Solution-phase polymerization process

Abstract

This disclosure describes a continuous solution-phase polymerization process for providing an ethylene polymer product comprising a first ethylene polymer and a second ethylene polymer. The continuous solution-phase polymerization process is carried out by injecting a crosslinked metallocene catalyst formulation, ethylene, and a process solvent into a first reactor, and injecting a second mixed feed stream containing the first heterogeneous catalyst formulation, ethylene, and the process solvent into a second reactor. The second feed stream is injected into the second reactor at a specified ethylene concentration and temperature range, thereby reducing the frequency of non-oxidized polyethylene defects in the final ethylene polymer product.

Description

[Technical Field]

[0001] Provided herein is a continuous solution-phase polymerization process for producing a multicomponent ethylene polymer product characterized by a reduced level of non-oxidized polyethylene defects, utilizing at least two reactors with a crosslinked metallocene catalyst formulation and a first heterogeneous catalyst formulation. [Background technology]

[0002] It is well known to those skilled in the art that it is desirable to provide ethylene polymer products with a wide melting interval, which is particularly advantageous for improving performance in film applications, such as heat sealing applications. One method for obtaining such ethylene polymer products is to use two or more different polymerization catalysts in one or more polymerization reactors. For example, it is known to use metallocene-type polymerization catalysts and heterogeneous-type polymerization catalysts in at least two different solution-phase polymerization reactors. These processes may generate very small amounts of ultra-high molecular weight polymers (i.e., polymer species with a weight-average molecular weight greater than 10⁶ g / mol) that may have a different chemical composition from the bulk ethylene polymer product produced. These species are generally miscible with the ethylene polymer product and result in visual defects in thin-walled articles and films. Therefore, there is still a need for improved solution-phase polymerization processes to reduce the tendency for these ultra-high molecular weight species to be generated and mixed in. [Overview of the Initiative]

[0003] Provided in a first embodiment of the present disclosure is a continuous solution-phase polymerization process for providing an ethylene polymer product, wherein the ethylene polymer product comprises a first ethylene polymer and a second ethylene polymer, the process comprising: a) injecting a crosslinked metallocene catalyst formulation, a process solvent, and ethylene into a first reactor to generate a first outlet stream containing the first ethylene polymer in the process solvent; and b) passing the first outlet stream through a second reactor and injecting a first heterogeneous catalyst formulation and a second feed stream into the second reactor to generate a second outlet stream containing the second ethylene polymer and the first ethylene polymer in the process solvent, the second feed stream being produced by combining the process solvent and ethylene, wherein the ethylene concentration in the second feed stream is 25% by weight or less based on the total weight of the second feed stream injected into the second reactor per unit time, and the temperature of the second feed stream is 60°C or higher and 90°C or lower.

[0004] Provided in a second aspect of the present disclosure is a continuous solution-phase polymerization process for providing an ethylene polymer product, wherein the ethylene polymer product comprises a first ethylene polymer and a second ethylene polymer, the process comprising: a) injecting a crosslinked metallocene catalyst formulation, a process solvent, and ethylene into a first reactor to generate a first outlet stream containing the first ethylene polymer in the process solvent; b) injecting a first heterogeneous catalyst formulation and a second feed stream into a second reactor to generate a second outlet stream containing the second ethylene polymer in the process solvent, the second feed stream being produced by combining the process solvent and ethylene; and c) combining the first outlet stream and the second outlet stream to form a third outlet stream, wherein the ethylene concentration in the second feed stream is 25% by weight or less based on the total weight of the second feed stream injected into the second reactor per unit time, and the temperature of the second feed stream injected into the second reactor is 60°C or higher and 90°C or lower.

[0005] In some embodiments, the process involves one or more C3-C3s in the first reactor.10 further comprises injecting an α-olefin of

[0006] In some embodiments, the second feed stream has a relative concentration of ethylene to one or more C3-C 10 α-olefins of 0.15 or more and 2 or less based on the ratio of the weight percentage of ethylene and the weight percentage of one or more C3-C 10 α-olefins.

[0007] In some embodiments, the C3-C 10 α-olefin is selected from 1-hexene, 1-octene, or a mixture of 1-hexene and 1-octene.

[0008] In some embodiments, the second feed stream injected into the second reactor contains hydrogen at a concentration of 0.1 to 20 ppm based on the total weight of the second feed stream injected into the second reactor per unit time.

[0009] In some embodiments, the crosslinked metallocene catalyst formulation comprises component A defined by formula (I):

Chemical formula

[0010] In some embodiments, the crosslinked metallocene catalyst formulation comprises component A defined by formula (II): [ka] (In the formula, G is a Group 14 element selected from carbon, silicon, germanium, tin, or lead; R1 is a hydrogen atom, C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radicals, or C 6-10 It is an aryl oxide radical; R2 and R3 are hydrogen atoms, C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 Independently selected from aryl oxide radicals; R4 and R5 are hydrogen atoms, unsubstituted C 1-20 Hydrocarbyl radical, substituted C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 The catalyst comprises an aryl oxide radical (independently selected from aryl oxide radicals; Q is independently an activatable leaving ligand), an almoxane cocatalyst, a boron ionic activator, and optionally a hindered phenol.

[0011] In some embodiments, the molar ratio of the boron ionic activator to component A in the first reactor is 0.1:1 to 10:1, the molar ratio of the almoxane cocatalyst to component A in the first reactor is 1:1 to 1000:1, and, if present, the molar ratio of the hindered phenol to the almoxane cocatalyst in the first reactor is 0.0:1 to 10:1.

[0012] In some embodiments, the almoxane cocatalyst is a methylalmoxane.

[0013] In some embodiments, the boron ionic surfactant is trityltetrakis(pentafluorophenyl)borate.

[0014] In some embodiments, the first heterogeneous catalyst formulation is a first in-line Ziegler-Natta catalyst formulation.

[0015] In some embodiments, the first in-line Ziegler-Natta catalyst formulation is formed by an in-line process, the in-line process comprising: a first step of the first heterogeneous catalyst assembly, in which flow S1 and flow S2 are combined to form a first product mixture, and the first product mixture is equilibrated for HUT-1 seconds, wherein flow S1 contains a magnesium compound and an aluminum alkyl in the process solvent, and flow S2 contains a chloride compound in the process solvent; and a second step of the first heterogeneous catalyst assembly, the first product mixture is flowed The process comprises: a step of combining with S3 to form a second product mixture and equilibrating the second product mixture for HUT-2 seconds, wherein flow S3 contains a metal compound in the process solvent; and a step of combining the second product mixture with flow S4 in a third stage of the first heterogeneous catalyst assembly to form a first in-line Ziegler-Natta catalyst formulation and equilibrating the in-line Ziegler-Natta catalyst formulation for HUT-3 seconds before injecting it into a second reactor, wherein flow S4 contains an alkylaluminum co-catalyst in the process solvent.

[0016] In some embodiments, the first in-line Ziegler-Natta catalyst formulation is formed in an in-line process, the in-line process comprising: a first step of the first heterogeneous catalyst assembly, in which flow S1 is combined with flow S2 to form a first product mixture, and the first product mixture is equilibrated for HUT-1 seconds, wherein flow S1 contains a magnesium compound and an aluminum alkyl in the process solvent, and flow S2 contains a chloride compound in the process solvent; and a second step of the first heterogeneous catalyst assembly, the first product The process comprises: forming a second product mixture by combining a mixture with flow S3, and equilibrating the second product mixture for HUT-2 seconds, wherein flow S3 contains a metal compound in the process solvent; and forming a first in-line Ziegler-Natta catalyst formulation in a second reactor, wherein the second product mixture is further equilibrated for HUT-3 seconds in a third stage of the first heterogeneous catalyst assembly and injected into the second reactor, and flow S4 containing an alkylaluminum co-catalyst in the process solvent is independently injected into the second reactor.

