylene interpolymer, and optionally a third ethylene interpolymer (as described above, in parallel mode, stream 112d is the third outlet stream). As shown in Figure 4, in parallel mode, catalyst deactivator B is added to the fourth outlet stream 117b via catalyst deactivator tank 118B to produce an inactivation solution B stream 119, except that catalyst deactivator B is not added if catalyst deactivator A is added upstream of reactor 117.

[0128] In Figure 4, inactivation solution A (stream 112e) or B (stream 119) passes through the vacuum device 120 and the heat exchanger 121. Optionally, a passivating agent may be added via tank 122 to form passivation solution 123.

[0129] Inactivation solution A, inactivation solution B, or passivation solution 123 passes through a vacuum device 124 and enters the first V / L separator 125. In the first V / L separator, two streams are formed: a first bottom stream 127 containing a solution rich in ethylene interpolymer, and a first gaseous top stream 126 rich in ethylene, solvent, an optional α-olefin, and an optional hydrogen.

[0130] The first bottom stream enters the second V / L separator 128. In the second V / L separator, two streams are formed: a second bottom stream 130 containing a solution richer in ethylene interpolymer and with less process solvent compared to the first bottom stream 127, and a second gaseous top stream 129.

[0131] The second bottom stream 130 flows into the third V / L separator 131. In the third V / L separator, two streams are formed: a product stream 133 containing ethylene interpolymer products, inactivated catalyst residue, and less than 5% by weight of residual process solvent; and a third gaseous top stream 132. The product stream 133 proceeds to the polymer recovery operation.

[0132] Other embodiments include the use of one or more V / L separators operating under reduced pressure, i.e., at an operating pressure lower than atmospheric pressure, and / or embodiments in which heat is applied during the devolitation process, i.e., one or more heat exchangers are used upstream of or within one or more V / L separators. Such embodiments facilitate the removal of residual process solvents and comonomers such that the residual volatile matter in the ethylene interpolymer product is less than 500 ppm.

[0133] The product stream 133 proceeds to a polymer recovery operation. Examples of polymer recovery operations, though not limited to these, include one or more gear pumps, a single-screw extruder, or a twin-screw extruder forcing the molten ethylene interpolymer product into a pelletizer. Other embodiments include the use of a defoliation extruder, which can remove residual process solvents and optional α-olefins so that the volatile matter in the ethylene interpolymer product is less than 500 ppm. Once pelletized, the solidified ethylene interpolymer product is typically transported to a product silo.

[0134] By optimizing the proportions of each of the four catalytic components, component A, component M, component B, and component P, a highly active crosslinked metallocene catalyst formulation was generated. The term "highly active" means that the catalyst formulation is highly efficient in the conversion of olefins to polyolefins. In practice, the objective of the optimization is to maximize the following ratio: (pounds of ethylene interpolymer product produced) per (pounds of catalyst consumed). For a single CSTR, the amount of the bulky ligand-metal complex, component A, added to reactor R1 was expressed as parts per million (ppm) of component A in the total mass of the solution in R1, i.e., "R1 catalyst (ppm)" as listed in Table 5A. The upper limit of ppm for component A may be 5, in some cases 3, and in other cases 2. The lower limit for ppm for component A may be 0.02, in some cases 0.05, and in other cases 0.1. In the case of two CSTRs, the amount of component A added to R1 and R2 was controlled and expressed as parts per million (ppm) of component A in R1 and R2, and optionally, the amount of component A added to R3 was also controlled and expressed as parts per million (ppm) of component A in R3.

[0135] The proportions of catalyst component B and ionic activator added to R1 were optimized by controlling the molar ratio ([B] / [A]) of (ionic activator) in the R1 solution. The upper limit of R1([B] / [A]) may be 10, 5 in some cases, and 2 in others. The lower limit of R1([B] / [A]) may be 0.3, 0.5 in some cases, and 1.0 in others. The proportion of catalyst component M was optimized by controlling the molar ratio ([M] / [A]) of (almoxane) in the R1 solution. The almoxane cocatalyst was generally added in molar excess relative to component A. The upper limit of R1([M] / [A]) may be 300, 200 in some cases, and 100 in others. The lower limit of R1([M] / [A]) may be 1, 10 in some cases, and 30 in others. The addition of catalyst component P (hindered phenol) to R1 is optional. When added, the proportion of component P was optimized by controlling the (hindered phenol) / (almoxane)([P] / [M]) molar ratio in R1. The upper limit of R1([P] / [M]) may be 1, 0.75 in some cases, and 0.5 in others. The lower limit of R1([P] / [M]) may be 0.0, 0.1 in some cases, and 0.2 in others.

[0136] In embodiments using two CSTRs and two homogeneous catalyst assemblies, a second crosslinked metallocene catalyst formulation may be prepared independently of the first crosslinked metallocene catalyst formulation and optimized as described above. Optionally, the crosslinked metallocene catalyst formulation may be used in a tubular reactor and optimized as described above.

[0137] In the embodiment of the continuous solution process shown in Figures 3 and 4, various solvents may be used as process solvents, and are not limited to linear, branched, or cyclic C5-C5 solvents. 12 Includes alkanes. Examples of α-olefins (not limited to those mentioned) include 1-propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, and 1-decene. Suitable catalyst solvents include aliphatic and aromatic hydrocarbons. Examples of aliphatic catalyst solvents (not limited to those mentioned) include linear, branched, or cyclic C11s.5~12 Aliphatic hydrocarbons, such as pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, hydrolyzed naphtha, or combinations thereof. Not limited examples of aromatic catalyst solvents include benzene, toluene (methylbenzene), ethylbenzene, o-xylene (1,2-dimethylbenzene), m-xylene (1,3-dimethylbenzene), p-xylene (1,4-dimethylbenzene), mixtures of xylene isomers, hemelitene (1,2,3-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), mixtures of trimethylbenzene isomers, prehenitene (1,2,3,4-tetramethylbenzene), julen (1,2,3,5-tetramethylbenzene), mixtures of tetramethylbenzene isomers, pentamethylbenzene, hexamethylbenzene, and combinations thereof.

[0138] It is well known to those skilled in the art that the reactor feed stream (solvent, monomer, α-olefin, hydrogen, catalyst formulation, etc.) must be substantially free of catalyst-deactivating toxins, and not limited to examples of toxins, include trace amounts of oxygenated substances, such as water, fatty acids, alcohols, ketones, and aldehydes. Such toxins are removed from the reactor feed stream using standard purification practices, not limited to examples including molecular sieve beds, alumina beds, and oxygen removal catalysts for the purification of solvents, ethylene, and α-olefins, etc.

[0139] Referring to the first reactor shown in Figure 3, or the first and second reactors shown in Figure 4, the supply streams, more specifically any combination of streams 1-4 in Figure 3 and streams 101-104 and 106-109 in Figure 4, may be heated or cooled. The upper limit of the reactor supply stream temperature may be 90°C, 80°C in other cases, and 70°C in yet other cases. The lower limit of the reactor supply stream temperature may be 20°C, 35°C in other cases, and 50°C in yet other cases.

[0140] Any combination of the streams supplied to the tubular reactor, for example, streams 13-16 in Figure 3 and streams 113-116 in Figure 4, may be heated or cooled. In some cases, the tubular reactor supply streams are tempered, i.e., heated to at least above ambient temperature. The upper temperature limit for the tubular reactor supply streams is 200°C in some cases, 170°C in others, and 140°C in yet other cases, and the lower temperature limit for the tubular reactor supply streams is 60°C in some cases, 90°C in others, and 120°C in yet other cases, provided that the temperature of the tubular reactor supply streams is lower than the temperature of the process streams entering the tubular reactor.

[0141] The operating temperatures of the solution polymerization reactors, such as reactors 111a(R1) and 112a(R2) in Figure 4, can vary over a wide range. For example, the upper limit of the reactor temperature may be 300°C in some cases, 280°C in others, and 260°C in yet other cases, and the lower limit may be 80°C in some cases, 100°C in others, and 125°C in yet other cases. The second reactor, reactor 112a(R2), operates at a higher temperature than the first reactor 111a(R1). The maximum temperature difference (T) between these two reactors is... R2 -T R1 ) is 120°C in some cases, 100°C in others, and 80°C in yet other cases, with the minimum (T R2 -T R1The temperature is 1°C in some cases, 5°C in other cases, and 10°C in yet other cases. An optional tubular reactor, reactor 117(R3), may operate at a temperature 100°C higher than R2 in some cases, 60°C higher than R2 in other cases, 10°C higher than R2 in yet other cases, and 0°C higher, i.e., the same temperature as R2, in an alternative case. The temperature in the optional R3 may increase along its length. The maximum temperature difference between the inlet and outlet of R3 is 100°C in some cases, 60°C in other cases, and 40°C in yet other cases. The minimum temperature difference between the inlet and outlet of R3 is 0°C in some cases, 3°C in other cases, and 10°C in yet other cases. In some cases R3 operates in an adiabatic manner, and in other cases R3 is heated.

[0142] The pressure inside the polymerization reactor should be high enough to maintain the polymerization solution as a single-phase solution and to provide upstream pressure to push the polymer solution out of the reactor through the heat exchanger to the polymer recovery operation. Referring to the embodiments shown in Figures 3 and 4, the operating pressure of the solution polymerization reactor can vary over a wide range. For example, the upper limit of the reactor pressure may be 45 MPag in some cases, 30 MPag in others, and 20 MPag in yet other cases, and the lower limit may be 3 MPag in some cases, 5 MPag in others, and 7 MPag in yet other cases.

[0143] Referring to the embodiments shown in Figures 3 and 4, before entering the first V / L separator, the inactivating solution A, inactivating solution B, or passivation solution may have a maximum temperature of 300°C in some cases, 290°C in other cases, and 280°C in yet other cases, and a minimum temperature of 150°C in some cases, 200°C in other cases, and 220°C in yet other cases. Immediately before entering the first V / L separator, the inactivating solution A, inactivating solution B, or passivation solution may have a maximum pressure of 40 MPag in some cases, 25 MPag in other cases, and 15 MPag in yet other cases, and a minimum pressure of 1.5 MPag in some cases, 5 MPag in other cases, and 6 MPag in yet other cases.

[0144] The first V / L separator (tanks 25 and 125 in Figures 3 and 4, respectively) can operate over a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the first V / L separator may be 300°C in some cases, 285°C in others, and 270°C in yet other cases, and the minimum operating temperature may be 100°C in some cases, 140°C in others, and 170°C in yet other cases. The maximum operating pressure of the first V / L separator may be 20 MPag in some cases, 10 MPag in others, and 5 MPag in yet other cases, and the minimum operating pressure may be 1 MPag in some cases, 2 MPag in others, and 3 MPag in yet other cases.

[0145] The second V / L separator can operate over a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the second V / L separator may be 300°C in some cases, 250°C in others, and 200°C in yet other cases, and the minimum operating temperature may be 100°C in some cases, 125°C in others, and 150°C in yet other cases. The maximum operating pressure of the second V / L separator may be 1000kPag in some cases, 900kPag in others, and 800kPag in yet other cases, and the minimum operating pressure may be 10kPag in some cases, 20kPag in others, and 30kPag in yet other cases.

[0146] The third V / L separator (tanks 31 and 131 in Figures 3 and 4, respectively) can operate over a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the third V / L separator may be 300°C in some cases, 250°C in others, and 200°C in yet other cases, and the minimum operating temperature may be 100°C in some cases, 125°C in others, and 150°C in yet other cases. The maximum operating pressure of the third V / L separator may be 500 kPag in some cases, 150 kPag in others, and 100 kPag in yet other cases, and the minimum operating pressure may be 1 kPag in some cases, 10 kPag in others, and 25 kPag in yet other cases.

[0147] The embodiment of the continuous solution polymerization process shown in Figures 3 and 4 exhibits three V / L separators. However, the continuous solution polymerization embodiment may include a configuration comprising at least one V / L separator.

[0148] The ethylene interpolymer products generated in a continuous solution polymerization process can be recovered using conventional devolatilization systems well known to those skilled in the art, including, but not limited to, flash devolatilization systems and devolatilization extruders.

[0149] Any reactor shape or design can be used for reactors 111a(R1) and 112a(R2) in Figure 4, including, but not limited to, unagitated or agitated spherical, cylindrical or tank-like vessels, and tubular or recirculating loop reactors. The maximum commercial-scale volume of R1 may be about 20,000 gallons (about 75,710 L) in some cases, about 10,000 gallons (about 37,850 L) in others, and about 5,000 gallons (about 18,930 L) in yet other cases. The minimum commercial-scale volume of R1 may be about 100 gallons (about 379 L) in some cases, about 500 gallons (about 1,893 L) in others, and about 1,000 gallons (about 3,785 L) in yet other cases. At pilot plant scale, reactor volumes are typically much smaller; for example, the volume of R1 at pilot scale may be less than about 2 gallons (less than about 7.6 L). In this disclosure, the volume of reactor R2 is expressed as a percentage of the volume of reactor R1. The upper limit of the volume of R2 may be about 600% of R1 in some cases, about 400% of R1 in other cases, and about 200% of R1 in yet other cases. For clarity, if the volume of R1 is 5,000 gallons and R2 is 200% of the volume of R1, then R2 has a volume of 10,000 gallons. The lower limit of the volume of R2 may be about 50% of R1 in some cases, about 100% of R1 in other cases, and about 150% of R1 in yet other cases. In the case of a continuous stirred-tank reactor, the stirring speed can vary over a wide range, in some cases about 10 rpm to about 2000 rpm, in other cases about 100 to about 1500 rpm, and in yet other cases about 200 to about 1300 rpm. In this disclosure, the volume of the tubular reactor R3 is expressed as a percentage of the volume of reactor R2. The upper limit of the volume of R3 may be about 500% of R2 in some cases, about 300% of R2 in other cases, and in yet other cases about 100% of R2. The lower limit of the volume of R3 may be about 3% of R2 in some cases, about 10% of R2 in other cases, and in yet other cases about 50% of R2.

[0150] The "average reactor residence time," a parameter commonly used in the technical field of the chemical industry, is defined by the first moment of the reactor residence time distribution, which is a probability distribution function that explains the time spent by fluid elements in the reactor. The average reactor residence time can vary widely depending on the process flow rate and the reactor mixing, design, and capacity. The upper limit of the average reactor residence time for a solution in R1 may be 600 seconds in some cases, 360 seconds in others, and 180 seconds in yet other cases. The lower limit of the average reactor residence time for a solution in R1 may be 10 seconds in some cases, 20 seconds in others, and 40 seconds in yet other cases. The upper limit of the average reactor residence time for a solution in R2 may be 720 seconds in some cases, 480 seconds in others, and 240 seconds in yet other cases. The lower limit of the average reactor residence time for a solution in R2 may be 10 seconds in some cases, 30 seconds in others, and 60 seconds in yet other cases. The upper limit of the average reactor residence time for the solution in R3 may be 600 seconds in some cases, 360 seconds in others, and 180 seconds in yet other cases. The lower limit of the average reactor residence time for the solution in R3 may be 1 second in some cases, 5 seconds in others, and 10 seconds in yet other cases.

[0151] Optionally, additional reactors (e.g., CSTRs, loops, or tubes) may be added to the embodiment of the continuous solution polymerization process shown in Figure 4. The number of reactors is not particularly important in this disclosure.

[0152] In the operation of the embodiment of the continuous solution polymerization process shown in Figure 4, the total amount of ethylene supplied to the process can be distributed or divided among the three reactors R1, R2, and R3. This operating variable is referred to as ethylene division (ES), i.e., "ES R1 "ES" R2 " and "ES R3 " refers to the weight percentage of ethylene injected into R1, R2, and R3, respectively, however, ES R1 +ES R2 +ES R3=100%. This is achieved by adjusting the ethylene flow rate in the following streams: Stream 102 (R1), Stream 107 (R2), and Stream 114 (R3). ES R1 The upper limit is approximately 60% in some cases, approximately 55% in others, and approximately 50% in yet other cases, ES R1 The lower limit is approximately 10% in some cases, approximately 15% in others, and approximately 20% in yet other cases. R2 The upper limit is approximately 90% in some cases, approximately 80% in others, and approximately 70% in yet other cases, ES R2 The lower limit is approximately 20% in some cases, approximately 30% in others, and approximately 40% in yet other cases. R3 The upper limit is approximately 30% in some cases, approximately 25% in others, and approximately 20% in yet other cases, ES R3 The lower limit is 0% in some cases, about 5% in others, and about 10% in yet another case.

[0153] In the operation of the embodiment of the continuous solution polymerization process shown in Figure 4, the ethylene concentration in each reactor is also controlled. The ethylene concentration in reactor 1 is hereafter referred to as EC R1 Although it is called EC, it is defined as the weight of ethylene in reactor 1 divided by the total weight of all substances added to reactor 1. R2 and EC R3 The same definition applies to reactors (EC) R1 or EC R2 or EC R3 The ethylene concentration within the ) can vary between approximately 7 wt.% and 25 wt.% in some cases, between approximately 8 wt.% and 20 wt.% in others, and between approximately 9 wt.% and 17 wt.% in yet other cases.