[0017] In some embodiments, HUT-1 is approximately 5 seconds to approximately 70 seconds, HUT-2 is approximately 2 seconds to approximately 50 seconds, and HUT-3 is approximately 0.5 seconds to approximately 15 seconds.

[0018] In some embodiments, the magnesium compound is of the formula Mg(R 1 ) Defined by 2 (where R 1 The groups may be the same or different), aluminum alkyl, formula Al(R 3 ) Defined in 3 (in the formula, R 3 The groups may be the same or different), the chloride compound is of formula R 2 Defined by Cl, metal compounds are given by formula M * (X) n Or M * O(X) n Defined by (where M *represents titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, or a mixture thereof, O represents oxygen, X represents chloride or bromide, and n is an integer that satisfies the oxidation state of metal M * (), the alkylaluminum cocatalyst has the formula Al(R 4 ) p (OR 5 ) q (X) r defined by (where the R 4 groups may be the same or different, the OR 5 groups may be the same or different, and (p + q + r) = 3, provided that p is greater than 0), where R 1 , R 2 , R 3 , R 4 , and R 5 represent hydrocarbyl groups having 1 to 10 carbon atoms.

[0019] In some embodiments, M * in the metal compound represents titanium, zirconium, hafnium, vanadium, chromium, or a mixture thereof.

[0020] In some embodiments, the ethylene concentration in the second feed stream injected into the second reactor is less than 21 weight percent and greater than 15 weight percent based on the total weight of the second feed stream injected into the second reactor per unit time.

[0021] In some embodiments, the first outlet stream has a first temperature T1, the second outlet stream has a second temperature T2, and T1 and T2 satisfy the inequality 45 < T2 - T1 < 70.

[0022] In some embodiments, the process further includes passing a second outlet stream from step b) of the process as defined in the first embodiment through a third reactor and optionally injecting ethylene, a process solvent, one or more α-olefins, hydrogen, and a second heterogeneous catalyst mixture into the third reactor to generate a fourth outlet stream containing any third ethylene polymer, second ethylene polymer, and first ethylene polymer in the process solvent.

[0023] In some embodiments, the process further includes passing a third outlet stream from step c) of the process as defined in the second embodiment through a third reactor and optionally injecting ethylene, a process solvent, one or more α-olefins, hydrogen, and a second heterogeneous catalyst mixture into the third reactor to generate a fourth outlet stream containing any third ethylene polymer, second ethylene polymer, and first ethylene polymer in the process solvent.

[0024] In some embodiments, the second heterogeneous catalyst formulation, if present, is the first in-line Ziegler-Natta catalyst.

[0025] In some embodiments, the first and second reactors are operated adiabatically.

[0026] In some embodiments, the third reactor is operated adiabatically. [Brief explanation of the drawing]

[0027] [Figure 1] This disclosure shows a continuous solution-phase polymerization process according to one embodiment. [Modes for carrying out the invention]

[0028] <Definition of Terms> Unless otherwise stated, all numbers or expressions relating to the quantities of ingredients, process conditions, etc., used herein and in the claims shall be understood in all cases to be modified by the term “approximately.” Therefore, unless otherwise stated, the numerical parameters described herein and in the appended claims are approximations that may vary depending on the desired characteristics that various embodiments wish to achieve. Each numerical parameter should be interpreted, at least by applying ordinary rounding techniques, taking into account the reported significant figures, not as an attempt to limit the application of the doctrine of equivalents to the claims. The numerical values ​​described in the specific examples are reported as accurately as possible. However, each numerical value inherently contains errors that inevitably arise from the standard deviation found in each test measurement. It should be understood that any numerical range described herein is intended to include all subranges contained therein. For example, the range “1 to 10” is intended to include all subranges between the stated minimum value of 1 and the stated maximum value of 10, i.e., the minimum value is greater than or equal to 1 and the maximum value is less than or equal to 10.

[0029] Since the disclosed numerical ranges are continuous, they include all values ​​between the minimum and maximum values. Unless otherwise specified, the various numerical ranges specified in this application are approximations.

[0030] All compositional ranges expressed herein are in practice limited to a total of 100 percent (volume or weight) and not exceeding 100 percent. Where multiple components may be present in a composition, the sum of the maximum amounts of each component may exceed 100 percent, assuming, as is readily apparent to those skilled in the art, that the amounts of components actually used conform to a maximum of 100 percent.

[0031] To form a more complete understanding of this disclosure, the following terms are defined and should be used together with the accompanying drawings and the descriptions of the various embodiments throughout.

[0032] As used herein, the term “monomer” refers to a small molecule that can react chemically and chemically bond with itself or other monomers to form polymers. As used herein, the terms “α-olefin” or “alpha-olefin” are used to describe monomers having a linear hydrocarbon chain containing 3 to 20 carbon atoms with a double bond at one end of the chain; the equivalent term is “linear α-olefin.”

[0033] As used herein, the term “ethylene polymer” refers to a polymer produced from ethylene monomer and optionally one or more additional monomers, regardless of the specific catalyst or process used to produce the ethylene polymer.

[0034] In the field of polyethylene, one or more additional monomers are called "comonomers" and often include α-olefins. The term "homopolymer" refers to a polymer containing only one monomer. "Ethylene homopolymers" are made using only ethylene as the polymerizable monomer. The term "copolymer" refers to a polymer containing two or more monomers. "Ethylene copolymers" are made using ethylene and one or more other types of polymerizable monomers.

[0035] Common ethylene polymers include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), extremely low-density polyethylene (ULDPE), plastomers, and elastomers.

[0036] The term "ethylene polymer" also includes ethylene terpolymers, which contain two or more comonomers in addition to ethylene. The term "ethylene polymer" also includes combinations or blends of the above polymers.

[0037] The term "heterogeneously branched ethylene polymers" refers to a subset of polymers in the ethylene polymer group produced using heterogeneous catalytic systems, and non-limiting examples include Ziegler-Natta or chromium catalysts, both of which are well known in the art.

[0038] The term "uniformly branched ethylene polymer" refers to a subset of polymers in the ethylene polymer group produced using single-site catalysts, and non-limiting examples include non-crosslinked metallocene catalysts, crosslinked metallocene catalysts, and phosphine imine catalysts, all of which are well known in the art.

[0039] Typically, uniformly branched ethylene polymers have a narrow molecular weight distribution, and for example, in conventional gel permeation chromatography (GPC) w / M n The value is less than approximately 2.8, especially less than approximately 2.3, but exceptions may occur, M w and M n These refer to weight-average molecular weight and number-average molecular weight, respectively.

[0040] In contrast, the M of heterogeneously branched ethylene polymers w / M n Typically, this is a homogeneous ethylene polymer M w / M n It is larger than that. Generally, uniformly branched ethylene polymers have a narrow compositional distribution, meaning that each polymer within the molecular weight distribution has a similar comonomer content. Often, the Compositional Distribution Breadth Index (CDBI) is used to quantify how comonomers are distributed within an ethylene polymer and to distinguish ethylene polymers produced by different catalysts or processes.

[0041] "CDBI" 50" is defined as the percentage of ethylene polymer whose composition is within 50 wt% of the median comonomer composition, and this definition is consistent with the definition set forth in WO93 / 03093, assigned to Exxon Chemical Patents Inc. CDBI of Ethylene Copolymers 50 This can be calculated from the TREF (Temperature Rising Elution Fractionation) curve, and the TREF method is described in Wild et al., J. Polym. Sci., Part B, Polym. Phys., Vol. 20(3), pp. 441-455.