[0154] In the operation of the embodiment of the continuous solution polymerization process shown in Figure 4, the total amount of ethylene converted in each reactor is monitored. R1 The term "Q" refers to the percentage of ethylene added to R1 that is converted to ethylene interpolymer by the catalyst formulation. Similarly, QR2 and Q R3 Q represents the percentage of ethylene added to R2 and R3 that was converted to ethylene interpolymer in each reactor. The ethylene conversion rate can vary considerably depending on various process conditions, such as catalyst concentration, catalyst composition, impurities, and toxins. R1 and Q R2 The upper limits for both are approximately 99% in some cases, approximately 95% in others, and approximately 90% in yet other cases, Q R1 and Q R2 The lower limits for both are approximately 65% ​​in some cases, approximately 70% in others, and approximately 75% in yet other cases. R3 The upper limit is approximately 99% in some cases, approximately 95% in others, and approximately 90% in yet other cases, Q R3 The lower limit is 0% in some cases, about 5% in others, and about 10% in yet another case. T The term "Q" represents the overall or total ethylene conversion rate across the entire continuous solution polymerization plant, i.e., Q T = 100 × [weight of ethylene in the interpolymer product] / ([weight of ethylene in the interpolymer product] + [weight of unreacted ethylene]). Q T The upper limit is approximately 99% in some cases, approximately 95% in others, and approximately 90% in yet other cases, Q T The lower limit is approximately 75% in some cases, approximately 80% in others, and approximately 85% in yet another case.

[0155] Referring to Figure 4, α-olefins may optionally be added to the continuous solution polymerization process. If added, the α-olefins may be distributed or split among R1, R2, and R3. This operating variable is referred to as comonomer (α-olefin) splitting (CS), i.e., "CS R1 "CS R2 " and "CS R3 " refers to the weight percentage of α-olefin comonomers injected into R1, R2, and R3, respectively, however, CS R1 +CS R2 +CS R3=100%. This is achieved by adjusting the α-olefin flow rate in the following streams: Stream 103 (R1), Stream 108 (R2), and Stream 115 (R3). CS R1 The upper limit is 100% in some cases (i.e., 100% of the α-olefin is injected into R1), about 95% in other cases, and about 90% in yet other cases. R1 The lower limit is 0% (ethylene homopolymer produced in R1) in some cases, about 5% in others, and about 10% in yet other cases. R2 The upper limit is approximately 100% in some cases (i.e., 100% of the α-olefin is injected into reactor 2), approximately 95% in other cases, and approximately 90% in yet other cases. R2 The lower limit is 0% in some cases, about 5% in others, and about 10% in yet other cases. R3 The upper limit is 100% in some cases, about 95% in others, and about 90% in yet other cases. R3 The lower limit is 0% in some cases, about 5% in others, and about 10% in yet another case.

[0156] In the continuous polymerization process described herein, polymerization is terminated by adding a catalyst deactivator. The embodiment in Figure 4 shows catalyst deactivation occurring (a) upstream of the tubular reactor by adding catalyst deactivator A from catalyst deactivator tank 118A, or (b) downstream of the tubular reactor by adding catalyst deactivator B from catalyst deactivator tank 118B. Catalyst deactivator tanks 118A and 118B may contain untreated (100%) catalyst deactivator, a solution of catalyst deactivator in a solvent, or a slurry of catalyst deactivator in a solvent. The chemical compositions of catalyst deactivators A and B may be the same or different. Suitable solvents, though not limited to certain examples, include linear or branched C5-C 12This includes alkanes. In this disclosure, how the catalyst deactivator is added is not particularly important. When added, the catalyst deactivator substantially halts the polymerization reaction by converting the active catalyst species into an inactive form. Suitable deactivators are well known in the art and include, but are not limited to, amines (e.g., Zboril et al., U.S. Patent No. 4,803,259); alkali or alkaline earth metal salts of carboxylic acids (e.g., Machan et al., U.S. Patent No. 4,105,609); water (e.g., Bernier et al., U.S. Patent No. 4,731,438); hydrotalcite, alcohols and carboxylic acids (e.g., Miyata, U.S. Patent No. 4,379,882); or combinations thereof (Sibtain et al., U.S. Patent No. 6,180,730). In this disclosure, the amount of catalyst deactivator added is determined by the following catalyst deactivator molar ratio: 0.3 ≤ (catalyst deactivator) / ((total catalyst metal) + (alkylaluminum cocatalyst) + (aluminum alkyl)) ≤ 2.0, where total catalyst metal is the total moles of catalyst metal added to the solution process. The upper limit of the catalyst deactivator molar ratio may be 2, in some cases 1.5, and in other cases 0.75. The lower limit of the catalyst deactivator molar ratio may be 0.3, in some cases 0.35, and in yet other cases 0.4. In general, the catalyst deactivator is added in the minimum amount necessary to deactivate the catalyst and quench the polymerization reaction.

[0157] A passivating agent or acid scavenger may be added to inactivation solution A or B to form a passivation solution, i.e., a passivation solution stream 123 as shown in Figure 4. An optional passivating agent tank 122 may contain untreated (100%) passivating agent, a solution of passivating agent in a solvent, or a slurry of passivating agent in a solvent. Suitable solvents, though not limited to linear or branched C5-C5, are linear or branched C5-C5. 12This includes alkanes. In this disclosure, the method of adding the passivator is not particularly important. Suitable passivators are well known in the art, and examples therein include alkali or alkaline earth metal salts of carboxylic acids or hydrotalcite. The amount of passivator added can vary widely. The amount of passivator added was determined by the total moles of the chloride compound added to the solution process, i.e., “compound (vi)”, which is a chloride compound, and “compound (vii)”, which is a metal compound used to produce a heterogeneous catalyst formulation. The upper limit of the (passivator) / (total chloride) molar ratio may be 15, in some cases 13, and in other cases 11. The lower limit of the (passivator) / (total chloride) molar ratio may be about 5, in some cases about 7, and in yet other cases about 9. In general, the passivator is added in the minimum amount necessary to substantially passivate the inactivation solution.

[0158] In this disclosure, a non-crosslinked single-site catalyst formulation was used in a comparative solution process to produce a comparative ethylene interpolymer product. The four catalyst components were: component C, component M C (Superscript " C (This indicates a non-crosslinked single-site catalyst formulation), component B C and component P C By optimizing the proportions of each component, an extremely active non-crosslinked single-site catalyst formulation was generated.

[0159] In the case of a single CSTR, the amount of the bulky ligand metal complex, component C, added to the first reactor (R1) was expressed as parts per million (ppm) of component C in the total mass of the solution in R1, i.e., "R1 catalyst (ppm)". In the case of two CSTRs, the amounts of component C added to R1 and R2 were controlled and expressed as parts per million (ppm) of component C in R1 and R2, and optionally, the amount of component C added to R3 was controlled and expressed as parts per million (ppm) of component C in R3. The upper limit of ppm of component C in any reactor may be 5, in some cases 3, and in other cases 2. The lower limit of ppm of component C in any reactor may be 0.02, in some cases 0.05, and in other cases 0.1.

[0160] Catalyst component B C The ratio is the molar ratio ((ionic activator) / (bulky ligand-metal complex) in the reactor ([B C Optimized by controlling ] / [C]). Reactor ([B C The upper limit of ] / [C]) may be 10, 5 in some cases, and 2 in others. Reactor ([B C The lower limit of ] / [C]) may be 0.3, 0.5 in some cases, and 1.0 in others. Catalyst component M C The ratio is the molar ratio (almoxane) / (bulky ligand-metal complex) in the reactor ([M C The reactor ([M C The upper limit of the molar ratio of ] / [C] may be 1000, 500 in some cases, and 200 in others. Reactor ([M C The lower limit of the molar ratio of ] / [C] may be 1, 10 in some cases, and 30 in others. Catalyst component P C The addition of component P is optional. If added, component P C The ratio is the molar ratio (hindered phenol) / (almoxane) in any reactor ([P C ] / [M COptimized by controlling the reactor ([P C ] / [M C The upper limit of the molar ratio may be 1.0, 0.75 in some cases, and 0.5 in others. Reactor ([P C ] / [M C The lower limit of the molar ratio may be 0.0, 0.1 in some cases, and 0.2 in others.

[0161] Interpolymer The first ethylene interpolymer was synthesized using a crosslinked metallocene catalyst formulation. Referring to the embodiment shown in Figure 3, if no optional α-olefin is added to reactor 11a(R1), the first ethylene interpolymer is an ethylene homopolymer. If an α-olefin is added, the following weight ratio is one parameter for controlling the density of the first ethylene interpolymer: ((α-olefin) / (ethylene)) R1 ((α-olefin) / (ethylene)) R1 The upper limit may be approximately 3, approximately 2 in other cases, and approximately 1 in yet other cases. ((α-olefin) / (ethylene)) R1 The lower limit may be 0, approximately 0.25 in other cases, and approximately 0.5 in yet other cases. Hereafter, the symbol "σ" will be used. 1 " refers to R1, which is the density of the first ethylene interpolymer produced in reactor 11a in Figure 3 or reactor 111a in Figure 4. σ 1 The upper limit may be 0.975 g / cc, 0.965 g / cc in some cases, and 0.955 g / cc in others. 1The lower limit may be 0.855 g / cc, 0.865 g / cc in some cases, and 0.875 g / cc in others. The density decreases as the content of one or more α-olefins in the first ethylene interpolymer increases. The α-olefin content is expressed as the molar percentage of α-olefins in the first ethylene interpolymer. The upper limit of the molar percentage of α-olefins (one or more) in the first ethylene interpolymer may be 25%, 23% in some cases, and 20% in others. The lower limit of the molar percentage of α-olefins in the first ethylene interpolymer is 0%, i.e., no α-olefins are added to the solution polymerization process, and the first ethylene interpolymer is an ethylene homopolymer.

[0162] CDBI of ethylene interpolymers 50 Methods for determining the Composition Distribution Branching Index (CDBI) are well known to those skilled in the art. 50 CDBI was defined as the percentage of ethylene interpolymer in which the comonomer (α-olefin) composition is no more than 50% of the central comonomer composition. 50 CDBI of α-olefin-containing ethylene interpolymer produced using heterogeneous catalyst formulations 50 It is also well known to those skilled in the art that it is higher than the first ethylene interpolymer. 50 The upper limit may be 98%, 95% in other cases, and 90% in yet other cases. CDBI of the first ethylene interpolymer 50 The lower limit may be 70%, 75% in other cases, and 80% in yet other cases.

[0163] M of the first ethylene interpolymer w / M n The upper limit may be 2.4, 2.3 in other cases, and 2.2 in yet other cases. M of the first ethylene interpolymer w / M n The lower limit may be 1.7, 1.8 in other cases, and 1.9 in yet other cases.

[0164] The first ethylene interpolymer contains long-chain branching characterized by a melt-flow-intrinsic viscosity index value (MFIVI), as well as fully explained above in (Equation 1). The upper limit of the MFIVI of the first ethylene interpolymer may be 0.8, otherwise 0.7, and still otherwise 0.6. The lower limit of the MFIVI of the first ethylene interpolymer is 0.05 or greater.

[0165] The first ethylene interpolymer has an unsaturated total SUM in the range of 0.005 to less than 0.047 unsaturated / 100C. U (Formula 7) is present. SUM of the first ethylene interpolymer U The upper limit of the value may be less than 0.047, less than 0.046 in other cases, and less than 0.045 in yet other cases for unsaturated / 100C. SUM of the first ethylene interpolymer U The lower limit of the value may be 0.0050 or higher, 0.007 or higher in other cases, and 0.010 or higher in yet other cases for unsaturated / 100C.

[0166] The first ethylene interpolymer contained a “residual catalyst metal” that reflected the chemical composition of the crosslinked metallocene catalyst compound injected into the first reactor. The residual catalyst metal was quantified by neutron activation analysis (NAA), i.e., parts per million (ppm) of the catalyst metal in the first ethylene interpolymer, and the catalyst metal originated from the metal in component A (formula (I)), which is “metal A R1 It is called "metal A". R1 Examples of which are not limited to include Group 4 metals, titanium, zirconium, and hafnium. In the case of an ethylene interpolymer product containing one interpolymer, namely a first ethylene interpolymer, the residual catalyst metal is ppm metal A in the ethylene interpolymer product. R1 It is equal to Metal A in the first ethylene interpolymer. R1The upper limit of ppm may be 5.0 ppm, 4.0 ppm in other cases, and 3.0 ppm in yet other cases. Metal A in the first ethylene interpolymer R1 The lower limit of ppm may be 0.03 ppm, 0.09 ppm in other cases, and 0.15 ppm in yet other cases.

[0167] The amount of hydrogen added to R1 is, in the continuous solution process, I2 thereafter. 1 The melt index, referred to as H2, can vary over a wide range, resulting in the production of different first ethylene interpolymers (the melt index is measured at 190°C using a 2.16 kg load, following the procedure outlined in ASTM D1238). This is achieved by adjusting the hydrogen flow rate in stream 4 (Figure 3) or stream 104 (Figure 4). The amount of hydrogen added to the reactor is expressed (for example) as parts per million (ppm) of hydrogen in R1 relative to the total mass in reactor R1, and hereafter referred to as H2 R1 It is referred to as (ppm). In some cases, H2 R1 (ppm) is in the range of 100 ppm to 0 ppm, 50 ppm to 0 ppm in other cases, 20 ppm to 0 ppm in alternative cases, and 2 ppm to 0 ppm in yet other cases. I2 1 The upper limit may be 200 dg / min, 100 dg / min in some cases, 50 dg / min in others, and 1 dg / min in yet other cases. I2 1 The lower limit may be 0.01 dg / min, 0.05 dg / min in some cases, 0.1 dg / min in others, and 0.5 dg / min in yet another case.

[0168] The upper limit of the wt.% of the first ethylene interpolymer in the ethylene interpolymer product may be 100 wt.%, 60 wt.% in some cases, 55 wt.% in others, and 50 wt.% in yet other cases. The lower limit of the wt.% of the first ethylene interpolymer in the ethylene interpolymer product may be 5 wt.%, 8 wt.% in others, and 10 wt.% in yet other cases.

[0169] Referring to Figure 4, the second ethylene interpolymer was synthesized by injecting a crosslinked metallocene catalyst formulation into the second solution polymerization reactor 112a (or R2). If no optional α-olefin was added to reactor 112a (R2) via a fresh α-olefin stream 108 or carried over from reactor 111a (R1) in stream 111e (series mode), the second ethylene interpolymer was an ethylene homopolymer. When α-olefin was present in R2, the following weight ratio was one parameter for controlling the density of the second ethylene interpolymer: ((α-olefin) / (ethylene)) R2 ((α-olefin) / (ethylene)) R2 The upper limit may be 3, 2 in other cases, and 1 in yet other cases. ((α-olefin) / (ethylene)) R2 The lower limit may be 0, 0.25 in other cases, and 0.5 in yet other cases. Hereafter, the symbol "σ" will be used. 2 " refers to the density of the second ethylene interpolymer. σ 2 The upper limit may be 0.975 g / cc, 0.965 g / cc in some cases, and 0.955 g / cc in others. 2 The lower limit may be 0.855 g / cc, 0.865 g / cc in some cases, and 0.875 g / cc in others. The upper limit of the molar percentage of one or more α-olefins in the second ethylene interpolymer may be 25%, 23% in some cases, and 20% in others. The lower limit of the molar percentage of α-olefins in the second ethylene interpolymer is 0%, i.e., no α-olefins are added to the solution polymerization process, and the second ethylene interpolymer is an ethylene homopolymer.

[0170] CDBI of the second ethylene interpolymer 50 The upper limit may be 98%, 95% in other cases, and 90% in yet other cases. CDBI of the second ethylene interpolymer 50 The lower limit may be 70%, 75% in other cases, and 80% in yet other cases.

[0171] M of the second ethylene interpolymer w / M n The upper limit may be 2.4, 2.3 in other cases, and 2.2 in yet other cases. M of the second ethylene interpolymer w / M n The lower limit may be 1.7, 1.8 in other cases, and 1.9 in yet other cases.

[0172] The second ethylene interpolymer contains long-chain branching characterized by a melt-flow-intrinsic viscosity index value (MFIVI), as well as fully explained above in (Equation 1). The upper limit of the MFIVI for the second ethylene interpolymer may be 0.8, 0.7 in other cases, and 0.6 in yet other cases. The lower limit of the MFIVI for the second ethylene interpolymer is 0.05 or greater.

[0173] The second ethylene interpolymer has an unsaturated total SUM in the range of 0.005 to less than 0.047 unsaturated / 100C. U (Formula 7) is present. SUM of the second ethylene interpolymer U The upper limit of the value may be less than 0.047 for unsaturated / 100C, less than 0.046 in other cases, and less than 0.045 in yet other cases. SUM of the second ethylene interpolymer U The lower limit of the value may be 0.0050 or higher, 0.007 or higher in other cases, and 0.010 or higher in yet other cases for unsaturated / 100C.

[0174] The catalyst residue in the second ethylene interpolymer reflects the amount of crosslinked metallocene catalyst compound used in R2 or the amount of component A used in R2. R2 The species of component A (formula (I)) containing " may be different from the species of component A used in the first reactor. In the case of a pure sample of the second ethylene interpolymer, metal A in the second ethylene interpolymer R2The upper limit of ppm may be 5.0 ppm, 4.0 ppm in other cases, and 3.0 ppm in yet other cases; on the other hand, metal A in the second ethylene interpolymer R2 The lower limit of ppm may be 0.03 ppm, 0.09 ppm in other cases, and 0.15 ppm in yet other cases.

[0175] Referring to the embodiment shown in Figure 4, the amount of hydrogen added to R2 is, in the continuous solution polymerization process, I2 2 The melt index, referred to as H2, can vary over a wide range, resulting in the production of a second ethylene interpolymer with a different melt index. This is achieved by adjusting the hydrogen flow rate in stream 109. The amount of hydrogen added is expressed as parts per million (ppm) of hydrogen in R2 relative to the total mass in reactor R2, and hereafter referred to as H2 R2 It is referred to as (ppm). In some cases, H2 R2 (ppm) ranges from 100 ppm to 0 ppm, in some cases from 50 ppm to 0 ppm, in other cases from 20 ppm to 0 ppm, and in yet other cases from 2 ppm to 0 ppm. 2 The upper limit may be 1000 dg / min, 750 dg / min in some cases, 500 dg / min in others, and 200 dg / min in yet other cases. I2 2 The lower limit may be 0.3 dg / min, 0.4 dg / min in some cases, 0.5 dg / min in others, and 0.6 dg / min in yet other cases.

[0176] The upper limit of the weight percentage (wt.%) of the second ethylene interpolymer in the ethylene interpolymer product may be 95 wt.%, 92 wt.%, or 90 wt.% in other cases. The lower limit of the wt.% of the second ethylene interpolymer in the ethylene interpolymer product may be 0 wt.%, 20 wt.%, 30 wt.%, or 40 wt.% in other cases.

[0177] Referring to Figure 3, a third ethylene interpolymer was produced in reactor 17. Referring to Figure 4, a third ethylene interpolymer was produced in reactor 117 when the catalyst deactivator was not added upstream of reactor 117. When α-olefin was not added, the third ethylene interpolymer was an ethylene homopolymer. When α-olefin was present in R3, the following weight ratio was one parameter that determined the density of the third ethylene interpolymer: ((α-olefin) / (ethylene)) R3 ((α-olefin) / (ethylene)) R3 The upper limit may be 3, 2 in other cases, and 1 in yet other cases. ((α-olefin) / (ethylene)) R3 The lower limit may be 0, 0.25 in other cases, and 0.5 in yet other cases. Hereafter, the symbol "σ" will be used. 3 This refers to the density of the third ethylene interpolymer. σ 3 The upper limit may be 0.975 g / cc, 0.965 g / cc in some cases, and 0.955 g / cc in others. 3 The lower limit may be 0.855 g / cc, 0.865 g / cc in some cases, and 0.875 g / cc in others. The upper limit of the molar percentage of one or more α-olefins in the third ethylene interpolymer may be 25%, 23% in some cases, and 20% in others. The lower limit of the molar percentage of α-olefins in the third ethylene interpolymer is 0%, i.e., no α-olefins are added to the solution polymerization process, and the third ethylene interpolymer is an ethylene homopolymer.

[0178] Referring to Figure 4, one or more of the following homogeneous catalyst formulations may be injected into R3: a crosslinked metallocene catalyst formulation, a non-crosslinked single-site catalyst formulation, or a homogeneous catalyst formulation containing a bulky ligand-metal complex that is not a member of the type defined by formula (I) or formula (II). Figure 4 shows the injection of a homogeneous catalyst formulation into reactor 117 via stream 140. The disclosure includes embodiments in which a heterogeneous catalyst formulation is injected into a third reactor (R3). In Figure 4, a heterogeneous catalyst assembly (streams 134a-134e and 134h) is used to generate and inject an online Ziegler-Natta catalyst formulation into reactor 117.

[0179] CDBI, the third ethylene interpolymer 50 The upper limit may be 98%, 95% in other cases, and 90% in yet other cases. CDBI of an optional third ethylene interpolymer 50 The lower limit may be 35%, 40% in other cases, and 45% in yet other cases.

[0180] The third ethylene interpolymer M w / M n The upper limit of Mw / Mn may be 5.0, 4.8 in other cases, and 4.5 in yet other cases. The lower limit of Mw / Mn for the optional third ethylene interpolymer may be 1.7, 1.8 in other cases, and 1.9 in yet other cases.

[0181] When a crosslinked metallocene catalyst compound is used in a third reactor to synthesize a third ethylene interpolymer, the third ethylene interpolymer has a melt-flow-intrinsic viscosity index value in the range of 0.05 to 0.80, characterized by long-chain branching as MFIVI (Equation 1), the upper limit of the MFIVI of the third ethylene interpolymer may be 0.8, 0.7 in other cases, or 0.6 in yet other cases, and the lower limit of the MFIVI of the third ethylene interpolymer is 0.05 or higher. Optionally, the third ethylene interpolymer may be synthesized using a catalyst formulation that does not generate long-chain branching (i.e., not a crosslinked metallocene catalyst formulation), in which case the upper limit of the MFIVI of the third ethylene interpolymer may be 0.05, 0.025 in other cases, or 0.0 in yet other cases, and the lower limit of the MFIVI of the third ethylene interpolymer may be -0.05, -0.025 in other cases, or 0.0 in yet other cases, i.e., undetectable levels of long-chain branching.

[0182] When a crosslinked metallocene catalyst compound is used in the third reactor to synthesize the third ethylene interpolymer, the third ethylene interpolymer has an unsaturated total sum in the range of 0.005 to less than 0.047. U Characterized by (Equation 7). SUM of the third ethylene interpolymer U The upper limit of the value may be less than 0.047, less than 0.046 in other cases, and less than 0.045 in yet other cases. SUM of the third ethylene interpolymer U The lower limit of the value may be 0.0050 or higher, 0.007 or higher in other cases, and 0.010 or higher in yet other cases. Optionally, the third ethylene interpolymer is the unsaturated sum of the third ethylene interpolymer in the range of 0.005 or higher and less than 0.047. U The synthesis may also be performed using alternative catalyst formulations (not cross-linked metallocene catalyst formulations) characterized by the above.

[0183] The catalyst residue in the third ethylene interpolymer reflects the catalyst used in its production. If a crosslinked metallocene catalyst compound is used, the "metal A" used in the third reactor will reflect the catalyst used in its production. R3 The type of component A (formula (I)) containing " may differ from the type used in R1, or R1 and R2. In other words, the catalyst metal used in R3 may differ from the catalyst metal used in R1 and / or R2. In the case of a pure sample of the third ethylene interpolymer, metal A in the third ethylene interpolymer R3 The upper limit of ppm may be 5.0 ppm, 4.0 ppm in other cases, and 3.0 ppm in yet other cases; on the other hand, metal A in the third ethylene interpolymer R3 The lower limit of ppm may be 0.03 ppm, 0.09 ppm in other cases, and 0.15 ppm in yet other cases.

[0184] The third ethylene interpolymer consists of component C and catalyst "metal C R3 It may also be synthesized using a non-crosslinked single-site catalyst formulation containing "metal C". R3 Examples that are not limited to these include Group 4 metals, titanium, zirconium, and hafnium. In the case of a pure sample of the third ethylene interpolymer, metal C in the third ethylene interpolymer. R3 The upper limit of ppm may be 3.0 ppm, 2.0 ppm in other cases, and 1.5 ppm in yet other cases. Metal C in the third ethylene interpolymer R3 The lower limit of ppm may be 0.03 ppm, 0.09 ppm in other cases, and 0.15 ppm in yet other cases.

[0185] The third ethylene interpolymer is a metal "B" that is not a member of the type defined by formula (I) or formula (II). R3 It may also be synthesized using a homogeneous catalyst formulation containing a bulky ligand-metal complex including ". Metal B R3 Examples of which are not limited include Group 4 metals, titanium, zirconium, and hafnium. In the case of a pure sample of the third ethylene interpolymer, metal B in the third ethylene interpolymer.R3 The upper limit of ppm may be 5.0 ppm, 4.0 ppm in other cases, and 3.0 ppm in yet other cases. Metal B in the third ethylene interpolymer R3 The lower limit of ppm may be 0.03 ppm, 0.09 ppm in other cases, and 0.15 ppm in yet other cases.

[0186] The third ethylene interpolymer may also be synthesized using a heterogeneous catalyst formulation, and Figure 4 shows an example, not limited to, inline Ziegler-Natta catalyst formulation injected into reactor 117. The inline Ziegler-Natta catalyst formulation contains a metal compound (component (vii)) and "metal Z R3 The term "metal" refers to the metal in this compound. R3 Examples that are not limited include metals selected from groups 4 through 8 of the periodic table. In the case of a pure sample of the third ethylene interpolymer, metal Z in the third ethylene interpolymer. R3 The upper limit of ppm may be 12 ppm, 10 ppm in other cases, and 8 ppm in yet other cases; on the other hand, metal Z in the third ethylene interpolymer R3 The lower limit of ppm may be 0.5 ppm, 1 ppm in other cases, and 3 ppm in yet other cases.

[0187] Referring to the embodiments shown in Figures 3 and 4, optional hydrogen can be injected into tubular reactors 17 or 117, respectively, via stream 16 or stream 116. The amount of hydrogen added to R3 can vary over a wide range. R3 By adjusting the amount of hydrogen in R3, referred to as (ppm), the continuous solution process is subsequently performed in I2 3 This can produce a third ethylene interpolymer with a wide range of melt indices, referred to as I2. The amount of optional hydrogen added to R3 is in the range of 100 ppm to 0 ppm, 50 ppm to 0 ppm in some cases, 20 ppm to 0 ppm in others, and 2 ppm to 0 ppm in yet another case. 3The upper limit may be 2000 dg / min, 1500 dg / min in some cases, 1000 dg / min in others, and 500 dg / min in yet other cases. I2 3 The lower limit may be 0.4 dg / min, 0.6 dg / min in some cases, 0.8 dg / min in others, and 1.0 dg / min in yet other cases.

[0188] The upper limit of the weight percentage (wt.%) of the optional third ethylene interpolymer in the ethylene interpolymer product may be 30 wt.%, 25 wt.%, or 20 wt.% in other cases. The lower limit of the wt.% of the optional third ethylene interpolymer in the ethylene interpolymer product may be 0 wt.%, 5 wt.%, or 10 wt.% in other cases.

[0189] Refer to the final ethylene interpolymer product of the Disclosure. Embodiments of the ethylene interpolymer product disclosed herein include at least two ethylene interpolymers synthesized using a crosslinked metallocene catalyst formulation. Additional embodiments of the ethylene interpolymer product include at least two ethylene interpolymers synthesized using a crosslinked metallocene catalyst formulation, and a third ethylene interpolymer, the third ethylene interpolymer which may be synthesized using any catalyst formulation from which an ethylene interpolymer can be produced, including, but not limited to, crosslinked metallocene catalysts, non-crosslinked single-site catalyst formulations, homogeneous catalyst formulations containing bulky ligand-metal complexes that are not members of the types defined by formula (I) or formula (II) of the Disclosure, or heterogeneous catalyst formulations, such as Ziegler-Natta catalyst formulations.

[0190] Density of ethylene interpolymer product (ρ fThe upper limit of the density of the ethylene interpolymer product may be 0.975 g / cc, 0.965 g / cc in some cases, and 0.955 g / cc in others. The lower limit of the density of the ethylene interpolymer product may be 0.855 g / cc, 0.865 g / cc in some cases, and 0.875 g / cc in others. The upper limit of the molar percentage of one or more α-olefins in the ethylene interpolymer product may be 25%, 23% in some cases, and 20% in others. The lower limit of the molar percentage of α-olefins in the ethylene interpolymer product is 0%, meaning that no α-olefins were added to the solution polymerization process, and the ethylene interpolymer product was an ethylene homopolymer.

[0191] CDBI of ethylene interpolymer products 50 The upper limit may be 98%, 90% in other cases, and 85% in yet other cases. If α-olefins are not added to the continuous solution polymerization process, 97% CDBI 50 An ethylene interpolymer product having the following characteristics may be formed, in which case the ethylene interpolymer product is an ethylene homopolymer. CDBI of the ethylene interpolymer product 50 The lower limit may be 1%, 2% in other cases, and 3% in yet other cases.

[0192] M of ethylene interpolymer products w / M n The upper and lower limits depend on the process conditions used. M of the ethylene interpolymer product w / M n The upper limit may be 25, 20 in other cases, and 15 in yet other cases; M of the ethylene interpolymer product w / M n The lower limit may be 1.8, 1.9 in other cases, and 2.0 in yet other cases.

[0193] The ethylene interpolymer products of this disclosure include long-chain branching characterized by a melt-flow intrinsic viscosity index (MFIVI) ​​(Equation 1) in the range of 0.05 to 0.80. The upper limit of the MFIVI of the ethylene interpolymer product may be 0.8, otherwise 0.7, and still otherwise 0.6. The lower limit of the MFIVI of the ethylene interpolymer product is 0.05 or greater.

[0194] The ethylene interpolymer product is the first derivative of the melt flow distribution function at a load of 4000g, having a value between -1.51 and -1.15.

number

number

number

number

[0195] The ethylene interpolymer products of this disclosure are unsaturated total SUM U Characterized by (Equation 7). The ethylene interpolymer product has a sum in the range of 0.005 to less than 0.047. U It has a value. SUM of ethylene interpolymer productsU The upper limit of the value may be less than 0.047, less than 0.046 in other cases, and less than 0.045 in yet other cases. SUM of ethylene interpolymer products U The lower limit of the value may be 0.0050 or higher, 0.007 or higher in other cases, and 0.010 or higher in yet other cases. Example 44 of the ethylene interpolymer product is SUM 0.036 unsaturated / 100C. U The values ​​are as follows: The five samples in Example 44 campaign (Examples 43-47) have an average SUM of 0.0366 ± 0.0015 unsaturated / 100C. U The values ​​and the 3-σ range of 0.032 to 0.041 unsaturated / 100C represented a normally distributed variable with 99.73 percent accuracy.

[0196] Figure 9 shows the first derivative (Equation 4) of the melt flow distribution function at a load of 4000g in Examples 43-47 compared to Q1-Q4, W1 and W2, and previously disclosed Examples 1 and 2:

number

number

number

number

[0197] Table 4 discloses the typical amount of residual catalyst metal (approximately 1.5 ± 0.3 ppm Hf) in the ethylene interpolymer product Examples 43–47 campaign, as determined by neutron activation analysis (NAA), as well as the amounts of residual catalyst metal in comparative and previously disclosed Examples 1 and 2. In Examples 43–47, the same crosslinked metallocene catalyst formulations were injected into reactors 111a and 112a (Figure 4). Comparatives Q1–Q4 were produced using Hf-based catalyst formulations and contained 0.24–0.34 ppm Hf and undetectable Ti. Comparatives 2 and 3 were produced using Hf-based catalyst formulations in the first reactor and Ti-based catalyst formulations in the second reactor. The remaining comparatives in Table 4 were produced with various Ti-based catalyst formulations, namely comparatives R, S, U, V, 1, 4, and 5, with Ti content ranging from 0.14–7.14 ppm Ti.

[0198] In embodiments in which the same type of component A is used in two reactors, the upper limit of residual catalyst metal in the ethylene interpolymer product may be 5.0 ppm, 4.0 ppm in other cases, or 3.0 ppm in yet other cases, and the lower limit of residual catalyst metal in the ethylene interpolymer product may be 0.03 ppm, 0.09 ppm in other cases, or 0.15 ppm in yet other cases.

[0199] Three reactors are in operation, and each reactor contains a different type of component A (containing different metals), for example A R1 , A R1 , and A R1 In embodiments in which this is used, metal A in the ethylene interpolymer product R1 The upper limit of ppm may be 3.0 ppm, 2.5 ppm in other cases, and 2.0 ppm in yet other cases, while metal A in ethylene interpolymer productsR1 The lower limit of ppm may be 0.0015 ppm, 0.005 ppm in other cases, and 0.01 ppm in yet other cases, and metal A in ethylene interpolymer products. R2 The upper limit of ppm may be 5.0 ppm, 4.0 ppm in other cases, and 3.0 ppm in yet other cases, while metal A in ethylene interpolymer products R2 The lower limit of ppm may be 0.003 ppm, 0.01 ppm in other cases, and 0.015 ppm in yet other cases, and metal A in ethylene interpolymer products. R3 The upper limit of ppm for is 1.5 ppm, in other cases it may be 1.25 ppm, and in yet other cases it may be 1.0 ppm, on the other hand, metal A R3 The lower limit of ppm may be 0 ppm.

[0200] metal C R3 In embodiments in which a non-crosslinked single-site catalyst formulation containing metal C in the ethylene interpolymer product is injected into a tubular reactor, R3 The upper limit of ppm may be 1.0 ppm, 0.8 ppm in other cases, and 0.5 ppm in yet other cases. Metal B R3 In embodiments in which a homogeneous catalyst formulation containing metal B in the ethylene interpolymer product is injected into a tubular reactor, R3 The upper limit of ppm may be 1.5 ppm, 1.25 ppm in other cases, and 1.0 ppm in yet other cases. Metal Z R3 In embodiments in which a heterogeneous catalyst formulation containing metal Z is injected into a tubular reactor, the ethylene interpolymer product contains metal Z R3 The upper limit of ppm may be 3.5 ppm, 3 ppm in other cases, and 2.5 ppm in yet other cases. Metal A in ethylene interpolymer products R3 , C R3 B R3 or Z R3 The lower limit of ppm was 0.0.

[0201] The upper limit of the melt index of the ethylene interpolymer product may be 500 dg / min, 400 dg / min in some cases, 300 dg / min in others, and 200 dg / min in yet other cases. The lower limit of the melt index of the ethylene interpolymer product may be 0.3 dg / min, 0.4 dg / min in some cases, 0.5 dg / min in others, and 0.6 dg / min in yet other cases.