[0042] Typically, CDBI of uniformly branched ethylene polymers. 50 The percentage is over 70% or over 75%. In contrast, the CDBI of heterogeneously branched ethylene polymers containing α-olefins is... 50 Generally, CDBI is a homogeneous ethylene polymer. 50 It is lower than that. For example, the CDBI of a non-uniformly branched ethylene polymer. 50 This could be less than approximately 75%, or less than approximately 70%.

[0043] As is well known to those skilled in the art, uniformly branched ethylene polymers are often further subdivided into “linear homogeneous ethylene polymers” and “substantially linear homogeneous ethylene polymers.” Long-chain branches are essentially polymers, i.e., their length is similar to the polymer to which they are bonded. Hereinafter, the terms “uniformly branched polyethylene” or “uniformly branched ethylene polymer” refer to both linear homogeneous ethylene polymers and substantially linear homogeneous ethylene polymers.

[0044] As used herein, the terms “hydrocarbyl,” “hydrocarbyl radical,” or “hydrocarbyl group” refer to linear or cyclic aliphatic, olefin, acetylene, and aryl (aromatic) radicals comprising hydrogen and one hydrogen-deficient carbon.

[0045] As used herein, “alkyl radical” includes linear, branched, and cyclic paraffinic radicals lacking one hydrogen radical, and non-limiting examples include methyl (-CH3) and ethyl (-CH2CH3) radicals. The term “alkenyl radical” refers to linear, branched, and cyclic hydrocarbons containing at least one carbon-carbon double bond lacking one hydrogen radical.

[0046] As used herein, the term “aryl” group includes phenyl, naphthyl, pyridyl, and other radicals whose molecules have an aromatic ring structure, with non-limiting examples including naphthylene, phenanthrene, and anthracene. An “arylalkyl” group is an alkyl group pendanted by an aryl group, with non-limiting examples including benzyl, phenethyl, and tolylmethyl. An “alkylaryl” group is an aryl group pendanted by one or more alkyl groups, with non-limiting examples including tolyl, xylyl, mesityl, and cumyl.

[0047] 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 radical that contains a heteroatom and may contain one or more identical 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. Non-limiting examples of heteroatom-containing groups include radicals such as imines, amines, oxides, phosphines, ethers, ketones, oxoazoline heterocyclic compounds, oxazolines, and thioethers. The term “heterocyclic” refers to a cyclic 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.

[0048] As used herein, the term “unsubstituted” means that a hydrogen radical is bonded to the molecular group following the term “unsubstituted.” The term “substituted” means that the group following the term has one or more moieties (non-hydrogen radicals) that replace one or more hydrogen radicals at any position within the group. Non-exclusive examples of moieties include halogen radicals (F, Cl, Br), hydroxyl groups, carbonyl groups, carboxyl groups, silyl groups, amine groups, phosphine groups, alkoxy groups, phenyl groups, naphthyl groups, C1-C 30 Alkyl alkyl groups, C2-C 30 This includes alkenyl groups and combinations thereof. Non-limiting examples of substituted alkyl and aryl include acyl radicals, alkylsilyl radicals, alkylamino radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- and dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, arylamino radicals, and combinations thereof.

[0049] <Detailed explanation> This disclosure provides an ethylene polymer product by a continuous solution-phase polymerization process, the ethylene polymer product comprising a first ethylene polymer and a second ethylene polymer. This process uses a first reactor and a second reactor, which may be configured in series or in parallel with each other. A crosslinked metallocene catalyst formulation produces a first ethylene polymer in the first reactor, and a first heterogeneous catalyst formulation produces a second ethylene polymer in the second reactor. In some embodiments, the ethylene polymer product may further include an optional third ethylene polymer produced in a third reactor. The optional third ethylene polymer may be produced using a second heterogeneous catalyst formulation, which may be the same as or different from the first heterogeneous catalyst formulation.

[0050] The ethylene polymer product, the ethylene polymer components constituting the ethylene polymer product, and the catalyst formulation used to produce the ethylene polymer components will be described further below.

[0051] <Cross-linked metallocene catalyst formulation> In one embodiment of the present disclosure, the crosslinked metallocene catalyst formulation comprises component A having formula (I): [ka]

[0052] In formula (I), M is a group 4 metal selected from titanium, zirconium, or hafnium; G is a group 14 element selected from carbon, silicon, germanium, tin, or lead; R1 is a hydrogen atom, C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radicals, or C 6-10 It is an aryl oxide radical; R2 and R3 are hydrogen atoms, C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 Independently selected from aryl oxide radicals; R4 and R5 are hydrogen atoms, unsubstituted C 1-20 Hydrocarbyl radical, substituted C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 It is independently selected from the aryl oxide radical; Q is independently an activatable leaving ligand.

[0053] In one embodiment, R4 and R5 are independently aryl groups.

[0054] In one embodiment, R4 and R5 are independently a phenyl group or a substituted phenyl group.

[0055] In one embodiment, R4 and R5 are phenyl groups.

[0056] In one embodiment, R4 and R5 are independently substituted phenyl groups.

[0057] In one embodiment, R4 and R5 are substituted phenyl groups, and the phenyl groups are substituted with substituted silyl groups.

[0058] In one embodiment, R4 and R5 are substituted phenyl groups, and the phenyl groups are substituted with trialkylsilyl groups.

[0059] In one embodiment, R4 and R5 are substituted phenyl groups, and the phenyl groups are substituted with a trialkylsilyl group at the para position. In one embodiment, R1 and R2 are substituted phenyl groups, and the phenyl groups are substituted with a trimethylsilyl group at the para position. In one embodiment, R1 and R2 are substituted phenyl groups, and the phenyl groups are substituted with a triethylsilyl group at the para position.

[0060] In one embodiment, R4 and R5 are independently alkyl groups.

[0061] In one embodiment, R4 and R5 are independently alkenyl groups.

[0062] In one embodiment, R1 is hydrogen.

[0063] In one embodiment, R1 is an alkyl group.

[0064] In one embodiment, R1 is an aryl group.

[0065] In one embodiment, R1 is an alkenyl group.

[0066] In one embodiment, R2 and R3 are independently hydrocarbyl groups having 1 to 30 carbon atoms.

[0067] In one embodiment, R2 and R3 are independently aryl groups.

[0068] In one embodiment, R2 and R3 are independently alkyl groups.

[0069] In one embodiment, R2 and R3 are independently alkyl groups having 1 to 20 carbon atoms.

[0070] In one embodiment, R2 and R3 are independently a phenyl group or a substituted phenyl group.

[0071] In one embodiment, R2 and R3 are tert-butyl groups.

[0072] In one embodiment, R2 and R3 are hydrogen.

[0073] In one embodiment, M is hafnium (Hf).

[0074] In one embodiment of the present disclosure, the crosslinked metallocene catalyst formulation comprises component A having formula (II): [ka]

[0075] In formula (II), G is a Group 14 element selected from carbon, silicon, germanium, tin, or lead; R1 is a hydrogen atom, C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radicals, or C 6-10 It is an aryl oxide radical; R2 and R3 are hydrogen atoms, C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 Independently selected from aryl oxide radicals; R4 and R5 are hydrogen atoms, unsubstituted C 1-20 Hydrocarbyl radical, substituted C 1-20 Hydrocarbyl radical, C 1-20 Alkyl radical or C 6-10 It is independently selected from the aryl oxide radical; Q is independently an activatable leaving ligand.

[0076] In the present disclosure, the term "activatable" means that the ligand Q can be cleaved from the metal center M via a protolysis reaction, or can be withdrawn from the metal center M by an appropriate acidic or electrophilic catalytically active compound (also known as a "cocatalyst" compound), respectively, and examples of each are described below. The activatable ligand Q can also be converted into another ligand that is cleaved or withdrawn from the metal center M (e.g., a halide can be converted into an alkyl group). Without wishing to be bound by a single theory, the protolysis or withdrawal reaction produces an active "cationic" metal center that can polymerize olefins.

[0077] In an embodiment of the present disclosure, the activatable ligand Q is independently selected from the group consisting of: a hydrogen atom; a halogen atom; C 1~20 hydrocarbyl radical, C 1~20 alkoxy radical, and C 6-10 aryl or aryloxy radical, where each of the hydrocarbyl, alkoxy, aryl, or aryloxide radical may be unsubstituted or further substituted with one or more halogens or other groups; C 1-8 alkyl; C 1-8 alkoxy; C 6-10 aryl or aryloxy; an amide or phosphide radical, provided that Q is not cyclopentadienyl. Also, two Q ligands may be bonded to each other to form, for example, a substituted or unsubstituted diene ligand (e.g., 1,3-butadiene); or a delocalized heteroatom-containing group such as an acetate or acetamidinato group. In a preferred embodiment of the present disclosure, each Q is independently selected from the group consisting of a halide atom, C 1~4 alkyl radical and benzyl radical. Particularly suitable activatable ligands Q are monoanionic, such as halides (e.g., chloride) or hydrocarbyls (e.g., methyl, benzyl).

[0078] In one embodiment of this disclosure, component A is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dichloride having the following molecular formula: [(2,7-tBu2Flu)Ph2C(Cp)HfCl2].

[0079] In one embodiment of this disclosure, component A is diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafniumdimethyl having the following molecular formula: [(2,7-tBu2Flu)Ph2C(Cp))HfMe2].

[0080] In addition to the crosslinked metallocene catalyst molecule itself (component A as defined above), the crosslinked metallocene catalyst compound may further contain one or more of the following: alkylaluminoxane co-catalyst (component M) and boron ionic activator (component B). The homogeneous catalyst system may optionally contain hindered phenol (component P).

[0081] Although the precise structure of alkylaluminoxanes is unknown, experts in the field generally agree that they are oligomeric species containing repeating units of the following general formula: (R)2AlO-(Al(R)-O) n -Al(R)2 (wherein the formula, the R group may be the same or different linear, branched, or cyclic hydrocarbyl radicals containing 1 to 20 carbon atoms, and n is 0 to about 50). A non-limiting example of alkylaluminoxane is methylaluminoxane (or MAO), where each R group is a methyl radical.

[0082] In one embodiment of the present disclosure, R of the alkylaluminoxane is a methyl radical, and m is 10 to 40.

[0083] In one embodiment of this disclosure, the cocatalyst is a modified methylaluminoxane (MMAO).

[0084] It is well known in the art that an alkylaluminoxane can serve a dual role as both an alkylating agent and an activator. Thus, alkylaluminoxane cocatalysts are often used in combination with activatable ligands such as halogens.

[0085] Generally, boron ionic activators are composed of a cation and a bulky anion, the latter being substantially non-coordinating. Non-limiting examples of boron ionic activators are four-coordinate boron ionic activators having four ligands bonded to a boron atom. Non-limiting examples of boron ionic activators include the following plurality of formulas: [R 5 + [B(R 7 )4] - (where B represents a boron atom, R 5 is an aromatic hydrocarbyl (e.g., triphenylmethyl cation), and each R 7 is independently selected from: phenyl radicals substituted with 3 to 5 substituents selected from unsubstituted or fluorine atoms, C 1~4 alkyl or alkoxy radicals unsubstituted or substituted with fluorine atoms, and silyl radicals of the formula -Si(R 9 )3, where each R 9 is independently selected from a hydrogen atom and C 1-4 alkyl radicals), and [(R 8 ) t ZH] + [B(R 7 )4] - (where B is a boron atom, H is a hydrogen atom, Z is a nitrogen or phosphorus atom, t is 2 or 3, R 8 is a C 1~8 alkyl radical, a phenyl radical unsubstituted or substituted with up to 3 C 1-4 alkyl radicals, or one R 8 may form anilinium radical together with a nitrogen atom, R 7 ​(This is defined above).

[0086] In both equations, R 7A non-limiting example is the pentafluorophenyl radical. In general, boron ionic surfactants can be described as salts of tetra(perfluorophenyl)boron, and non-limiting examples include anilinium, carbonium, oxonium, phosphonium, and sulfonium salts of tetra(perfluorophenyl)boron with anilinium and trityl (or triphenylmethylium). Additional non-limiting examples of boroionic 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-diethylanilinium tetra(phenyl)boron. Tylanilinium 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 tetrakisspentafluorophenylborate, triphenylmethylium tetrakisspentafluorophenylborate, benzene(diazonium) tetrakisspentafluorophenylborate, tropylium tetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium) tetrakis(3,4,Examples include 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 commercially produced boron ionic surfactants include N,N-dimethylanilinium tetrakispentafluorophenyl borate and triphenylmethylium tetrakispentafluorophenyl borate.

[0087] Non-limiting examples of hindered phenols include butylated phenol antioxidants, butylated hydroxytoluene, 2,6-di-tert-butyl-4-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.

[0088] To produce an active crosslinked metallocene catalyst formulation, the amounts and molar ratios of three or four components, component A, component M, component B, and any component P, are optimized.

[0089] <First and second heterogeneous catalyst formulations> Suitable first and second heterogeneous catalyst formulations include numerous heterogeneous catalyst formulations well known to those skilled in the art. Non-limiting examples include Ziegler-Natta catalysts and chromium catalyst formulations.

[0090] Embodiments of this disclosure include in-line Ziegler-Natta catalyst formulations. The term “in-line Ziegler-Natta catalyst formulation” refers to the continuous synthesis of a small amount of activated Ziegler-Natta catalyst and the immediate injection of this catalyst into at least one continuous-operating reactor, where the catalyst polymerizes ethylene with one or more optionally selected α-olefins to produce an ethylene polymer in the reactor. For example, a second ethylene polymer may be produced in a second reactor, or an arbitrary third ethylene polymer may be produced in a third reactor.

[0091] 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 described herein are not limited to the specific compounds disclosed.

[0092] The activated Ziegler-Natta catalyst formulation can be formed from a magnesium compound, a chloride compound, a metal compound, an alkylaluminum co-catalyst, and an aluminum alkyl compound. In this disclosure, "(v)" refers to the magnesium compound which is "component (v)", "(vi)" refers to the chloride compound which is "component (vi)", "(vii)" refers to the metal compound which is "component (vii)", "(viii)" refers to the alkylaluminum co-catalyst which is "component (viii)", and "(ix)" refers to the aluminum alkyl compound which is "component (ix)". As will be understood by those skilled in the art, the Ziegler-Natta catalyst formulation may also contain additional components, non-limiting examples of which are electron donors, such as amines or ethers.