[0202] manufactured goods The ethylene interpolymer products disclosed herein can be converted into flexible products such as single-layer or multi-layer films. Examples of processes for preparing such films, not limited to these, include blow film processes, double-bubble processes, triple-bubble processes, cast film processes, tenter-frame processes, and flow direction orientation (MDO) processes.

[0203] In the blow film extrusion process, an extruder heats, melts, mixes, and transports a thermoplastic material or thermoplastic blend. Once melted, the thermoplastic material is pushed through an annular die to produce a thermoplastic tube. In co-extrusion, multiple extruders are used to produce a multi-layer thermoplastic tube. The temperature of the extrusion process is determined primarily by the thermoplastic material or thermoplastic blend being processed, for example, by the melting point or glass transition temperature of the thermoplastic material and the desired viscosity of the molten material. For polyolefins, a typical extrusion temperature is 330°F to 550°F (166°C to 288°C). After exiting the annular die, the thermoplastic tube is inflated with air, cooled, solidified, and drawn through a pair of nip rollers. Due to the air expansion, the diameter of the tube increases, forming a bubble of the desired size. Due to the drawing action of the nip rollers, the bubble is stretched in the flow direction. Thus, the bubble is stretched in two directions: the width direction (TD) where the expanding air increases the diameter of the bubble, and the flow direction (MD) where the nip rollers stretch the bubble. As a result, the properties of the blown film are typically anisotropic, meaning that the properties differ in the MD and TD directions, for example, the tear strength and tensile properties of the film typically differ in the MD and TD directions. In some prior art documents, the terms “transverse direction” or “CD” are used, but these terms are equivalent to the terms “width direction” or “TD” used in this disclosure. In the blown film process, air is also blown onto the periphery of the external bubble to cool the thermoplastic material as it exits the annular die. The final width of the film is determined by controlling the expanding air or internal bubble pressure, in other words, by increasing or decreasing the bubble diameter. The film thickness is controlled primarily by increasing or decreasing the speed of the nip roller to control the downward speed. After exiting the nip roller, the bubble or tube may deflate and be cut in the flow direction to form a sheet. Each sheet may be wound onto a roll of film. Each roll may be further cut to form a film of a desired width. Each roll of film may be further processed into various consumer products, as described below.

[0204] The cast film process is similar in that one or more extruders may be used, but various thermoplastic materials are weighed into a flat die and extruded into single or multilayer sheets instead of tubes. In the cast film process, the extruded sheets are solidified on cooling rolls.

[0205] In a double-bubble process, a first blown film bubble is formed and cooled, then the first bubble is heated and re-expanded to form a second blown film bubble, which is then cooled. The ethylene interpolymer products disclosed herein are also suitable for a triple-bubble blow process. Further film conversion processes suitable for the disclosed ethylene interpolymer products include processes that include a flow direction orientation (MDO) step, for example, a process that includes blowing or casting a film, quenching the film, and then subjecting a film tube or film sheet to an MDO process at any stretch ratio. Furthermore, the ethylene interpolymer product films disclosed herein are suitable for use in tenter-frame processes and other processes that introduce biaxial orientation.

[0206] Depending on the end use, the disclosed ethylene interpolymer products can be converted into films of a wide range of thicknesses. Examples, not limited to these, include food packaging films that may have thicknesses ranging from 0.5 mil (13 μm) to 4 mil (102 μm), and heavy-duty bags that may have film thicknesses ranging from 2 mil (51 μm) to 10 mil (254 μm).

[0207] The single layer in the single-layer film may contain two or more ethylene interpolymer products and / or one or more additional polymers, the additional polymers including, but not limited to, ethylene polymers and propylene polymers. The lower limit of the weight percentage of ethylene interpolymer products in the single-layer film may be 3 wt.%, otherwise 10 wt.%, and still otherwise 30 wt.%. The upper limit of the weight percentage of ethylene interpolymer products in the single-layer film may be 100 wt.%, otherwise 90 wt.%, and still otherwise 70 wt.%.

[0208] The ethylene interpolymer products disclosed herein may also be used in one or more layers of a multilayer film, and examples of multilayer films, not limited to those with 3, 5, 7, 9, 11 or more layers. The disclosed ethylene interpolymer products are also suitable for use in processes using micro-laminated dies and / or feed blocks, such processes can produce films with many layers, including, not limited to, 10 to 10,000 layers.

[0209] The thickness of a particular layer (containing ethylene interpolymer products) within the multilayer film may be 5% of the total multilayer film thickness, 15% in other cases, or 30% in yet other cases. In other embodiments, the thickness of a particular layer (containing ethylene interpolymer products) within the multilayer film may be 95% of the total multilayer film thickness, 80% in other cases, or 65% in yet other cases. Each individual layer of the multilayer film may contain two or more ethylene interpolymer products and / or additional thermoplastics.

[0210] Additional embodiments include lamination and coating, in which a single-layer or multilayer film containing the disclosed ethylene interpolymer product is subjected to extrusion lamination, adhesive lamination, or extrusion coating. In extrusion lamination or adhesive lamination, two or more substrates are joined to each other with a thermoplastic or adhesive. In extrusion coating, a thermoplastic is applied to the surface of the substrate. These processes are well known to those skilled in the art. Often, adhesive lamination or extrusion lamination is used to join dissimilar materials, including, but not limited to, the joining of a paper web to a thermoplastic web, or an aluminum foil-containing web to a thermoplastic web, or the joining of two chemically incompatible thermoplastic webs, such as the joining of an ethylene interpolymer product-containing web to a polyester or polyamide web. Prior to lamination, the web containing the disclosed ethylene interpolymer product(s) may be single-layer or multilayer. Prior to lamination, individual webs may be surface-treated to improve the bond, and an example of such surface treatment is corona treatment. A primary web or film may be laminated to an upper surface, a lower surface, or both the upper and lower surfaces having a secondary web. Secondary and tertiary webs may be laminated to the primary web, and the secondary and tertiary webs may have different chemical compositions. In examples that are not limited, the secondary or tertiary web may include a web containing a barrier resin layer such as polyamide, polyester and polypropylene, or EVOH. Such a web may also include a vapor-deposited barrier layer, such as silicon dioxide (SiO₂). x ) or aluminum oxide (AlO x ) may include thin layers. A multilayer web (or film) may contain 3, 5, 7, 9, 11 or more layers.

[0211] The ethylene interpolymer products disclosed herein may be used in a wide range of products comprising one or more films (single-layer or multi-layer). Examples of such products, not limited to these, include food packaging films (for fresh and frozen foods, liquids, and granular foods), self-standing pouches, retort packaging, and bag-in-box packaging; barrier films (for oxygen, moisture, aroma, oil, etc.) and controlled atmosphere packaging; simple and robust shrink films and wraps, collation shrink films, pallet shrink films, shrink bags, shrink bundling, and shrink shrouds; simple and robust stretch films, hand stretch wraps, machine stretch wraps, and stretch hood films. film; high transparency film; heavy-duty bags; household wrap, overlap film and sandwich bags; industrial and facility films, garbage bags, can liners, magazine overlap, newspaper bags, mailbags, large bags and envelopes, bubble wrap, carpet film, furniture bags, clothing bags, coin bags, automotive panel films; medical applications such as gowns, draping and surgical gowns; architectural films and sheets, asphalt films, insulation bags, masking films, landscaping films and bags; geomembrane liners for municipal waste treatment and mining applications; batch inclusion bags; agricultural films, mulch films and greenhouse films; in-store packaging, self-service bags, clothing store bags, shopping bags, take-out bags and T-shirt bags; including functional film layers in oriented films, flow direction orientation (MDO) films, biaxial orientation films and oriented polypropylene (OPP) films, such as sealants and / or toughening layers. Additional products comprising one or more films containing at least one ethylene interpolymer product include laminates and / or multilayer films; sealants and tie layers in multilayer films and composites; laminations with paper; aluminum foil laminates or laminates containing vacuum-deposited aluminum; polyamide laminates; polyester laminates; extruded coating laminates; and hot-melt adhesive formulations.The products summarized in this paragraph include at least one film (monolayer or multilayer) comprising at least one embodiment of the disclosed ethylene interpolymer product.

[0212] The desired film properties (single-layer or multi-layer) typically depend on the intended application. Examples of desirable film properties, though not limited to specifics, include optical properties (gloss, haze, and clarity), darting impact resistance, Elmendorf tear strength, modulus of elasticity (1% and 2% secant moduli), tensile properties (yield strength, breaking strength, elongation at break, toughness, etc.), and heat-seal properties (heat-seal initiation temperature, SIT, and hot tack). In high-speed vertical and horizontal bag-making and filling processes for loading and sealing commercially available products (liquids, solids, pastes, parts, etc.) into pouch-like packaging, specific hot tack and heat-seal properties are desirable.

[0213] In addition to the desired film properties, it is desirable that the disclosed ethylene interpolymer product is easily processable on a film line. Those skilled in the art often use the term "processability" to distinguish polymers with improved processability from those with lower processability. The evaluation criterion commonly used to quantify processability is extrusion pressure, and more specifically, polymers with improved processability have lower extrusion pressures (on a blow film or cast film extrusion line) compared to polymers with lower processability.

[0214] The ethylene interpolymer products disclosed herein have improved bubble stability compared to, for example, the product of Comparative 1 disclosed herein. This improved bubble stability allows for the production of single-layer or multi-layer films at higher production rates. Melt strength, measured in centinewtons (cN), is often used as a criterion for evaluating bubble stability; that is, higher melt strength indicates higher bubble stability.

[0215] The films used in the products described in this section may optionally contain additives and adjuvants depending on their intended use. Examples of additives and adjuvants, not limited to them, include antiblocking agents, antioxidants, heat stabilizers, slip agents, processing aids, antistatic additives, colorants, dyes, fillers, light stabilizers, light absorbers, lubricants, pigments, plasticizers, nucleating agents, and combinations thereof.

[0216] The processes disclosed herein can also produce ethylene interpolymer products having a useful combination of desired physical properties for use in rigid applications or rigid articles. Examples of rigid articles, not limited to these, include: food containers, margarine tub containers, beverage cups and agricultural product trays; household and industrial containers, cups, bottles, pails, crates, tanks, drums, bumpers, lids, industrial bulk containers, industrial tanks, material handling containers, bottle cap liners, bottle caps, integrated hinge closures; toys, playground equipment, amusement equipment, boats, marine and security equipment; wire and cable applications, e.g., power cables, communication cables and conduits; flexible tubes and hoses; pipe applications, including both pressure pipe and non-pressure pipe markets, e.g., natural gas distribution, water mains, indoor plumbing, storm drains, sewer pipes, corrugated pipes and conduits; foam articles manufactured from foam sheets or vanfoam; military packaging (equipment and instant food); personal care packaging, diapers and hygiene products; cosmetic, pharmaceutical and medical packaging; and truck bed liners, pallets and automotive linings. The rigid products summarized in this paragraph include one or more of the ethylene interpolymer products disclosed herein, or a blend of at least one of the ethylene interpolymer products disclosed herein with at least one other thermoplastic material.

[0217] Such rigid products may be manufactured using the following, but not limited to, processes: injection molding, compression molding, blow molding, rotational molding, shape extrusion, pipe extrusion, sheet thermoforming, and foaming processes using chemical or physical foaming agents.

[0218] The desired properties of a rigid manufactured product depend on the intended application. Examples of desired properties, though not limited to specific ones, include: flexural modulus (1% and 2% secant modulus); tensile toughness; environmental stress crack resistance (ESCR); slow crack growth resistance (PENT); abrasion resistance; Shore hardness; temperature of deflection under load; VICAT softening point; IZOD impact strength; ARM impact resistance; Charpy impact resistance; and color (whiteness and / or yellowness).

[0219] The rigid products described in this section may optionally contain additives and adjuvants depending on their intended use. Examples of additives and adjuvants, not limited to them, include antioxidants, slip agents, processing aids, antistatic additives, colorants, dyes, fillers, heat stabilizers, light stabilizers, light absorbers, lubricants, pigments, plasticizers, nucleating agents, and combinations thereof.

[0220] Description of the Embodiment The following paragraphs disclose embodiments of the disclosed ethylene interpolymer products.

[0221] An ethylene interpolymer product comprising at least two types of ethylene interpolymers, a) Dimensionless melt flow intrinsic viscosity index (MFIVI) ​​between 0.05 and 0.80, as defined by Equation 1.

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[0222] Embodiments of ethylene interpolymer products include (i) an ethylene interpolymer product comprising first and second ethylene interpolymers produced using a crosslinked metallocene catalyst; or (ii) an ethylene interpolymer product comprising first and third ethylene interpolymers produced using a crosslinked metallocene catalyst formulation; or (iii) an ethylene interpolymer product comprising first and second ethylene interpolymers produced using a crosslinked metallocene catalyst, and a third ethylene interpolymer produced using a homogeneous or heterogeneous catalyst formulation. The disclosed ethylene interpolymer product may include 5 to 60 weight percent of a first ethylene interpolymer having a melt index of 0.01 to 200 dg / min and a density of 0.855 g / cc to 0.975 g / cc; 20 to 95 weight percent of a second ethylene interpolymer having a melt index of 0.3 to 1000 dg / min and a density of 0.855 g / cc to 0.975 g / cc; and optionally, 0 to 30 weight percent of a third ethylene interpolymer having a melt index of 0.5 to 2000 dg / min and a density of 0.855 g / cc to 0.975 g / cc, where the weight percentage is obtained by dividing the weight of the first, second, or the optional third ethylene interpolymer by the weight of the ethylene interpolymer product, respectively. The disclosed embodiments of ethylene interpolymer products have a melt index of about 0.3 to about 500 dg / min, a density of about 0.855 to about 0.975 g / cc, and a molecular weight of about 1.7 to about 25 M w / M n and approximately 1% to approximately 98% of CDBI 50 The ethylene interpolymer product may contain 0 to about 25 mole percent of one or more α-olefins, and not limited examples of α-olefins include C3 to C3. 10 The disclosed ethylene interpolymer products may be produced in a solution polymerization process using one or more reactors. An embodiment of the crosslinked metallocene catalyst formulation is given by formula (I): [ka] It contains component A as defined by the formula, where M is a metal selected from titanium, hafnium, and zirconium; G is the element carbon, silicon, germanium, tin, or lead; X represents a halogen atom, and R6 groups are independently hydrogen atoms, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy group or C 6~10 Selected from aryloxide groups, these groups may be linear, branched, or cyclic, or they may be halogen atoms, C 1~10 Alkyl alkyl group, C 1~10 Alkoxy group, C 6~10 It may be further substituted with an aryl or aryloxy group; R1 is a hydrogen atom, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy group, or C 6~10 Represents an aryl oxide group; R2 and R3 are independently hydrogen atoms, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy group or C 6~10 Selected from aryl oxide groups; R4 and R5 are independently hydrogen atoms, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy group or C 6~10 An aryl oxide group, or at least one silicon atom and C 3~30 The crosslinked metallocene catalyst formulation is selected from alkylsilyl groups containing carbon atoms. The crosslinked metallocene catalyst formulation may further contain component M containing an almoxane cocatalyst; component B containing a boron ionic activator; and optionally component P containing a hindered phenol.

[0223] The types of formula (I) and (Ia) may be used to synthesize a first ethylene interpolymer, and the types of formula (I) and (Ib) may be used to synthesize a second or third ethylene interpolymer, and the types of (Ia) and (Ib) may be the same or different.

[0224] The third ethylene interpolymer may be synthesized using a homogeneous or heterogeneous catalyst formulation, with examples of homogeneous catalyst formulations including crosslinked metallocene catalyst formulations or non-crosslinked single-site catalyst formulations, and examples of heterogeneous catalyst formulations including in-line Ziegler-Natta catalyst formulations or batch Ziegler-Natta catalyst formulations.

[0225] Other embodiments include: i) injecting ethylene, a process solvent, a crosslinked metallocene catalyst compound, optionally one or more α-olefins and optionally hydrogen into a first reactor to generate a first outlet stream containing a first ethylene interpolymer in the process solvent; ii) passing the first outlet stream through a second reactor and injecting ethylene, the process solvent, the crosslinked metallocene catalyst compound, optionally one or more α-olefins and optionally hydrogen into the second reactor to generate a second outlet stream containing a second ethylene interpolymer and the first ethylene interpolymer in the process solvent; iii) passing the second outlet stream through a third reactor; The continuous solution polymerization process comprises: (a) optionally injecting ethylene, a process solvent, one or more α-olefins, hydrogen, and a homogeneous or heterogeneous catalyst formulation into the third reactor to generate a third outlet stream containing a third ethylene interpolymer, a second ethylene interpolymer, and a first ethylene interpolymer in the process solvent; and (iv) phase-separating the third outlet stream to recover an ethylene interpolymer product containing the first ethylene interpolymer, a second ethylene interpolymer, and the optional third ethylene interpolymer, wherein the continuous solution polymerization process is improved by having (a) and / or (b): (a) A reduction of at least 70% in the weight ratio of [α-olefin / ethylene] as defined by the following formula

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[0226] Other embodiments include: i) injecting ethylene, a process solvent, a crosslinked metallocene catalyst compound, optionally one or more α-olefins, and optionally hydrogen into a first reactor to generate a first outlet stream containing a first ethylene interpolymer in the process solvent; ii) injecting ethylene, the process solvent, the crosslinked metallocene catalyst compound, optionally one or more α-olefins, and optionally hydrogen into a second reactor to generate a second outlet stream containing a second ethylene interpolymer in the process solvent; iii) combining the first and second outlet streams to form a third outlet stream; and iv) passing the third outlet stream through a third reactor, optionally, The continuous solution polymerization process comprises: v) injecting ethylene, a process solvent, one or more α-olefins, hydrogen, and a homogeneous or heterogeneous catalyst formulation into the third reactor to generate a fourth outlet stream containing an optional third ethylene interpolymer in the process solvent, the second ethylene interpolymer, and the first ethylene interpolymer; v) phase-separating the fourth outlet stream to recover an ethylene interpolymer product containing the first ethylene interpolymer, the second ethylene interpolymer, and the optional third ethylene interpolymer, wherein the continuous solution polymerization process is improved by having one or more of the following, namely (a) and / or (b): (a) A reduction of at least 70% in the weight ratio of [α-olefin / ethylene] as defined by the following formula

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[0227] Additional steps of this process may include: a) optionally adding catalyst deactivator A to the third outlet stream downstream of the second reactor to form inactivation solution A; b) adding catalyst deactivator B to the fourth outlet stream downstream of the third reactor to form inactivation solution B (wherein step b) is skipped if catalyst deactivator A is added in step a); c) phase-separating the inactivation solutions A or B to recover the ethylene interpolymer product. If a heterogeneous catalyst formulation is added to the third reactor, additional process steps may include: d) adding a passivator to the inactivation solutions A or B to form a passivation solution (wherein step d) is skipped if the heterogeneous catalyst formulation is not added to the third reactor); and e) phase-separating the inactivation solutions A or B, or the passivation solution, to recover the ethylene interpolymer product. Ethylene interpolymer products can be produced using embodiments of the solution polymerization process disclosed in this paragraph.