[0093] Non-limiting examples of active in-line Ziegler-Natta catalyst formulations can be prepared as follows: In the first step, a solution of a magnesium compound (component (v)) is reacted with a solution of a chloride compound (component (vi)) to form a magnesium chloride support suspended in solution. Non-limiting examples of magnesium compounds include Mg(R1 )2 is given, and in the formula, R 1 The groups may be the same or different, and may be linear, branched, or cyclic hydrocarbyl radicals containing 1 to 10 carbon atoms. Non-limiting examples of chloride compounds include R 2 Cl is mentioned, and in the formula, R 2 represents a linear, branched, or cyclic hydrocarbyl radical containing a hydrogen atom or 1 to 10 carbon atoms. In the first step, the solution of the magnesium compound may contain an aluminum alkyl (component (ix)). Non-limiting examples of aluminum alkyl include Al(R 3 )3 is given, and in the formula, R 3 The groups may be the same or different, and may be linear, branched, or cyclic hydrocarbyl radicals containing 1 to 10 carbon atoms. In the second step, a solution of the metal compound is added to a solution of magnesium chloride to support the metal compound (component (vii)) on the magnesium chloride. Non-limiting examples of suitable metal compounds include M * (X) n Or M * O(X) n These are listed, and in the formula, M * ∫ represents a metal selected from groups 4-8 of the periodic table, or a mixture of metals selected from groups 4-8, where 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 non-limiting examples of suitable metal compounds include group 4-8 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 suitable, as represented by the following formula (C): Al(R 4 ) p (OR 5 ) q (X) r (C) (In the formula, R4 The groups may be the same or different, and may be hydrocarbyl groups having 1 to 10 carbon atoms, OR 5 The groups may be the same or different, and may be an alkoxy group or an aryloxy group, R 5 X is a hydrocarbyl group having 1 to 10 carbon atoms bonded to oxygen, where X is a chloride or bromide, and (p+q+r)=3, where p is greater than 0. Non-limiting examples of commonly used alkylaluminum cocatalysts include trimethylaluminum, triethylaluminum, tributylaluminum, dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide, dimethylaluminum chloride or bromide, diethylaluminum chloride or bromide, dibutylaluminum chloride or bromide, and ethylaluminum dichloride or dibromide.

[0094] The process described in the above paragraph for synthesizing the activated in-line Ziegler-Natta catalyst formulation can be carried out in a variety of solvents, and non-limiting examples of solvents include linear or branched C5-C 12 Alkanes or mixtures thereof are examples. The amounts and molar ratios of five components, (v) through (ix), are optimized to produce an active in-line Ziegler-Natta catalyst formulation.

[0095] Additional embodiments of heterogeneous catalyst formulations include formulations in which the "metal compound" is a chromium compound, with non-limiting examples including silyl chromate, 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, with non-limiting examples of co-catalysts including trialkylaluminum, alkylaluminoxane, and dialkoxyalkylaluminum compounds.

[0096] <Solution-phase polymerization process> Embodiments of the present disclosure include a continuous solution-phase polymerization process for producing an ethylene polymer product, the ethylene polymer product comprising a first ethylene polymer and a second ethylene polymer.

[0097] In one embodiment of a continuous solution-phase polymerization process, a process solvent, monomer(s), and catalyst compound are continuously supplied to a reactor where an ethylene polymer is formed in solution. In Figure 1, the process solvent (1), ethylene (2), and an optional α-olefin (3) are combined to generate a first feed stream (RF1), which flows into the first reactor (11a). In Figure 1, any stream or any embodiment is shown by a dotted line.

[0098] In this disclosure, the formation of a combined first supply flow (RF1) is not particularly important. In one embodiment of this disclosure, flows (1) through (3) are injected independently into the reactor (11a).

[0099] Optionally, hydrogen may be injected into reactor (11a) through flow (104). Hydrogen is typically added to control the molecular weight of the first ethylene polymer produced in reactor (11a). Reactor (11a) is continuously stirred by a stirring assembly (11b) which includes an external motor and an internal stirrer. In the art, such a reactor is often called a CSTR (Continuous Stirred Tank Reactor).

[0100] The crosslinked metallocene catalyst formulation is injected into the reactor (11a) through flow (5e). The crosslinked metallocene catalyst formulation component flows 5d, 5c, 5b, and any 5a refer to an ionic activator (component B), a Kasai ligand-metal complex (component A), an almoxane cocatalyst (component M), and an optional hindered phenol (component P), respectively. The crosslinked metallocene catalyst formulation component flows can be arranged in any possible configuration, including embodiments in which flows 5d through 5a are injected independently into the first reactor (11a). Each crosslinked metallocene catalyst formulation component is dissolved in a catalyst component solvent. The catalyst component solvent may be the same or different for component A, and for components M, B, and P. The catalyst component solvent is selected so that no precipitate is formed in any process flow depending on the combination of catalyst components (for example, so that no precipitate of the crosslinked metallocene catalyst component is formed in flow 5e). Optimization of the crosslinked metallocene catalyst formulation is described below.

[0101] The first reactor (11a) produces a flow (11c), which is the first outlet flow, containing the first ethylene polymer dissolved in the process solvent, as well as unreacted ethylene, unreacted α-olefin (if present), unreacted hydrogen (if present), active crosslinked metallocene catalyst, deactivated crosslinked metallocene catalyst, residual catalyst components, and other impurities (if present). The melt index range and density range of the produced first ethylene polymer are described below in the section "First Ethylene Polymer".

[0102] The continuous solution-phase polymerization process shown in Figure 1 includes two embodiments in which reactors (11a) and (12a) can be operated in series mode or parallel mode. In series mode, 100% of flow (11c), i.e., the first outlet flow, passes through the flow control device (11d) to form flow (11e) entering the second reactor (12a). In contrast, in parallel mode, 100% of flow (11c) passes through the flow control device (11f) to form flow (11g). Flow (11g) bypasses reactor (12a) and combines with flow 12c, i.e., the second outlet flow, to form flow 12d, i.e., the third outlet flow.

[0103] A reactor feed stream is injected into reactor (12a) and combined with process solvent (6), ethylene (7), and an optional α-olefin (8) to generate a reactor feed stream (RF2). In this disclosure, the formation of flow RF2, i.e., the combination of reactor feed streams (6) to (8), is particularly important for the reasons detailed below. Optionally, hydrogen may be injected into reactor (12a) through flow (9) to control the molecular weight of a second ethylene polymer produced in the second reactor (12a). In another embodiment, flow (9) is combined with process solvent (6) and combined with ethylene (7) and an optional α-olefin (8) to generate a reactor feed stream (RF2) not shown in Figure 1. * The reactor (12a) is continuously stirred by a stirring assembly (12b) which includes an external motor and an internal stirrer.

[0104] The first in-line heterogeneous catalyst mixture is injected into reactor (12a) through flow (10f), and the second ethylene polymer is formed in reactor (12a). The components constituting the first in-line heterogeneous catalyst mixture are introduced through flows (10a), (10b), (10c), and (10d). The first multi-stage heterogeneous catalyst assembly, defined by conduits and flow control devices associated with flow (10a) to flow (10h), is operated as described below. In the case of the Ziegler-Natta catalyst, the first heterogeneous catalyst assembly generates an efficient first in-line Ziegler-Natta catalyst formulation 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 it takes for these compounds to react and reach equilibrium.