[0228] An additional embodiment of the present disclosure is Embodiment F, which includes a film comprising at least one layer containing an ethylene interpolymer product comprising at least two ethylene interpolymers, wherein the ethylene interpolymer product comprises a to d below: a) Dimensionless melt flow intrinsic viscosity index (MFIVI) ​​between 0.05 and 0.80, as defined by Equation 1.

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[0229] In Embodiment F, the ethylene interpolymer product comprises a first ethylene interpolymer, a second ethylene interpolymer, and optionally a third ethylene interpolymer, wherein the first and second ethylene interpolymers or the first and third ethylene interpolymers are synthesized using a crosslinked metallocene catalyst formulation containing component A as defined by formula (I): [ka] During the ceremony, M is Ti, Hf, or Zr; G is C, Si, Ge, Sn, or Pb; X is a halogen atom; Each time R6 appears, H and C appear independently. 1~20 Hydrocarbyl group, C1~20 Alkoxy group, or C 6~10 Selected from aryloxide groups, these groups may be linear, branched, or cyclic, or they may be halogen atoms, C 1~10 Alkyl alkyl group, C 1~10 Alkoxy group, C 6~10 It may also be further substituted with an aryl or aryloxy group; R1 is H, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy group, C 6~10 An aryl oxide group, or at least one silicon atom and C 3~30 It is an alkylsilyl group containing a carbon atom; R2 and R3 are independently H, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy group, C 6~10 An aryl oxide group, or at least one silicon atom and C 3~30 Selected from alkylsilyl groups containing carbon atoms; R4 and R5 are independently H, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy group, C 6~10 An aryl oxide group, or at least one silicon atom and C 3~30 Selected from alkylsilyl groups containing carbon atoms, The types of formula (I) and (Ia) are used to synthesize the first ethylene interpolymer, and the types of formula (I) and (Ib) are used to synthesize the second or third ethylene interpolymer, and the types of (Ia) and (Ib) may be the same or different.

[0230] The film of embodiment F is a) Film gloss at 45° that is 10% to 30% higher than a comparative film of the same composition, except that the first and second ethylene interpolymers, or the first and third ethylene interpolymers, are replaced with a comparative ethylene interpolymer; b) 30% to 50% lower film haze compared to the comparison film. It may be characterized by one or more of the following: Comparative ethylene interpolymers are synthesized by replacing the crosslinked metallocene catalyst formulations used to produce the first and second ethylene interpolymers, or the first and third ethylene interpolymers, with non-crosslinked single-site catalyst formulations.

[0231] The ethylene interpolymer product in Embodiment F may be characterized by a melt index of 0.3 to 500 dg / min, a density of 0.855 to 0.975 g / cc, and an α-olefin content of 0 to 25 mole percent, with preferred α-olefins being C3 to C3. 10 The ethylene interpolymer product comprises α-olefins, or a blend of α-olefins such as 1-hexene and 1-octene, and has a polydisperse M of 1.7 to 25. w / M n , and 1% to 98% of CDBI 50 Embodiment F may include at least one layer further comprising at least one second polymer, the preferred second polymer being an ethylene polymer, such as an ethylene polymer or a propylene polymer, or a mixture thereof. The film of Embodiment F may have a thickness of 0.5 mil to 10 mil. The film of Embodiment F may comprise 2 to 11 layers, at least one of which comprises the ethylene interpolymer product.

[0232] Test method Prior to testing, each test specimen was conditioned at 23±2°C and 50±10% relative humidity for at least 24 hours, and then tested at 23±2°C and 50±10% relative humidity. Here, the term "ASTM conditions" refers to a laboratory maintained at 23±2°C and 50±10% relative humidity, where the test specimens were conditioned for at least 24 hours prior to testing. ASTM refers to the American Society for Testing and Materials.

[0233] density The density of the ethylene interpolymer product was determined using ASTM D792-13 (November 1, 2013).

[0234] Melt Index The melt index of the ethylene interpolymer product was determined using ASTM D1238 (August 1, 2013). Using weights of 2.16 kg, 6.48 kg, 10 kg, and 21.6 kg, the melt indices were I2, I6, and I2, respectively. 10 and I 21 It was measured at 190°C. Here, the term "stress index" or its abbreviation "S.Ex" is used. S.Ex.=log(I6 / I2) / log(6480 / 2160) It is defined by the relationship, where I6 and I2 are the melt flow rates measured at 190°C using loads of 6.48 kg and 2.16 kg, respectively.

[0235] Conventional size exclusion chromatography (SEC) A polymer solution (1-3 mg / mL) was prepared by heating an ethylene interpolymer product sample (polymer) in 1,2,4-trichlorobenzene (TCB) and rotating it on a wheel in a furnace at 150°C for 4 hours. To stabilize the polymer against oxidative degradation, an antioxidant (2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture. The BHT concentration was 250 ppm. The polymer solution was chromatographically treated at 140°C using a PL220 high-temperature chromatography unit equipped with four SHODEX® columns (HT803, HT804, HT805, and HT806) with TCB as the mobile phase at a flow rate of 1.0 mL / min, and a differential refractive index (DRI) was used as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect the SEC column from oxidative degradation. The sample injection volume was 200 μL. The SEC column was calibrated with a narrow-distribution polystyrene standard. As described in ASTM Standard Test Method D6474-12 (December 2012), polystyrene molecular weight was converted to polyethylene molecular weight using the Mark-Houwink formula. SEC raw data was processed with Cirrus GPC software, and the molar mass average (M) was calculated. n M w Mz ) and molar mass distribution (e.g., polydisperse M w / M n ) was produced. In the field of polyethylene technology, the commonly used equivalent term to SEC is GPC, or gel permeation chromatography.

[0236] Triple detection size exclusion chromatography (3D-SEC) A polymer solution (1-3 mg / mL) was prepared by heating an ethylene interpolymer product sample (polymer) in 1,2,4-trichlorobenzene (TCB) and rotating it on a wheel at 150°C for 4 hours in a furnace. To stabilize the polymer against oxidative degradation, an antioxidant (2,6-di-tert-butyl-4-methylphenol (BHT)) was added to the mixture. The BHT concentration was 250 ppm. The sample solution was chromatographically treated at 140°C in a PL220 high-temperature chromatography unit equipped with a differential refractive index (DRI) detector, a dual-angle light scattering detector (15° and 90°), and a differential viscometer. The intrinsic viscosity IV in Equation 1 (above) could be determined from the signal obtained from the latter. The SEC columns used were either four SHODEX columns (HT803, HT804, HT805, and HT806) or four PL mixed ALS or BLS columns. TCB was the mobile phase at a flow rate of 1.0 mL / min, and BHT was added to the mobile phase at a concentration of 250 ppm to protect the SEC column from oxidative degradation. The sample injection volume was 200 μL. Raw SEC data was processed with CIRRUS® GPC software to generate absolute molar mass and intrinsic viscosity ([η]). The term "absolute" molar mass was used to distinguish the absolute molar mass determined by 3D-SEC from the molar mass determined by conventional SEC. Viscosity-average molar mass M determined by 3D-SEC v We used Equation 1 (above) to determine MFIVI (Equation 1).

[0237] GPC-FTIR Polymer solutions (2-4 mg / mL) were prepared by heating ethylene interpolymer products (polymers) in 1,2,4-trichlorobenzene (TCB) and rotating them on a wheel in a furnace at 150°C for 4 hours. To stabilize the polymer against oxidative degradation, the antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture. The BHT concentration was 250 ppm. The sample solution was chromatographically treated at 140°C using a Waters GPC 150C chromatography unit equipped with four SHODEX columns (HT803, HT804, HT805, and HT806) with TCB as the mobile phase at a flow rate of 1.0 mL / min. An FTIR spectrometer and a heated FTIR flow-through cell connected to the chromatography unit via a heated transfer line were used as the detection system. BHT was added to the mobile phase at a concentration of 250 ppm to protect the SEC column from oxidative degradation. The sample injection volume was 300 μL. Raw FTIR spectra were processed with OPUS FTIR software, and polymer concentrations and methyl content were calculated in real time using OPUS-associated Chemometric Software (PLS technology). Polymer concentrations and methyl content were then obtained and baseline-corrected using CIRRUS GPC software. SEC columns were calibrated with narrow-distribution polystyrene standards. Polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink formula, as described in ASTM standard test method D6474. Comonomer content was calculated based on the polymer concentrations and methyl content predicted by PLS technology, as described in Paul J. DesLauriers, Polymer 43, pp. 159–170 (2002), incorporated herein by reference.

[0238] The GPC-FTIR method measures the total methyl content, which includes methyl groups located at the ends of each polymer chain, i.e., methyl-terminated groups. Therefore, raw GPC-FTIR data must be corrected by subtracting the contribution from methyl-terminated groups. More specifically, raw GPC-FTIR data overestimates the amount of short-chain branching (SCB), and this overestimation increases as the molecular weight (M) decreases. In this disclosure, raw GPC-FTIR data were corrected using a 2-methyl correction. At a given molecular weight (M), the number of methyl-terminated groups (N) is calculated. E ) is, formula: N E =Calculated using 28000 / M, N E The (M-dependency) was subtracted from the raw GPC-FTIR data to generate SCB / 1000C (2-methyl corrected) GPC-FTIR data.

[0239] Compositional Distribution Branching Index (CDBI) The “composition distribution branching index,” hereafter referred to as CDBI, for the disclosed examples and comparative examples was measured using a CRYSTAF / TREF 200+ unit equipped with an IR detector, hereafter referred to as CTREF. The acronym “TREF” stands for temperature-induced elution fractionation. The CTREF was supplied by PolymerChar SA (Valencia Technology Park, Gustave Eiffel, 8, Paterna, E-46980 Valencia, Spain). The CTREF operated in TREF mode, which measured the elution temperature, Co / Ho ratio (copolymer / homopolymer ratio), and CDBI (composition distribution width index), i.e., CDBI 50 and CDBI 25The chemical composition of the polymer sample was generated as a function of . A polymer sample (80-100 mg) was placed in a CTREF reaction vessel. 35 ml of 1,2,4-trichlorobenzene (TCB) was packed into the reaction vessel, and the polymer was dissolved by heating the solution at 150°C for 2 hours. Then, an aliquot (1.5 mL) of the solution was added to a CTREF column packed with stainless steel beads. The column containing the sample was stabilized at 110°C for 45 minutes. The polymer was then crystallized from the solution in the column by lowering the temperature to 30°C at a cooling rate of 0.09°C / min. The column was then equilibrated at 30°C for 30 minutes. The crystallized polymer was then eluted from the column by gradually heating the column from 30°C to 120°C at a heating rate of 0.25°C / min while flowing TCB through the column at a rate of 0.75 mL / min. Raw CTREF data was processed using Polymer Char software, an Excel spreadsheet, and proprietary CTREF software. CDBI 50 It is defined as the percentage of polymers whose composition is within 50% of the central comonomer (α-olefin) composition, and is included in the CDBI. 50 This was calculated from the composition distribution curve and the normalized cumulative integral of the composition distribution curve, as described in U.S. Patent No. 5,376,439. Those skilled in the art will understand that a calibration curve is necessary to convert the CTREF elution temperature to the comonomer content, i.e., the amount of comonomer in the ethylene / α-olefin polymer fraction that elutes at a specific temperature. The generation of such a calibration curve is described in the prior art, for example, Wild et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20(3), pp. 441-455, which is incorporated herein by reference in its entirety. CDBI 25 Similarly, CDBI is calculated. 25This is defined as the percentage of polymer whose composition is within 25% of the central comonomer composition. At the end of each sample analysis, the CTREF column was cleaned for 30 minutes, specifically by running TCB through the column for 30 minutes (0.75 mL / min) at a CTREF column temperature of 160°C. CTREF deconvolution was performed, and the branching amount (BrF(#C6 / 1000C)) and density of the first ethylene interpolymer were determined using the following formula: BrF(#C6 / 1000C) = 74.29 - 0.7598(T P CTREF )(in the formula, T P CTREF (where is the peak elution temperature of the first ethylene interpolymer in the CTREF chromatogram), and BrF(#C6 / 1000C) = 9341.8(ρ 1 ) 2 -17766(ρ 1 )+8446.8(in the formula, ρ 1 (where is the density of the first ethylene interpolymer). The BrF(#C6 / 1000C) and density of the second ethylene interpolymer were determined using a blending rule, taking into account the overall BrF(#C6 / 1000C) and density of the ethylene interpolymer product. The BrF(#C6 / 1000C) and density of the second and third ethylene interpolymers were assumed to be the same.

[0240] Neutron activation (elemental analysis) Using neutron activation analysis, hereafter referred to as NAA, the catalyst residue in ethylene interpolymer products was determined as follows: The ethylene interpolymer product sample was packed into a radiation vial (made of ultra-high-purity polyethylene, 7 mL internal volume), and the sample weight was recorded. Using a pneumatic transfer system, the sample was placed into a SLOWPOKE® reactor (Atomic Energy of Canada Limited, Ottawa, Ontario, Canada) and irradiated for 30-600 seconds for elements with short half-lives (e.g., Ti, V, Al, Mg, and Cl) or 3-5 hours for elements with long half-lives (e.g., Zr, Hf, Cr, Fe, and Ni). The average thermal neutron flux in the reactor was 5 × 10⁻¹⁶.11 / cm 2 The radiation level was per second. After irradiation, the sample was removed from the reactor and aged to allow the radioactivity to decay. Elements with short half-lives were aged for 300 seconds, while elements with long half-lives were aged for several days. After aging, the gamma-ray spectrum of the sample was recorded using a germanium semiconductor gamma-ray detector (Ortec model GEM55185, Advanced Measurement Technology Inc., Oak Ridge, TN, USA) and a multi-channel analyzer (Ortec model DSPEC Pro). The amount of each element in the sample was calculated from the gamma-ray spectrum and recorded in parts per million relative to the total weight of the ethylene interpolymer product sample. The NAA system was calibrated with the Specpure standard (1000 ppm solution of the desired element (purity over 99%)). 1 mL of the solution (of the target element) was pipetteed onto a 15 mm × 800 mm rectangular filter paper and air-dried. The filter paper was then placed in a 1.4 mL polyethylene irradiation vial and analyzed using the NAA system. The sensitivity of the NAA procedure was determined using a standard (counts / μg).

[0241] unsaturated The amount of unsaturated groups, i.e., double bonds, in ethylene interpolymer products was determined according to ASTM D3124-98 (published March 2011) and ASTM D6248-98 (published July 2012). The ethylene interpolymer product samples were subjected to the following steps: a) overnight carbon disulfide extraction to remove any additives that could interfere with the analysis; b) the samples (in pellet, film, or granular form) were pressed into plaques of uniform thickness (0.5 mm); c) the plaques were analyzed by FTIR to quantify the amounts of terminal (vinyl) and internally unsaturated (trans-vinylene); and d) the sample plaques were brominated and re-analyzed by FTIR to quantify the amount of side-chain unsaturated (vinylidene). The IR resonances of these groups were 908 cm⁻¹, respectively. -1 , 965cm -1 and 888cm -1This procedure is based on Beer's Law: A=abdc, where a is the extinction coefficient of the specific unsaturated plaque being measured, b is the plaque thickness, d is the plaque density, and c is the selected unsaturated plaque. Experimentally, weight and area are measured rather than density and thickness of the plaque.

[0242] Comonomer (α-olefin) content: Fourier transform infrared (FTIR) spectroscopy The amount of comonomers in the ethylene interpolymer product was determined by FTIR and reported as the short-chain branched (SCB) content with dimensions of CH3# / 1000C (number of methyl branches per 1000 carbon atoms). This test was completed according to ASTM D6645-01 (2001) using compression-molded polymer plaques and a Thermo-Nicolet 750 Magna-IR Spectrophotometer. The polymer plaques were prepared according to ASTM D4703-16 (April 2016) using a compression molding device (Wabash-Genesis Series press).

[0243] Dynamic mechanical analysis (DMA) Vibrational shear measurements were performed under small strain amplitudes to obtain linear viscoelastic functions at 5 points per 10 degrees Celsius over a strain amplitude of 10% and a frequency range of 0.02 to 126 rad / s, under an N2 atmosphere at 190°C. Frequency sweep experiments were performed using a TA Instruments DHR3 stress-controlled rheometer with a cone-plane geometry having a 5° cone angle, a 137 μm truncation, and a 25 mm diameter. In these experiments, sinusoidal strain waves were applied, and the stress response was analyzed with respect to the linear viscoelastic function. The zero shear rate viscosity (η0) based on the DMA frequency sweep results was predicted using the Ellis model (see RB Bird et al., "Dynamics of Polymer Liquids. Volume 1: Fluid Mechanics," Wiley-Interscience Publications (1987), p. 228) or the Carreau-Yasuda model (see K. Yasuda (1979) PhD paper, IT Cambridge).

[0244] In this disclosure, shear fluidization τ (seconds) -1 The start of the 3-parameter Ellis model (η 0、 τ and η) DMA data (complex viscosity (η) at 190°C * ) versus frequency (ω): that is (η * =η0 / (1+(ω / τ) (n-1) This was determined by fitting it to the following:

[0245] The fluid activation energy (FAE), having dimensions of J / mol, was also determined. Data was generated using Rheometrics RDSII, from which the FAE was calculated. Specifically, melt viscosity-flow curves (0.05–100 rad / sec, 7 data points per 10) were measured at four different temperatures (160°C, 175°C, 190°C, and 205°C). Using 190°C as the reference temperature, a time-temperature-superposition shift was performed to obtain the shift factor. The FAE for each sample was calculated using TTS (time-temperature superposition (see Markovitz, H., "Superposition in Rheology," J. Polym. Sci., Polymer Symposium Series 50, 431–456 (1975)) shifting of the flow curves, as well as fitting of the Arrhenius equation to the zero shear viscosity at each temperature using RheoPlus and Orchestrator software.

[0246] creep test Creep measurements were performed at 190°C using an Anton Paar MCR 501 rheometer in an N2 atmosphere with a 25 mm parallel plate geometry. In this experiment, a 1.8 mm thick compression-molded circular plaque was placed between preheated upper and lower measuring fixtures and allowed to reach thermal equilibrium. The upper plate was then lowered to 50 μm above the 1.5 mm test gap size. At this point, excess material was trimmed, and the upper fixture was lowered to the measurement gap size. A 10-minute waiting period was applied after sample placement and trimming to avoid residual stress causing strain drift. In the creep experiment, the shear stress was instantaneously increased from 0 Pa to 20 Pa, and the strain was recorded against time. The sample continued to deform under a constant shear stress until it reached a steady-state strain rate. Creep data were reported in terms of creep compliance (J(t)), which has units of the reciprocal of the elastic modulus. The zero shear rate viscosity was calculated based on linear regression of data points in the last 10% time window of the creep experiment, using the reciprocal of the slope of J(t) in the steady-state creep mode.

[0247] To determine whether the sample decomposed during the creep test, frequency sweep experiments were performed under small strain amplitudes (10%) before and after the creep phase over a frequency range of 0.1–100 rad / s. The difference in the magnitude of the complex viscosity at 0.1 rad / s before and after the creep phase was used as an indicator of thermal decomposition. For the zero shear rate viscosity determined by creep to be considered acceptable, the difference should be less than 5%. In the creep experiment, it was confirmed that the reference line shown in Figure 2 for linear ethylene interpolymers is also valid when the η0 determined by creep rather than the η0 determined by DMA is used.

[0248] Melt strength The accelerated-haul-off (AHO) melt strength (MS), with dimensions of centinewtons (cN), was measured using a Rosand RH-7 capillary rheometer (available from Malvern Instruments Ltd, Worcestershire, UK) with a 15 mm barrel diameter, a 2 mm diameter flat die, a 10:1 L / D ratio, and a 10,000 psi (68.95 MPa) pressure converter. The polymer molten material was extruded through the capillary die at a constant rate (constant piston speed of 5.33 mm / min at 190°C), thereby forming an extruded polymer filament. The polymer filament was then passed through a set of rollers and stretched by increasing the take-up rate until it broke. More specifically, the initial polymer filament speed was 50–80 m / min. 2 The polymer filament was increased from 0 m / min at a constant acceleration until it broke. During this experiment, the force on the roller was constantly measured; initially, the force increased rapidly, then plateaued before the filament broke. The maximum force in the plateau region of the force-time curve was defined as the melt strength of the polymer, measured in centinewtons (cN).

[0249] Vicat softening point (temperature) The Vicat softening point of ethylene interpolymer products was determined according to ASTM D1525-07 (published December 2009). This test determines the temperature at which a specific needle penetration occurs when the sample is subjected to the ASTM D1525-07 test conditions, namely heating rate B (120 ± 10 °C / hour) and a 938 gram load (10 ± 0.2 N load).

[0250] Thermal deflection temperature The thermal deflection temperature of the ethylene interpolymer product was determined according to ASTM D648-07 (approved March 1, 2007). The thermal deflection temperature is the temperature at which a deflection tool applying a stress of 0.455 MPa (66 PSI) to the center of a molded ethylene interpolymer plaque (3.175 mm (0.125 in) thick) deflects the plaque by 0.25 mm (0.010 in) when the plaque is heated at a constant rate in a medium.

[0251] Bending properties The bending properties, namely the secant and tangential moduli and bending strength, were determined using ASTM D790-10 (published April 2010).

[0252] Film Dirt Shock The film dart impact strength was determined using ASTM D1709-09 Method A (May 1, 2009). In this disclosure, the dart impact test used a hemispherical head dart with a diameter of 1.5 inches (38 mm).

[0253] Film tear The energy (J / mm) required for film "rupture," i.e., for the film to break, was determined using ASTM D5748-95 (initially adopted in 1995, reapproved in 2012).

[0254] Lub-Tef film rupture A "Lub-Tef rupture" test was performed using a specially designed Teflon probe at a rupture speed of 20 in / min. The purpose of this test was to determine the rupture resistance of a single-layer ethylene interpolymer product film. An MTS Insight / Instron Model 5 SL Universal Testing Machine with MTS Testworks 4 software was used, along with an MTS 1000N or 5000N load cell. Film samples were prepared according to ASTM standards for at least 24 hours prior to testing. Considering the roll of blown film, a 4.25-inch sample with the length of the film roll laid flat was cut in the width direction, and a label was attached to the outside of the film (the probe impacted the outside of the film). A Teflon-coated rupture probe was attached, and the test speed was set to 20 inches / min. The film sample was clamped, and a 1 cm mark was placed in the center of the film. 3 Apply the lubricant. With the crosshead in the starting test position, set the limit switches on the load cell frame 10 inches below and above the crosshead. Measure and record the thickness of the film sample and begin the tear test. Thoroughly clean the probe head before the next test. Repeat until at least five consistent tear results are obtained, i.e., a standard deviation of less than 10%. The lubricant used was Muko Lubricating Jelly, a water-soluble personal lubricant available from Cardinal Health Inc., 1000 Tesma Way, Vaughan, ON L4K 5R8 Canada. The probe head was machined Teflon with a 1.4-inch cone shape and a flat-ended tip.

[0255] Film tensile properties The following film tensile properties were determined using ASTM D882-12 (August 1, 2012): tensile breaking strength (MPa), elongation at break (%), tensile yield strength (MPa), and yield point tensile elongation (%). Tensile properties were measured in both the flow direction (MD) and width direction (TD) of the blown film.

[0256] Film secant modulus The secant modulus is a measure of film stiffness. The secant modulus was determined according to ASTM D882. The secant modulus is the slope of the line drawn between two points on the stress-strain curve, i.e., the secant. The first point on the stress-strain curve is the origin, i.e., the point corresponding to the origin (zero percent strain and zero stress), and the second point on the stress-strain curve corresponds to 1% strain. Considering these two points, the 1% secant modulus is calculated and expressed in units of force per unit area (MPa). The 2% secant modulus is calculated similarly. Since the stress-strain relationship of polyethylene does not follow Hooke's Law, i.e., the stress-strain behavior of polyethylene is nonlinear due to its viscoelastic properties, this method is used to calculate the film modulus. The secant modulus was measured using a conventional Instron tensile testing machine equipped with a 200 lbf load cell. For testing, strips of single-layer film samples were cut to dimensions of 14 inches in length, 1 inch in width, and 1 mil in thickness, and it was confirmed that there were no notches or cuts at the edges of the samples. The film samples were cut and tested in both the flow direction (MD) and the width direction (TD). The samples were prepared using ASTM conditions. The thickness of each film was accurately measured using a handheld micrometer and entered into the Instron software along with the sample name. The samples were placed in the Instron with a grip spacing of 10 inches and pulled out at a speed of 1 inch / min to generate strain-strain curves. The 1% and 2% secant moduli were calculated using the Instron software.

[0257] Film Elmendorf tear The film tear performance was determined according to ASTM D1922-09 (May 1, 2009), and the equivalent term for tear is "Elmendorf tear." Film tear was measured in both the flow direction (MD) and the width direction (TD) of the blown film.

[0258] Film tear propagation The tear propagation resistance of blown films was determined using ASTM D2582-09 (May 1, 2009). This test measures the blown film's resistance to snagging, or more precisely, to the propagation of dynamic ruptures and tears. Tear propagation resistance was measured in the flow direction (MD) and width direction (TD) of the blown film.

[0259] Film optical properties The optical properties of the film were measured as follows: haze, ASTM D1003-13 (November 15, 2013), and gloss, ASTM D2457-13 (April 1, 2013).

[0260] Film Dynatup Shock The impact test using the instrument was performed with a machine called a Dynatup impact tester, purchased from Illinois Test Works Inc., Santa Barbara, CA, USA, and is often referred to as a Dynatup impact test by those skilled in the art. The test was completed according to the following procedure: Test specimens were prepared by cutting strips 5 inches (12.7 cm) wide and 6 inches (15.2 cm) long from a roll of blow film. The film was 1 mil thick. Before the test, the thickness of each specimen was accurately measured and recorded using a handheld micrometer. ASTM conditions were used. The test specimens were mounted on the 9250 Dynatup Impact drop tower / tester using pneumatic clamps. A Dynatup tap #1, 0.5 inches (1.3 cm) in diameter was attached to the crosshead using the included Allen bolt. Before the test, the crosshead was raised to a height that resulted in a film impact velocity of 10.9 ± 0.1 ft / sec. Weight was applied to the crosshead as follows: 1) Crosshead deceleration, or tap deceleration, was 20% or less from the start of the test to the point of peak load, and 2) the tap had to penetrate the test specimen. If the tap did not penetrate the film, additional weight was added to the crosshead to increase the impact velocity. During each test, the Dynatup Impulse Data Acquisition System Software collected experimental data (load (lb) vs. time). At least five film specimens were tested, and the software reported the following average values: "Dynatup Maximum Load (lb)", i.e., the highest load measured during the impact test; "Dynatup Total Energy (ft·lb)", i.e., the area under the load curve from the start of the test to the end of the test (trend of the specimen); and "Dynatup Total Energy at Maximum Load (ft·lb)", i.e., the area under the load curve from the start of the test to the point of maximum load.

[0261] Cold seal strength The cold seal strength of a 3.5 mil (88.9 μm) 9-layer film was measured using a conventional Instron tensile testing machine. In this test, two multilayer films were sealed (1 layer to 1 layer) over a certain temperature range, and the seals were then aged at 73°F (23°C) for at least 24 hours before the tensile test. The following parameters were used in the cold seal strength test: width of the film test sample of 1 inch (25.4 mm); film sealing time of 0.5 seconds; 0.27 N / mm². 2 The film sealing pressure was measured within a temperature range of 90°C to 170°C and in 5°C or 10°C temperature increments. After aging, the seal strength was determined using the following tensile parameters: a draw-out (crosshead) speed of 12 in / min (30.48 cm / min); a grip spacing of 0.39 in (0.99 cm); and a draw-out direction of 90° relative to the seal. Four to eight samples of each multilayer film were also tested at each temperature increment, and the average value was calculated. In the cold seal test, the seal start temperature (SIT) was recorded in °C, where SIT was the temperature at which the seal strength reached 8.8 N / in.

[0262] Film hot tack strength The hot tack strength of a 3.5 mil (88.9 μm) 9-ply film was measured using a J&B Hot Tack tester (Jbi Hot Tack, Geloeslaan 30, B-3630 Maamechelen, Belgium, commercially available). The hot tack test measures the strength of the polymer-to-polymer seal immediately after heat-sealing two films together, i.e., when the polyolefin is semi-molten. This test simulates heat sealing in an automated packaging machine, such as a vertical or horizontal filling and sealing machine. The J&B Hot Tack test used the following parameters: width of the film sample (1 inch, 25.4 mm); film sealing time (0.5 seconds); and strength (0.27 N / mm²). 2The film sealing pressure; sealing time of 0.5 seconds; cooling time of 0.5 seconds; film peeling speed of 7.9 in / second (200 mm / second); temperature range of 90°C to 170°C; temperature increments of 5°C or 10°C. In addition, 4 to 8 samples of each multilayer film were tested at each temperature increment, and the average value was calculated. In this disclosure, the hot tack onset (HTO) temperature, measured in °C, was the temperature at which the hot tack force reached 1 N. Furthermore, the maximum hot tack force (Max. HTF) was recorded, i.e., the maximum hot tack force (N) during the hot tack experiment was recorded, and the temperature (°C) at which Max. HTF was observed was also recorded.

[0263] Film hexane extract The hexane extract was determined according to the Federal Regulatory Standards (Code of Federal Registration) 21 CFR §177.1520 Para(c) 3.1 and 3.2, which determine the amount of hexane-extractable material in the film by gravimetric method. Specifically, 2.5 grams of 3.5 mil (89 μm) single-layer film was placed in a stainless steel basket, and the film and basket were weighed (w i ). While still in the basket, the film was extracted with n-hexane at 49.5°C for 2 hours, dried in a vacuum furnace at 80°C for 2 hours, cooled in a desiccator for 30 minutes, and weighed (w f ). Percentage loss by weight, percentage hexane extract (w C6 ) is:w C6 =100 × (w i -w f ) / w i . [Examples]

[0264] Pilot plant polymerization The following examples are provided to illustrate selected embodiments of the present disclosure, and it should be understood that the examples shown hereafter do not limit the scope of the stated claims. Examples of ethylene interpolymer products were prepared in a continuous solution process pilot plant as described below.

[0265] The solution process conditions for Examples 44 and 1 and 2 are summarized in Tables 5A and 5B, and two CSTR reactors (R1 and R2) configured in series were used. The pressure in R1 varied from 14 MPa to 18 MPa, and R2 operated at a lower pressure to facilitate continuous flow from R1 to R2. The CSTR was stirred to give conditions for thorough mixing of the reactor contents. The process was operated continuously by supplying fresh process solvent, ethylene, 1-octene, and hydrogen to the reactors. Methylpentane was used as the process solvent (a commercially available blend of methylpentane isomers). The volume of the first CSTR reactor (R1) was 3.2 gallons (12 L), the volume of the second CSTR reactor (R2) was 5.8 gallons (22 L), and the volume of the tubular reactor (R3) was 0.58 gallons (2.2 L).

[0266] A crosslinked metallocene catalyst formulation was prepared using the following components: Component A, diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafniumdimethyl, [(2,7-tBu2Flu)Ph2C(Cp)HfMe2] (abbreviated as CpF-2); Component M, methylaluminoxane (MMAO-07); Component B, trityltetrakis(pentafluorophenyl)borate; and Component P, 2,6-di-tert-butyl-4-ethylphenol. The following catalyst solvents were used: methylpentane for components M and P; and xylene for components A and B.

[0267] Comparative ethylene interpolymer products were prepared using a non-crosslinked single-site catalyst formulation containing component C, cyclopentadienyltri(tert-butyl)phosphineimine titanium dichloride [Cp[(t-Bu)3PN]TiCl2] (abbreviated as PIC-1); component M, methylaluminoxane (MMAO-07); component B, trityltetrakis(pentafluorophenyl) borate; and component P, 2,6-di-tert-butyl-4-ethylphenol. The following catalyst solvents were used: methylpentane for components M and P; and xylene for components A and B.

[0268] In Example 44, Table 5A shows that the amount of CpF-2 in reactor 1 (R1) was 0.33 ppm, i.e., "R1 catalyst (ppm)". The efficiency of the crosslinked metallocene catalyst formulation was optimized by adjusting the molar ratio of the catalyst components and the R1 catalyst inlet temperature. As shown in Table 5A, the optimized molar ratios were ([M] / [A]), i.e., [(MMAO-07) / (CpF-2)]; ([P] / [M]), i.e., [(2,6-di-tert-butyl-4-ethylphenol) / (MMAO-07)]; and ([B] / [A]), i.e., [(trityltetrakis(pentafluorophenyl) borate) / (CpF-2)]. More specifically, in Example 44 (Table 5A), the molar ratios in R1 were R1([M] / [A])=50; R1([P] / [M])=0.42; and R1([B] / [A])=1.21. As shown in Table 5B, the R1 catalyst inlet temperature in Example 44 was 30.2°C. In Example 44, the second crosslinked metallocene catalyst formulation was injected into the second reactor (R2). Tables 5A and 5B disclose additional process parameters, such as ethylene and 1-octene splitting between reactors, as well as reactor temperature and ethylene conversion rate.