[0105] Flow (10a), i.e., flow S1, contains a two-component blend of a magnesium compound (component (v)) and an aluminum alkyl (component (ix)) in the process solvent. The upper limit of the (aluminum alkyl) / (magnesium compound) molar ratio in flow (10a) may be about 70, possibly about 50, and otherwise about 30. The lower limit of the (aluminum alkyl) / (magnesium compound) molar ratio may be about 3.0, possibly about 5.0, and otherwise about 10. Flow (10b), i.e., flow S2, contains a solution of a chloride compound (component (vi)) in the process solvent. In the first step, flow (10b) is combined with flow (10a), and the mixing of flow (10a) and flow (10b) produces a magnesium chloride catalyst support. The (chloride compound) / (magnesium compound) molar ratio is optimized to produce an efficient first in-line Ziegler-Natta catalyst (efficient for olefin polymerization). The upper limit of the (chloride compound) / (magnesium compound) molar ratio may be about 4, possibly about 3.5, or otherwise about 3.0. The lower limit of the (chloride compound) / (magnesium compound) molar ratio may be about 1.0, possibly about 1.5, or otherwise about 1.9. In the second stage, the time between the addition of the chloride compound via flow (10c), i.e., flow S3, and the addition of the metal compound (component (vii)) is controlled (hereinafter referred to as HUT-1 (first hold-up time)). HUT-1 is the time when flow (10a), i.e., flow S1, and flow (10b), i.e., flow S2, equilibrate to form a magnesium chloride support. The upper limit of HUT-1 may be about 70 seconds, possibly about 60 seconds, or otherwise about 50 seconds. The lower limit of HUT-1 may be about 5 seconds, possibly about 10 seconds, or otherwise about 20 seconds. HUT-1 is controlled by adjusting the length of the conduit between the flow (10b) injection port and the flow (10c) injection port, thereby controlling the flow rates of flow (10a) and flow (10b). In the third stage, the time between the addition of component (vii) via flow (10d), i.e., flow S4, and the addition of the alkylaluminum cocatalyst (component (viii)) is controlled (hereinafter referred to as HUT-2 (second hold-up time)).HUT-2 is the time it takes for the magnesium chloride support and flow 10c to react and reach equilibrium. The upper limit of HUT-2 may be about 50 seconds, possibly about 35 seconds, or otherwise about 25 seconds. The lower limit of HUT-2 may be about 2 seconds, possibly about 6 seconds, or otherwise about 10 seconds. HUT-2 is controlled by adjusting the length of the conduit between the flow (10c) injection port and the flow (10d) injection port, thereby controlling the flow rates of flow (10a), flow (10b), and flow (10c). 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, i.e., the (viii) / (vii) molar ratio. The upper limit of the (alkylaluminum cocatalyst) / (metal compound) molar ratio may be about 10, possibly about 7.5, or otherwise about 6.0. The lower limit of the (alkylaluminum cocatalyst) / (metal compound) molar ratio may be 0, possibly about 1.0, or otherwise about 2.0. In addition, the time between the addition of the alkylaluminum cocatalyst (flow S4) and the injection of the in-line Ziegler-Natta catalyst mixture into reactor (12a) is controlled (hereinafter referred to as HUT-3 (third hold-up time)). HUT-3 is the time for flow (10d) to mix and equilibrate to form the in-line Ziegler-Natta catalyst mixture. The upper limit of HUT-3 may be about 15 seconds, possibly about 10 seconds, or otherwise about 8 seconds. The lower limit of HUT-3 may be about 0.5 seconds, possibly about 1 second, or otherwise about 2 seconds. HUT-3 is controlled by adjusting the length of the conduit between the flow (10d) injection port and the catalyst injection port of reactor (12a), and by controlling the flow rate from flow (10a) to (10d). As shown in Figure 1, optionally, 100% of the alkylaluminum cocatalyst in flow (10d) may be directly injected into reactor (12a) via flow (10h), and the second product mixture is further equilibrated for HUT-3 seconds in the third stage of the first heterogeneous catalyst assembly before being injected into reactor (12a) via flow (10f).Optionally, a portion of flow (10d) may be directly injected into reactor (12a) via flow (10h), or the remaining portion of flow (10d) may be injected into reactor (12a) via flow (10f).

[0106] The equivalent term for reactor (12a) is "R2". The amount of the first in-line heterogeneous catalyst mixture added to R2 is expressed as parts per million (ppm) of the metal compound (component (vii)) in the reactor solution, hereafter referred to as "R2(vii)(ppm)". The upper limit of R2(vii)(ppm) may be about 10 ppm, possibly about 8 ppm, or otherwise about 6 ppm. The lower limit of R2(vii)(ppm) may be about 0.5 ppm, possibly about 1 ppm, or still otherwise about 2 ppm. The (aluminum alkyl) / (metal compound) molar ratio, or (ix) / (vii) molar ratio, in reactor (12a) is also controlled. The upper limit of the (aluminum alkyl) / (metal compound) molar ratio in the reactor is about 2, possibly about 1.5, or otherwise about 1.0. The lower limit of the (aluminum alkyl) / (metal compound) molar ratio may be about 0.05, in some cases about 0.075, and in other cases about 0.1.

[0107] Any combination of flows used to prepare and deliver the in-line heterogeneous catalyst formulation to R2, i.e., flows (10a) through (10h) (including flow (10g), i.e., optionally delivered to R3), as described below, may be heated or cooled. In some cases, the upper temperature limit for flows (10a) through (10g) may be about 90°C, in other cases about 80°C, and in yet other cases about 70°C, and in some cases the lower temperature limit may be about 20°C, in other cases about 35°C, and in yet other cases about 50°C. The flow rate through process flow (10f) or (5e) can vary over a wide range, for example, depending on the catalyst activity and reactor volume. In this disclosure, the flow rate through process flow (10f) is expressed as a percentage of the total amount of process solvent leaving (R2). The upper limit of the flow rate through the process flow (10f) is approximately (20%) of the total amount of process solvent leaving R2, approximately (15%) in other cases, and approximately (10%) in yet other cases. The lower limit of the flow rate through the process flow (10f) is approximately 0.01% of the total amount of process solvent leaving R2, approximately 0.05% in other cases, and approximately 0.1% in yet other cases.

[0108] By injecting an in-line heterogeneous catalyst mixture into the reactor (12a), a second ethylene polymer and a second outlet flow (12c) are generated.

[0109] When reactors (11a) and (12a) are operated in series mode, the second outlet flow (12c) contains the second and first ethylene polymers dissolved in the process solvent; as well as unreacted ethylene, unreacted α-olefins (if present), unreacted hydrogen (if present), active catalyst, deactivated catalyst, catalyst components, and other impurities (if present). Optionally, the second outlet flow (12c) is deactivated by adding catalyst deactivator A from catalyst deactivator tank (18A) to form deactivated solution A, flow (12e), in which case Figure 1 defaults to a double reactor solution process. If the second outlet flow (12c) is not deactivated, the second outlet flow enters the tubular reactor (17). Catalyst deactivator A is described below.

[0110] When reactors (11a) and (12a) are operated in parallel mode, the second outlet stream (12c) contains the second ethylene polymer dissolved in the process solvent. The second outlet stream (12c) combines with stream (11g) to form a third outlet stream (12d), the latter containing the second and first ethylene polymers dissolved in the process solvent; as well as unreacted ethylene, unreacted α-olefins (if present), unreacted hydrogen (if present), active catalyst, deactivated catalyst, catalyst components, and other impurities (if present). Optionally, the third outlet stream (12d) is deactivated by adding catalyst deactivator A from catalyst deactivator tank (18A) to form deactivated solution A, stream (12e), in which case Figure 1 defaults to a double reactor solution process. If the third outlet stream (12d) is not deactivated, it enters the tubular reactor (17).

[0111] The term “tubular reactor” refers to a simple tube having a length / diameter (L / D) ratio of at least 10 / 1. Optionally, one or more of the following reactor feed streams, namely process solvent (13), ethylene (14), and any α-olefin (15), may be injected into the tubular reactor (17). As shown in Figure 1, streams (13), (14), and (15) may be combined to form a reactor feed stream (RF3), which may be injected into the reactor (17). In this disclosure, it is not particularly important that a fresh feed stream RF3 is formed, i.e., the reactor feed streams can be combined in all possible combinations. Optionally, hydrogen may be injected into the reactor (17) through stream (16). Optionally, the first in-line heterogeneous catalyst mixture may be injected into the reactor (17) via a catalyst stream (10g), that is, a portion of the in-line heterogeneous catalyst enters the reactor (12a) through the stream (10f), and the remaining portion of the in-line heterogeneous catalyst enters the reactor (17) through the stream (10g).