[0269] 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. Representative or typical values ​​for the examples shown in Tables 5A and 5B are as follows: the average reactor residence times were 61 seconds in R1, 73 seconds in R2, and 7.3 seconds in R3 with a volume of 0.58 gallons (2.2 L).

[0270] 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 (caprylic acid), commercially available from P&G Chemicals, Cincinnati, OH, USA. The catalyst deactivator was added so that the molar amount of the fatty acid added was 50% of the total molar amount of catalyst metal and aluminum added to the polymerization process.

[0271] The ethylene interpolymer product was recovered from the process solvent using a two-stage devolitizing process. Specifically, two vapor / liquid separators were used, and the second bottom stream (from the second V / L separator) was passed through a gear pump / pelletizer combination.

[0272] Prior to pelletization, the ethylene interpolymer product was stabilized by adding 500 ppm of IRGANOX® 1076 (primary antioxidant) and 500 ppm of IRGAFOS® 168 (secondary antioxidant) based on the weight of the ethylene interpolymer product. The antioxidants were dissolved in the process solvent and added between the first V / L separator and the second V / L separator.

[0273] Example 44 (Figure 9) was prepared in the solution pilot plant described above, but the cross-linked metallocene catalyst mixture was injected into reactors 1 and 2, and ethylene splitting (ES) was performed. R1 =30%, ES R2 =50% and ES R3 =20%, and Octen partitioning is OS R1 =49.5%, OS R2 =40.5% and OS R3 =10%, and the final ethylene interpolymer product has a melt index of 1.25 dg / min, a density of 0.9113 g / cc, and a melt flow ratio of 31.7 (I 21 It had / I2). Examples 43 and 45-47 (Figure 9) were prepared in the same solution pilot plant campaign as Example 44, but with various process conditions, such as octene splitting (OS), changed.

[0274] Examples 1, 2, and 44 were characterized, and the results are shown in Table 6A. Table 6A also discloses Examples 4-6 and 15, prepared in the same solution pilot plant using the crosslinked metallocene catalyst formulations and reactor configuration described above for Examples 1 and 2. In Table 6A, the term "FAE (J / mol)" is the fluid activation energy as described in the Experiments section; "MS (cN)" is the melt strength; and τ (seconds) is the melt strength. -1)" reveals the rheological initiation of shear fluidization.

[0275] Table 6B shows the characterization of comparative ethylene interpolymer products. Comparison 1a is SURPASS FPs117-C, comparison 2a was produced in a solution pilot plant using a crosslinked metallocene catalyst formulation in the first reactor and a non-crosslinked single-site catalyst formulation in the second reactor, comparison 3a was produced in a solution pilot plant using a crosslinked metallocene catalyst formulation in the first reactor and an in-line Ziegler-Natta catalyst formulation in the second reactor, comparison 4a is SURPASS VPsK914, comparison 5a is SCLAIR® FP120, and comparisons 14-16 were produced in a solution pilot plant using non-crosslinked single-site catalyst formulations in reactors 1 and 2.

[0276] Table 6C shows the characterization of additional comparative samples. Comparative samples Q1-Q4 were QUEO products, specifically QUEO0201, QUEO8201, QUEO0203, and QUEO1001, respectively. The remaining comparative samples were as follows: Comparative sample R1 was AFFINITY PL1880; comparative sample S1 was ENABLE 20-05HH; comparative sample T1 was EXCEED 1018CA; comparative sample U1 was ELITE AT6202; and comparative sample V1 was ELITE 5401G.

[0277] There is a need to improve the continuous solution polymerization process, for example, to increase the production rate, which is the kilograms of ethylene interpolymer product produced per hour. Tables 7A and 7B disclose the conditions for a series two-reactor solution polymerization process that produced a product with a melt index (I2) of approximately 1.0 dg / min and a density of approximately 0.9175 g / cc. An improved continuous solution polymerization process is shown in Example 6 of Table 7A. Example 6 was an ethylene interpolymer product produced in a solution pilot plant (described above) by injecting a crosslinked metallocene catalyst formulation (CpF-2) into reactors 1 and 2.

[0278] The comparative continuous solution polymerization process is shown in Comparison 8 of Table 7A. Comparison 8 was the comparative ethylene interpolymer product produced in the same solution pilot plant by injecting a non-crosslinked single-site catalyst formulation (PIC-1) into reactors 1 and 2. The improved process yielded a production rate of 93.0 kg / hour PR A In contrast, the comparative process had a comparative production rate of 81.3 kg / hour. C The improved process had a 14.5% increase in production rate. I It had, that is, PR I =100×(PR A -PR C ) / PR C = 100 × ((93.0 - 81.3) / 81.3) = 14.5% That was the case.

[0279] Tables 8A and 8B disclose serial two-reactor solution polymerization process conditions that produced a product with a fractional melt index (I2) of approximately 0.8 dg / min and a density of approximately 0.9145 g / cc. Example 5 was synthesized using a crosslinked metallocene catalyst formulation, while, in contrast, Comparative 9 was synthesized using a non-crosslinked single-site catalyst formulation. In the case of Example 5, the improved serial solution polymerization process yielded a production rate PR of 93.9 kg / hour. A In contrast, the comparative process had a comparative production rate of 79.4 kg / hour. C The improved process had an 18.3% increase in production rate. I He possessed it.

[0280] There is a need to improve continuous solution polymerization processes, for example, to increase the molecular weight of ethylene interpolymer products produced at specific reactor temperatures. Furthermore, solution polymerization requires catalyst formulations that efficiently incorporate α-olefins into the increasing polymer chain. In other words, there is a need for catalyst formulations that produce ethylene interpolymer products with a specific density at lower (α-olefin / ethylene) ratios in the reactor.

[0281] Table 9 compares the solution polymerization conditions for Example 10, produced using a crosslinked metallocene catalyst formulation (CpF-2), and Comparative 10s, simulated using a non-crosslinked single-site catalyst formulation (PIC-1). Example 10 was produced in a continuous solution process pilot plant (described above) using one CSTR reactor. Compared to Example 10, Comparative 10s used the same reactor configuration, the same reactor temperature (165°C), the same hydrogen concentration (4 ppm), and the same ethylene conversion rate (90% (Q)). T The [α-olefin / ethylene] ratio was simulated by computer using )) and adjusted to produce an ethylene interpolymer product with the same branching frequency (approximately 16C6 / 1000C) as in Example 10. Considering Table 9, it is clear that Example 10 is characterized by an improved solution polymerization process compared to Comparative 10s, i.e., an improved "% reduced [α-olefin / ethylene]" ratio result. In detail, the [α-olefin / ethylene] ratio in Example 10 A The weight ratio is [α-olefin / ethylene] compared to 10s. C It was 83.8% lower (improved) compared to the weight ratio, meaning,

number

[0282] Similarly, Table 9 also compares the solution polymerization conditions of Example 11, prepared using a crosslinked metallocene catalyst formulation (CpF-2), with the simulated solution polymerization conditions of Comparative 10s using a non-crosslinked single-site catalyst formulation (PIC-1). Example 11 and Comparative 11s use the same reactor configuration, the same reactor temperature (165°C), the same hydrogen concentration (6 ppm), and the same ethylene conversion rate (85% (Q)). T Each was manufactured or simulated using )), and each [α-olefin / ethylene] ratio was adjusted to produce ethylene interpolymer products with approximately the same branching frequency (approximately 21.5C6 / 1000C). [α-olefin / ethylene] in Example 11 A The weight ratio is [α-olefin / ethylene] compared to 11s. C It was 72.7% lower (improved) compared to [another example]. Furthermore, the weight-average molecular weight (M) of Example 11 was also lower. w A ) is as shown in Table 9, the weight-average molecular weight (M) of comparative 11s. w C It was 199% higher (an improvement) compared to [the previous case].

[0283] Table 10 summarizes solution polymerization process data at higher and lower reactor temperatures compared to Table 9. For example, at a reactor temperature of 190°C, Example 12 can be compared to the simulated comparison 12s. Example 12 [α-olefin / ethylene] A The weight ratio is [α-olefin / ethylene] compared to 12s. C It was 90.8% lower compared to the weight ratio (improved). Furthermore, the weight-average molecular weight (M) of Example 12 w A ) is as shown in Table 10, the weight-average molecular weight (M) of comparative 12s. w C It was 70.4% higher compared to (an improvement).

[0284] Table 10 allows us to compare Example 13 with the simulated comparison 13s, both with a reactor temperature of 143°C. [α-olefin / ethylene] in Example 13 A The weight ratio is [α-olefin / ethylene] compared to 13s. C It is 88.9% lower (improved) compared to, and the weight-average molecular weight (M) of Example 13 w A ) is the weight-average molecular weight (M) of the comparative 13s. w C It was 182% higher (an improvement) compared to [the previous case].

[0285] Tables 11A and 11B compare the two-reactor solution polymerization conditions for Example 14 and Comparative Example 14. Table 11A discloses the process conditions for reactor 1, and Table 11B discloses the process conditions for reactor 2. Example 14 was a two-reactor ethylene interpolymer product containing a first ethylene interpolymer synthesized using a crosslinked metallocene catalyst formulation and a second ethylene interpolymer synthesized using a non-crosslinked single-site catalyst. Comparative Example 14 was a comparative two-reactor ethylene interpolymer product in which both the first and second ethylene interpolymers were synthesized using a non-crosslinked single-site catalyst. Table 11A shows that the reactor temperature (118.7°C ± 0.7%) and ethylene conversion rate (80.0%) were the same for Example 14 and Comparative Example 14, however, in the case of the crosslinked metallocene catalyst formulation, a (α-olefin / ethylene) weight fraction of 0.35 weight fraction was used in the first reactor, which was 87.3% lower compared to the non-crosslinked single-site catalyst formulation, i.e., 2.76 weight fraction. Furthermore, the amount of hydrogen used in reactor 1 was three times higher when using the crosslinked metallocene catalyst formulation compared to the non-crosslinked single-site catalyst formulation. Those skilled in the art know that hydrogen is involved in olefin polymerization. w It is recognized that hydrogen is very effective in controlling (or the melt index), that is, in stopping the increasing polymer and reducing the molecular weight of ethylene interpolymers.

[0286] Table 12 summarizes the SEC deconvolution results, namely, the deconvolution of two reactor examples 14 and comparative example 14 to the first and second ethylene interpolymers. Table 12 shows the weight-average molecular weight (M) of the first ethylene interpolymer. w ) was the same in Example 14 and Comparison 14, that is, in Example 14 it was 249,902M w And in comparison 14, 275,490M w This indicates that this M w The similarity was obtained even when 3 ppm of hydrogen was used to produce the former and no hydrogen was used to produce the latter. In other words, considering the data in Table 12, it was clear that the crosslinked metallocene catalyst formulation produced ethylene interpolymers with higher molecular weights at a given polymerization temperature, ethylene conversion rate, and hydrogen concentration compared to the non-crosslinked single-site catalyst formulation.

[0287] Table 12 also shows that the crosslinked metallocene catalyst formulations incorporated more α-olefins into the first ethylene interpolymer compared to the non-crosslinked single-site catalyst formulation (i.e., 22.9 BrF (C6 / 1000C)) (i.e., 27.8 BrF (C6 / 1000C) in Example 14). Note that this difference in branching frequency occurred even when far fewer α-olefins were used to produce the former compared to the latter, as shown in Table 11A. In other words, the crosslinked metallocene catalyst formulations are far more efficient than the non-crosslinked single-site catalyst formulations in incorporating α-olefins into the polymer.

[0288] Figure 5 compares the molecular weight distribution determined by SEC for Example 14 and Comparison 14, and the branching frequency determined by GPC-FTIR as a function of molecular weight. The branching distribution curve (BrF) for Example 14 shows a large difference in the α-olefin content of the first ethylene interpolymer, i.e., 27.8C6 / 1000C (density of the first ethylene interpolymer 0.8965 g / cc), and the α-olefin content of the second ethylene interpolymer, i.e., 0.924C6 / 1000C (0.9575 g / cc). This large difference in interpolymer density, i.e., Δρ = 0.0610 g / cc = (ρ 2 -ρ 1 )(where ρ 2 ρ is the density of the second ethylene interpolymer, 1 The density of the first ethylene interpolymer (where Δρ' is the density of the first ethylene interpolymer) reflects that Example 14 was produced in a parallel reactor mode and using different catalysts in reactors 1 and 2. A higher Δρ' is advantageous in several end applications, one non-limiting example being higher film stiffness while maintaining or improving film toughness. On the other hand, as shown in Table 12, the Δρ of Comparative 14 was an order of magnitude lower, i.e., 0.0062 g / cc.

[0289] Figure 6 shows the experimentally measured SEC chromatogram of Example 4, showing the deconvolution into three components: the first ethylene interpolymer, the second ethylene interpolymer, and the third ethylene interpolymer. Example 4 is characterized in Table 13. Example 4 was produced in a solution pilot plant (described above) using a crosslinked metallocene catalyst formulation (CpF-2), with a third reactor volume of 2.2 liters. More specifically, immediately after production, the ethylene interpolymer product Example 4 had the following overall values: I2 of 0.87 dg / min, density of 0.9112 g / cc, and M of 105449 as measured by SEC. w (7.53M w / M n ). As shown in Figure 6 and Table 13, Example 4 is M of 230042 wand 37 wt.% of the first ethylene interpolymer, 22418, having a branched content of 16.3C6 / 1000C. w and 57 wt.% of a second ethylene interpolymer having a branched content of 21.3C6 / 1000C, and M 22418 w It also contained 6 wt.% of a third ethylene interpolymer with a branching content of 21.3C6 / 1000C (the branching content was determined by deconvolution of GPC-FTIR data). The molecular weight distribution of the first, second, and third ethylene interpolymers was a Flory distribution, i.e., M w / M n Characterized by =2.0. Table 13 discloses two additional samples, Examples 5 and 6, produced in a solution pilot plant using the same crosslinked metallocene catalyst formulation. The SEC and GPC-FTIR curves of Examples 5 and 6 were also deconvolved into the first, second, and third ethylene interpolymers, as shown in Table 13.

[0290] Continuous polymerization unit (CPU) Small-scale continuous solution polymerization was performed using a continuous polymerization unit hereafter referred to as the CPU. These experiments compared the performance of a crosslinked metallocene catalyst formulation (containing component A, CpF-1) with that of a non-crosslinked single-site catalyst formulation (containing component C, PIC-1) in a single reactor.

[0291] The CPU's single reactor contained 71.5 mL of continuously stirred CSTR, polymerization was carried out at 160°C, and the reactor pressure was approximately 10.5 MPa. The CPU included a 20 mL upstream mixing chamber operating at a temperature 5°C lower than the downstream polymerization reactor. The upstream mixing chamber was used to preheat ethylene, an optional α-olefin, and a portion of the process solvent. The catalyst feed and the remaining solvent were added directly to the polymerization reactor as a continuous process. The total flow rate to the polymerization reactor was kept constant at 27 mL / min. The components of the crosslinked metallocene catalyst formulation (components A, M, B, and P) were added directly to the polymerization reactor to maintain the continuous polymerization process. More specifically, components A and B were pre-mixed in xylene and directly injected into the reactor, while components M and an optional component P were pre-mixed in the process solvent and directly injected into the reactor. In comparative experiments, the components of the non-crosslinked single-site catalyst formulation (components C, M, B, and P) were directly added to the polymerization reactor to maintain the continuous polymerization process. More specifically, components C and B were pre-mixed in xylene and directly injected into the reactor, while components M and an optional component P were pre-mixed in the process solvent and directly injected into the reactor. In the example, component A used was CpF-1[(2,7-tBu2Flu)Ph2C(Cp)HfCl2]. In the comparison, component C used was PIC-1([Cp[(t-Bu)3PN]TiCl2]). Components M, B, and P were methylaluminoxane (MMAO-07), trityltetrakis(pentafluorophenyl) borate, and 2,6-di-tert-butyl-4-ethylphenol, respectively. After injection, the catalyst was activated in situ (inside the polymerization reactor) in the presence of ethylene and an optional α-olefin comonomer. Component M was added so that the molar ratio of ([M] / [A]) or ([M] / [C]) was approximately 80; component B was added so that the molar ratio of ([M] / [A]) or ([M] / [C]) was approximately 1.0; and component P was added so that the molar ratio of ([P] / [M]) was approximately 0.4.

[0292] Ethylene was supplied to the reactor via a calibrated thermomass flow meter and dissolved in the reaction solvent before entering the polymerization reactor. Optional α-olefins (comonomers, i.e., 1-octene) were pre-mixed with ethylene before entering the polymerization reactor, with the (1-octene) / (ethylene) weight ratio varying from 0 to approximately 6.0. Ethylene was supplied to the reactor so that the ethylene concentration varied from approximately 7 to approximately 15% by weight, where weight percentage is calculated by dividing the weight of ethylene by the total weight of the reactor contents. The internal reaction temperature was monitored by thermocouples in the polymerization medium and controlled to a target setting point of ±0.5°C. All solvent, monomer, and comonomer streams were purified by a CPU system before entering the reactor.