[0112] Figure 1 shows an additional embodiment in which a second heterogeneous catalyst formulation produced by a second heterogeneous catalyst assembly is supplied to reactor (17). The second heterogeneous catalyst assembly refers to a combination of conduits and flow control devices, including flows (34a) to (34e) and (34h). The chemical compositions of the first and second heterogeneous catalyst formulations may be the same or different. In the case of a Ziegler-Natta catalyst, the second heterogeneous catalyst assembly produces a second in-line Ziegler-Natta catalyst formulation. For example, catalyst components (v) to (ix), molar ratios, and hold-up times may differ between the first and second heterogeneous catalyst assemblies. For the first heterogeneous catalyst assembly, the second heterogeneous catalyst assembly is operated in a similar manner, namely, the second heterogeneous catalyst assembly generates an efficient catalyst by optimizing the hold-up time and the following molar ratios: (aluminum alkyl) / (magnesium compound), (chloride compound) / (magnesium compound), (alkylaluminum cocatalyst) / (metal compound), and (aluminum alkyl) / (metal compound). For clarity, flow 34a contains a two-component blend of magnesium compound (component (v)) and aluminum alkyl (component (ix)) in the process solvent, flow (34b) contains chloride compound (component (vi)) in the process solvent, flow (34c) contains metal compound (component (vii)) in the process solvent, and flow (3 4d) contains an alkylaluminum cocatalyst (component (viii)) in the process solvent. Once prepared, the in-line Ziegler-Natta catalyst is injected into reactor (17) through flow (34e), and optionally, additional alkylaluminum cocatalyst is injected into reactor (17) through flow (34h). As shown in Figure 1, optionally, 100% of flow (34d), which is the alkylaluminum cocatalyst, may be injected directly into reactor (17) via flow (34h). Optionally, a portion of flow (34d) may be injected directly into reactor (17) via flow (34h), and the remainder of flow (34d) may be injected into reactor (17) via flow 34e. In Figure 1, the first or second heterogeneous catalyst assembly supplies 100% of the catalyst to reactor (17).Any combination of flows constituting the second heterogeneous catalyst assembly, namely flow (34a) to flow (34e) and flow (34h), may be heated or cooled, and the upper temperature limit of flows (34a) to flow (34e) and flow (34h) may be about 90°C in some cases, about 80°C in other cases, and about 70°C in yet other cases, and the lower temperature limit may be about 20°C in some cases, about 35°C in other cases, and about 50°C in yet other cases. The flow rate through process flow (34e) can vary over a wide range, for example, depending on the catalytic activity and reactor volume. In this disclosure, the flow rate through process flow (34e) is expressed as a percentage of the total amount of process solvent leaving R3. The upper limit of the flow rate through process flow (34e) is about 20% of the total amount of process solvent leaving R3, about 15% in other cases, and about 10% in yet other cases. The lower limit of the flow rate through process flow 34e is approximately 0.01% of the total amount of process solvent leaving R3, approximately 0.05% in other cases, and approximately 0.1% in yet other cases.

[0113] In reactor (17), a third ethylene polymer may or may not be formed. If catalyst deactivator A is added upstream of reactor (17) via catalyst deactivator tank (18A), no third ethylene polymer is formed. If catalyst deactivator B is added downstream of reactor (17) via catalyst deactivator tank (18B), a third ethylene polymer is formed.

[0114] Any third ethylene polymer produced in reactor (17) can be formed using various operating modes, provided that catalyst deactivator A is not added upstream of reactor (17). Non-limiting examples of operating modes include: (a) residual ethylene, an optional residual α-olefin, and a residual active catalyst entering reactor (17) react to form an optional third ethylene polymer; (b) fresh process solvent (13), fresh ethylene (14), and optionally fresh α-olefin (15) are added to reactor (17) and the residual active catalyst entering reactor (17) forms an optional third ethylene polymer; (c) a fresh second in-line heterogeneous catalyst formulation is added to reactor (17) via flow (10 g) or flow (34e) to polymerize residual ethylene and an optional residual α-olefin to form an optional third ethylene polymer; (d) fresh process solvent (13), ethylene (14), an optional α-olefin (15), and a fresh second heterogeneous catalyst formulation (10 g) or (34e) are added to reactor (17) to form an optional third ethylene polymer. Optionally, 100% alkylaluminum cocatalyst may be added to reactor 17 via flow (34h), or a portion of the alkylaluminum cocatalyst may be added to reactor (17) via flow (10g) or via flow (34h), with the remainder added via flow (34h). Optionally, fresh hydrogen (16) may be added to reduce the molecular weight of any third ethylene polymer.

[0115] In series mode, reactor (17) produces a third outlet stream (17b) containing a first ethylene polymer, a second ethylene polymer, and optionally a third ethylene polymer. As shown in Figure 1, catalyst deactivator B may be added to the third outlet stream (17b) via catalyst deactivator tank (18B) to produce deactivation solution B, stream (19). However, if catalyst deactivator A is added upstream of reactor (17), catalyst deactivator B is not added. Deactivation solution B may contain unreacted ethylene, unreacted any α-olefin, unreacted any hydrogen, and impurities, if present. As described above, if catalyst deactivator A is added, the stream (12e), which is deactivation solution A, exits the tubular reactor (17) as shown in Figure 1.

[0116] In parallel mode operation, reactor (17) produces a fourth outlet flow (17b) containing a first ethylene polymer, a second ethylene polymer, and optionally a third ethylene polymer. As described above, in parallel mode, flow (12d) is the third outlet flow. As shown in Figure 1, in parallel mode, catalyst deactivator B may be added to the fourth outlet flow (17b) via catalyst deactivator tank 18B to produce flow 19, which is deactivation solution B. However, if catalyst deactivator A is added upstream of reactor 17, catalyst deactivator B is not added.

[0117] In Figure 1, either the flow (12e) which is deactivating solution A, or the flow (19) which is deactivating solution B, passes through a pressure-reducing device (20) and a heat exchanger (21), where a passivator is added via a tank (22) to form a passivated solution (23). The passivator will be described below. The passivated solution passes through a pressure-reducing device (24) and enters the first vapor / liquid separator (25). Hereinafter, "V / L" is equivalent to vapor / liquid. In the first V / L separator, the following two flows are formed: a first bottom flow (27) containing a solution rich in ethylene polymer and also containing residual ethylene, any residual α-olefins, and catalyst residues, and a first gaseous overhead flow (26) containing ethylene, process solvent, any α-olefins, any hydrogen, oligomers, and light impurities (if present).

[0118] The first bottom flow enters the second V / L separator (28). In the second V / L separator, two flows are formed: a second bottom flow (30) containing a solution rich in ethylene polymer and less process solvent compared to the first bottom flow (27), and a second gaseous overhead flow (29) containing the process solvent, any α-olefins, ethylene, oligomers, and light impurities (if present).

[0119] The second bottom flow (30) flows into the third V / L separator (31). In the third V / L separator, two flows are formed: a product flow (33) containing ethylene polymer products, deactivated catalyst residue, and less than 5% by weight of residual process solvent, and a third gaseous overhead flow (32) essentially consisting of process solvent, any α-olefins, and light impurities (if present).

[0120] The product stream (33) proceeds to a polymer recovery operation. Non-limiting examples of polymer recovery operations include one or more gear pumps, single-screw extruders, or twin-screw extruders that push the molten ethylene polymer product into a pelletizer. A defoliation extruder may be used to remove small amounts of residual process solvent and any α-olefins (if present). Once pelletized, the solidified ethylene polymer product is typically dried and transported to a product silo.