[0293] Ethylene conversion rate Q CPU That is, the fraction of converted ethylene is determined by online gas chromatography (GC), and polymerization activity K has dimensions of [L / (mmol·min)]. p CPU We defined it as follows:

number

[0294] CPU conditions were adjusted to synthesize ethylene interpolymer products with nearly constant melt index and density. More specifically, ethylene interpolymer products were synthesized using a crosslinked metallocene catalyst formulation, and comparative ethylene interpolymer products were synthesized using a non-crosslinked single-site catalyst formulation. As shown in each row of Table 14, "% Improvement M w " is the M of the ethylene interpolymer product produced with the crosslinked metallocene catalyst formulation. w A And the M of comparative ethylene interpolymer products produced with non-crosslinked single-site catalyst formulations w C When compared, it was at least 10%.

[0295] As shown in Table 15, it was necessary to adjust the (α-olefin / ethylene) weight ratio of the reactor so that the ethylene interpolymer product was produced at the target density. More specifically, a crosslinked metallocene catalyst formulation was used to synthesize the ethylene interpolymer product at the target density. A It is necessary to use a non-crosslinked single-site catalyst formulation to synthesize comparative ethylene interpolymer products at the target density (α-olefin / ethylene). C This was necessary. As shown in each row of Table 15, the crosslinked metallocene catalyst formulations enabled operation of the continuous solution polymerization process at an improved (reduced) (α-olefin / ethylene) weight ratio compared to the control non-crosslinked single-site catalyst formulation, i.e., the % reduction in [α-olefin / ethylene] weight ratio was at least -70%.

[0296] Ethylene interpolymer product example 60 was also produced with the CPU described above. Example 60 demonstrates the ability of a crosslinked metallocene catalyst formulation containing CpF-2((2,7-tBu2Flu)Ph2C(Cp)HfMe2) to produce a low-density product that was essentially elastomeric, namely, Example 60 was characterized as follows: 0.8567 g / cc, 72.9 BrF C6 / 1000C, 14.6 mol percent of 1-octene and 40.6 wt percent of 1-octene.

[0297] Single-layer film Single-layer blown film samples of ethylene interpolymer product examples 1 and 2 and comparative examples 15 and 16 were prepared as disclosed in Table 16. Examples 1 and 2 have been previously described, while comparative examples 15 and 16 were pilot plant samples produced by injecting a non-crosslinked single-site catalyst formulation (PIC-1) into R1 and R2 (series mode). The single-layer blown films were produced in a Gloucester extruder with a barrier screw; a low-pressure 4-inch (10.16 cm) diameter die with a 35 mil (0.089 cm) die gap; and a Western Polymer Air ring, with a 2.5-inch (6.45 cm) barrel diameter and a ratio of 24 / 1 L / D (barrel length / barrel diameter). The extruder was equipped with the following screen packs: 20 / 40 / 60 / 80 / 20 mesh. By adjusting the extruder screw speed, blown film with a thickness of approximately 1.0 mil (25.4 μm) was produced at a constant output speed of approximately 100 lb / hour (45.4 kg / hour), and the frost line height (FLH) was maintained at 16–18 inches (40.64–45.72 cm) by adjusting the cooling air. Additional blown film processing conditions are disclosed in Table 16.

[0298] Considering Table 16, it is clear that the blow film extrusion pressures in Examples 1 and 2 were -16% to -29% lower than those in Comparisons 15 and 16. Lower blow film extruder pressures were advantageous because the output (lb / hour) of the blow film line could be limited by the extruder pressure. Furthermore, the extruder amperage in Examples 1 and 2 was -10% to -26% lower than that of Comparisons 15 and 16. Lower blow film extruder amperages were advantageous because the power consumption of the blow film line could be reduced when the ethylene interpolymer products disclosed herein are used.

[0299] The properties of the single-layer films, along with the selected properties of Examples 1 and 2 and Comparisons 15 and 16, are disclosed in Table 17. Ethylene interpolymer products with high melt strength were advantageous in the blow film conversion process. That is, blow film output is often limited by the bubble instability of the blow film, and bubble stability improves as the resin melt strength increases. The melt strength (measured in centinewtons (cN)) of Examples 1 and 2 was 25% to 65% higher than that of Comparisons 15 and 16. The flow activation energy (kJ / mol) of Examples 1 and 2 was 42% to 66% higher than that of Comparisons 15 and 16. A higher flow activation energy is desirable because such resins become responsive to changes in extrusion temperature; for example, considering a higher flow activation energy, the resin viscosity decreases more rapidly with a given increase in extruder temperature (reducing extruder pressure and amperage).

[0300] Desirable film properties include film optical properties, such as low film haze and high film gloss at 45°. Optical properties are important when consumers purchase goods packaged in polyethylene film. Specifically, packaging with better contact and / or transparency clarity has lower internal film haze and higher film gloss or shimmer. The optical properties of the film correlate with consumers' perception of product quality. Considering Table 17, it was clear that the haze of Examples 1 and 2 was 40% to 45% lower (improved) compared to Comparisons 15 and 16, and the 45° film gloss of Examples 1 and 2 was 16% to 21% higher (improved) compared to Comparisons 15 and 16. Additional blown film properties are summarized in Table 17.

[0301] Multilayer film Multilayer films were manufactured using a commercially available 9-layer line from Brampton Engineering (Brampton ON, Canada). The structure of the manufactured 9-layer film is shown in Table 18. Layer 1 contained the sealant resin under test. More specifically, Layer 1 contained 91.5 wt% sealant resin, 2.5 wt.% antiblocking agent masterbatch, 3 wt.% slip agent masterbatch, and 3 wt.% processing aid masterbatch, with the additive masterbatch carrier resin being LLDPE, with a melt index of approximately 2 (I2) and a concentration of approximately 0.918 g / cc. Layer 1 was the inner layer, i.e., it was inside the bubble when the multilayer film was manufactured on the blow film line. The total thickness of the 9-layer film was kept constant at 3.5 mils, with the thickness of layer 1 being 0.385 mils (9.8 μm), or 11% of 3.5 mils (Table 18). Layers 1-4 and 6-8 contained SURPASS FPs016-C, an ethylene / 1-octene copolymer available from NOVA Chemicals Corporation, with a density of approximately 0.917 g / cc and a melt index (I2) of approximately 0.60 dg / min. Layers 4, 6, and 8 also contained 20 wt.% BYNEL® 41E710, a maleic anhydride grafted LLDPE available from DuPont Packaging & Industrial Polymers, with a density of 0.912 g / cc and a melt index (I2) of 2.7 dg / min. Layers 5 and 9 contained Ultramid C40L, a nylon (polyamide 6 / 66) available from BASF Corporation, with a melt index (I2) of 1.1 dg / min. The multilayer die technology consisted of a pancake die, a FLEX-STACK co-extrusion die (SCD), with flow channels machined on both sides of the plate, a die tool diameter of 6.3 inches, a die gap of 85 mils consistently used in this disclosure, the film was produced at a blow-up ratio (BUR) of 2.5, and the line output speed was kept constant at 250 lb / hour.The specifications of the nine extruders were as follows: 1.5-inch diameter screw, 30 / 1 length-to-diameter ratio, 7-polyethylene screw and MADDDOX® mixer with single flight, 2-nylon screw, the extruders were air-cooled and equipped with 20-HP motors, and all extruders were equipped with gravitational blenders. The nip and folding frame included a DECATEX horizontal vibrating take and a pearl cooling slat directly below the nip. The line was equipped with a turret winder and vibrating slitter knife. Table 19 summarizes the temperature settings used. All die temperatures, i.e., layer section, mandrel bottom, mandrel, inner lip and outer lip, were maintained at a constant 480°F.

[0302] End users often desire improvements and / or a specific balance of several film properties. These include, but are not limited to, optical properties, melting point at a given density, heat seal and hot tack properties, etc. More specifically, in the packaging industry, there is a need to improve the heat seal and hot tack properties of films. For example, it is particularly desirable to lower the seal initiation temperature (SIT) and widen the hot tack window while maintaining or improving other film properties such as stiffness, toughness, and optical properties.

[0303] Table 20 discloses the cold seal data and seal start temperature (SIT) for four 9-layer films encoded as (i) to (iv). Layer 1 of film (i), which is the sealant layer, contained a binary blend of 70 wt.% Example 1 and 30 wt.% Comparative 5, the latter being SCLAIR FP120 (0.920 g / cc and 1.0I2), and layer 1 also contained the additives described above. Layer 1 of film (i) had a blend density of approximately 0.909 g / cc. Surprisingly, as shown in Figure 7, the cold seal curves of film (i) and comparative film (ii) were essentially equivalent, which is surprising considering that layer 1 of film (ii) was 0.906 g / cc. Furthermore, as shown in Table 20, the SITs of films (i) and (ii) are essentially equivalent, namely 92.4°C and 92.2°C, respectively, which is also surprising considering the difference in the density of layer 1, namely 0.909 g / cc versus 0.906 g / cc, respectively. More specifically, there are many examples in the field of polyethylene films that disclose that the seal onset temperature (SIT) increases as the density of the film (i.e., sealant layer) increases, and Figure 7 demonstrates this trend, namely that the cold seal curve of film (iv) with a layer 1 density of 0.914 g / cc shifts to a higher temperature, resulting in a SIT of 102.5°C (Table 20).

[0304] Figure 7 and Table 20 demonstrate at least two advantages of the ethylene interpolymer products disclosed herein, specifically, (a) that, at a given SIT, films (or layers) with higher density are preferable because they are more rigid and easier to process through packaging equipment than comparative films with lower density (film(i)), and (b) that the ethylene interpolymer products disclosed herein can be diluted with higher density LLDPE, i.e., the overall cost of the sealant resin formulation can be reduced.

[0305] In high-speed vertical and horizontal pouch-filling processes where products (liquids, solids, pastes, parts, etc.) are loaded and sealed into pouch-like packaging, specific hot tack characteristics are desired. For example, the packaging industry requires sealant resins with a wide hot tack window, meaning such resins consistently produce leak-proof packaging even when various parameters are changed in the packaging equipment. Furthermore, it is desirable that the hot tack onset temperature (HTO(°C)) occurs at the lowest possible temperature. High-temperature hot tack that maintains sufficient seal strength even at high temperatures is also desirable. Poor hot tack characteristics often limit the product speed on the packaging line.

[0306] Table 21 discloses hot tack data, hot tack start (HTO) temperature, and notes regarding the type of defect in the 9-layer film. Surprisingly, the HTO temperatures for films (iii) and (ii) were similar, namely 86.3°C and 86.8°C, respectively, which is surprising considering the difference in density of layer 1, namely 0.913 g / cc and 0.906 g / cc, respectively. This is surprising because, in the art of polyethylene films, it is disclosed that the HTO temperature of a film (or layer) increases as the film (or layer) density increases. The hot tack curves for film (iii), including Example 5, and film (ii), including Comparison 15, are shown in Figure 8. Even with a higher density in Example 5 (film (iii)), the width of the hot tack window for Example 5 was similar to that of Comparison 15 (film (ii)).

[0307] [Table 1] [Table 2A] [Table 2B] [Table 2C] Table 3 Table 4 Table 5A Table 5B Table 6A Table 6B Table 6C Table 7A Table 7B Table 8A Table 8B Table 9 Table 10 Table 11A [Table 11B] [Table 12] [Table 13] [Table 14] [Table 15] [Table 16] [Table 17] [Table 18] [Table 19] [Table 20] [Table 21] [Industrial applicability]

[0308] The ethylene interpolymer products disclosed herein have industrial applicability in a wide range of manufactured products, from flexible to rigid applications.

Claims

1. First ethylene interpolymer, second ethylene interpolymer, and an ethylene / α-olefin interpolymer product comprising a third ethylene interpolymer, The following ethylene / α-olefin interpolymer products, including a to d: a) Dimensionless melt flow - intrinsic viscosity index MFIVI between 0.05 and 0.6 as defined by Equation 1 [Math 1] (In the formula, f 二峰性 It is defined by equation 2, [Math 2] The polydispersibility of the ethylene / α-olefin interpolymer product is Pd (in formula 2) = M ｗ / M ｎ And M ｗ and M ｎ These are the weight-average and number-average molecular weights, respectively, and are determined by size exclusion chromatography (SEC); Correction factor C ｆ (In Equation 2) is determined according to the following two steps (i) and (ii): (i) Melt flow distribution function of the ethylene / α-olefin interpolymer product as defined by Equation 3 [Math 3] However, Log(1 / I ｎ It is determined by plotting ) versus Log (load), I ｎ These are the measured melt indices of the ethylene / α-olefin interpolymer product at loads of 21600, 10000, 6000, and 2160 grams, measured at 190°C according to ASTM D1238. (ii) The first derivative of the melt flow distribution function is defined by Equation 4, [Math 4a] The correction coefficient C ｆ (Equation 2) is the value of the first derivative (Equation 4) under a load of 4000 g; The comonomer weight percentage, comonomer Wt% (Formula 1) is the weight percentage of the comonomer in the ethylene / α-olefin interpolymer product, measured by FTIR according to ASTM D6645, and when the comonomer Wt% is greater than 14.95%, the comonomer coefficient f コモノマー (Equation 1) is defined by Equation 5, and when the comonomer Wt% is 14.95% or less, the comonomer coefficient is defined by Equation 6, [Math 5] The fitted melt index I of the ethylene / α-olefin interpolymer product ｆ Equation (1) is determined by the value of the melt flow distribution function (Equation 3) at a load of 4000 g; IV and M ｖ (Equation 1) represents the intrinsic viscosity and viscosity-average molar mass of the ethylene / α-olefin interpolymer product, respectively, as determined by 3D-SEC (triple detection size exclusion chromatography); b) The first derivative (Equation 4) at a load of 4000g having a value greater than -1.500 and less than or equal to -1.25; [Math 4B] c) The sum of unsaturated atoms defined by Equation 7, where the unsaturated concentration is 0.010 or more and less than 0.045 per 100 carbon atoms. Ｕ [Number 7] In the formula, I Ｕ SC Ｕ and T Ｕ These are the amounts of internal, side-chain, and terminal unsaturation per 100 carbon atoms in the ethylene / α-olefin interpolymer product as determined by ASTM D3124-98 and ASTM D6248-98, respectively; and d) A residual catalyst metal of hafnium in a concentration of 0.03 ppm or more and 5 ppm or less, which is measured using neutron activation.

2. The ethylene / α-olefin interpolymer product according to claim 1, wherein the ethylene / α-olefin interpolymer product has a melt index of 0.3 to 500 dg / min and a density of 0.855 to 0.975 g / cc, the melt index being measured according to ASTM D1238 (at a load of 2.16 kg and 190°C), and the density being measured according to ASTM D792.

3. The ethylene / α-olefin interpolymer product according to claim 1, further comprising 2.6 to 25 mole percent of one or more types of α-olefins.

4. One or more types of α-olefins are C ３ ~C １０ The ethylene / α-olefin interpolymer product according to claim 3, comprising an α-olefin.

5. The ethylene / α-olefin interpolymer product according to claim 4, wherein one or more α-olefins are 1-hexene, 1-octene, or a mixture of 1-hexene and 1-octene.

6. The ethylene / α-olefin interpolymer product has a polydisperse M of 1.7 to 25. ｗ / M ｎ It has a weight-average molecular weight M ｗ and number average molecular weight M ｎ The ethylene / α-olefin interpolymer product according to claim 1, wherein the size is measured using conventional size exclusion chromatography.

7. CDBI containing 1% to 98% ethylene / α-olefin interpolymer products ５０ It has CDBI ５０ This is measured using CRYSTAF (crystallization analysis fractionation) and TREF (temperature-induced elution fractionation), and the CDBI ５０ The ethylene / α-olefin interpolymer product according to claim 1, wherein is a percentage of ethylene interpolymer whose composition is within 50% of the central comonomer composition.

8. A method for producing the ethylene / α-olefin interpolymer product described in claim 1, The ethylene / α-olefin interpolymer product is produced by a solution polymerization process. The first ethylene interpolymer is produced in the first reactor, the second ethylene interpolymer is produced in the second reactor, and the third ethylene interpolymer is produced in the third reactor, and The first and second ethylene interpolymers, or the first and third ethylene interpolymers, are synthesized using a crosslinked metallocene catalyst formulation. method.

9. The method according to claim 8, wherein the crosslinked metallocene catalyst formulation comprises component A defined by formula (Ia) or formula (Ib): 【Chemistry 1】 or 【Chemistry 2】 During the ceremony, M is Hf; G is C, Si, Ge, Sn, or Pb; X is a halogen atom; R ６ Each time they appear, H and C appear independently. １～２０ Hydrocarbyl group, C １～２０ Alkoxy group, or C ６～１０ Selected from aryloxide groups, the group may be linear, branched, or cyclic, or a halogen atom, C １～１０ alkyl group, C １～１０ Alkoxy group, C ６～１０ Further substituted with an aryl or aryloxy group; R １ H, C １～２０ Hydrocarbyl group, C １～２０ Alkoxy group, C ６～１０ An aryl oxide group, or at least one silicon atom and C ３～３０ It is an alkylsilyl group containing a carbon atom; R ２ and R ３ These are H and C, independently. １～２０ Hydrocarbyl group, C １～２０ Alkoxy group, C ６～１０ An aryl oxide group, or at least one silicon atom and C ３～３０ Selected from alkylsilyl groups containing carbon atoms; R ４ and R ５ These are H and C, independently. １～２０ Hydrocarbyl group, C １～２０ Alkoxy group, C ６～１０ An aryl oxide group, or at least one silicon atom and C ３～３０ Selected from alkylsilyl groups containing carbon atoms, method.

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