[0121] The first, second, and third gaseous overhead flows shown in Figure 1 (flows (26), (29), and (32), respectively) are sent to a distillation column where the solvent, ethylene, and any α-olefins are separated for recycling, or the first, second, and third gaseous overhead flows are recycled to the reactor, or a portion of the first, second, and third gaseous overhead flows are recycled to the reactor and the remainder is sent to the distillation column.

[0122] In the embodiment of the continuous solution-phase polymerization process that produces the ethylene polymer product shown in Figure 1, various solvents can be used as process solvents, and non-limiting examples include linear, branched, or cyclic C5-C5 polymers. 12 Alkanes are included. Non-limiting examples of α-olefins include 1-propene, 1-butene, 1-pentene, 1-hexene, and 1-octene. Suitable catalytic solvents include aliphatic and aromatic hydrocarbons. Non-limiting examples of aliphatic catalytic solvents include linear, branched, or cyclic carbon atoms. 5-12 Aliphatic hydrocarbons, such as pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, naphtha hydrogenates, or combinations thereof, are included. Non-limiting 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, hemeritene (1,2,3-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), mixtures of trimethylbenzene isomers, prehenytene (1,2,3,4-tetramethylbenzene), durene (1,2,3,5-tetramethylbenzene), mixtures of tetramethylbenzene isomers, pentamethylbenzene, hexamethylbenzene, and combinations thereof.

[0123] It is well known to those skilled in the art that the reactor feedstream (solvent, monomer, α-olefin, hydrogen, catalyst formulation, etc.) should not essentially contain catalyst deactivation toxins, and non-limiting examples of toxins include trace amounts of oxygen-containing compounds such as water, fatty acids, alcohols, ketones, and aldehydes. Such toxins are removed from the reactor feedstream using standard purification methods, non-limiting examples of which include molecular sieve beds, alumina beds, and oxygen removal catalysts for purifying solvents, ethylene, and α-olefins, etc.

[0124] Referring to the first reactor in Figure 1, any combination of fresh feed flows to the first reactor (11a), more specifically, flows (1) through (4), may be heated or cooled. The upper limit of the temperatures through the fresh feed flows (1) through (4) to the first reactor may be about 90°C, in other cases about 80°C, and in yet other cases about 70°C. The lower limit of the temperature of the feed flows to the reactor may be about 0°C, in other cases about 10°C, and in yet other cases about 20°C.

[0125] Referring to the second reactor (R2) in Figure 1, the fresh feed stream to the second reactor 12a, more specifically, from stream (6) to stream (9), may be heated or cooled. The upper limit of the temperatures through the fresh feed streams (6) to (9) to the second reactor may be about 90°C, in other cases about 85°C, and in yet other cases about 80°C. The lower limit of the temperatures through the feed streams (6) to (9) to the second reactor may be about 60°C, in other cases about 65°C, and in yet other cases about 70°C. In some cases, a combined fresh feed stream RF2 or RF2 * Temperature T f The temperature range is 60°C to 90°C, or 60°C to 85°C, or 60°C to 80°C.

[0126] Any combination of flows supplied to the tubular reactor may be heated or cooled, specifically flows (13) through (16) in Figure 1. In some cases, the feed flows to the tubular reactor are regulated, i.e., the feed flows to the tubular reactor are heated to at least the ambient temperature. The upper limit temperature of the feed flows to the tubular reactor is sometimes about 200°C, sometimes about 170°C, and still other times about 140°C, and the lower limit temperature of the feed flows to the tubular reactor is sometimes about 60°C, sometimes about 90°C, and still other times about 120°C, provided that the temperature of the feed flows to the tubular reactor is below the temperature of the process flow entering the tubular reactor.

[0127] In the embodiment shown in Figure 1, the outlet temperatures of the solution polymerization reactor (container (11a), R1, and container (12a), R2) can vary over a wide range. For example, the upper limits of the first and second outlet temperatures may be about 300°C in some cases, about 280°C in other cases, and about 260°C in yet other cases, and the lower limits may be about 80°C in some cases, about 100°C in other cases, and about 125°C in yet other cases. The flow temperature (12c), which is the second outlet flow temperature, is higher than the first outlet flow temperature (11c). That is, the second outlet temperature is the second temperature T2, and the first outlet temperature is the first temperature T1, and T2 and T1 satisfy the inequality T2 > T1. The maximum temperature difference between these two outlet temperatures (T2-T1) is approximately 75°C in some cases, approximately 70°C in others, and approximately 68°C in yet other cases, while the minimum temperature difference between T2-T1 is approximately 45°C in some cases, approximately 48°C in others, and approximately 50°C in yet other cases.

[0128] In some cases, R1 and R2 are operated adiabatically.

[0129] The temperature T3 of the third outlet flow (in series mode operation) or fourth outlet flow (in parallel mode operation) exiting the tubular reactor, i.e., from reactor (17) R3, is sometimes about 100°C higher than T2, sometimes about 60°C higher than T2, sometimes about 10°C higher than T2, and sometimes 0°C higher, i.e., the same temperature as T2.

[0130] The temperature within any R3 can rise along its length. The maximum temperature difference between the inlet and outlet of R3 is approximately 100°C in some cases, approximately 60°C in others, and approximately 40°C in yet other cases. The minimum temperature difference between the inlet and outlet of R3 is approximately 0°C in some cases, approximately 3°C in others, and approximately 10°C in yet other cases.

[0131] In some cases, R3 is operated adiabatically.

[0132] The pressure inside the polymerization reactor must be high enough to maintain the polymerization solution as a single-phase solution and provide an upstream pressure to push the polymer solution out of the reactor through the heat exchanger to the polymer recovery operation. Referring to the embodiment shown in Figure 1, 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 about 45 MPag in some cases, about 30 MPag in other cases, and about 20 MPag in yet other cases, and the lower limit may be about 3 MPag in some cases, about 5 MPag in other cases, and about 7 MPag in yet other cases.

[0133] Referring to the embodiment shown in Figure 1, before entering the first V / L separator, the maximum temperature of the passivation solution (flow 23) may be about 300°C in some cases, about 290°C in other cases, and about 280°C in yet other cases, and the minimum temperature may be about 150°C in some cases, about 200°C in other cases, and about 220°C in yet other cases. Immediately before entering the first V / L separator, the maximum pressure of the passivation solution may be about 40 MPag in some cases, about 25 MPag in other cases, and about 15 MPag in yet other cases, and the minimum pressure may be about 1.5 MPag in some cases, about 5 MPag in other cases, and about 6 MPag in yet other cases.

[0134] The first V / L separator (container 25 in Figure 1) can be operated over a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the first V / L separator may be about 300°C in some cases, about 285°C in other cases, and about 270°C in yet other cases, and the minimum operating temperature may be about 100°C in some cases, about 140°C in other cases, and about 170°C in yet other cases. The maximum operating pressure of the first V / L separator may be about 20 MPag in some cases, about 10 MPag in other cases, and about 5 MPag in yet other cases, and the minimum operating pressure may be about 1 MPag in some cases, about 2 MPag in other cases, and about 3 MPag in yet other cases.

[0135] The second V / L separator, vessel (28) in Figure 1, can be operated over a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the second V / L separator may be about 300°C in some cases, about 250°C in other cases, and about 200°C in yet other cases, and the minimum operating temperature may be about 100°C in some cases, about 125°C in other cases, and about 150°C in yet other cases. The maximum operating pressure of the second V / L separator may be about 1000 kPag in some cases, about 900 kPag in other cases, and about 800 kPag in yet other cases, and the minimum operating pressure may be about 10 kPag in some cases, about 20 kPag in other cases, and about 30 kPag in yet other cases.

[0136] The third V / L separator, vessel (31) in Figure 1, can be operated over a relatively wide range of temperatures and pressures. For example, the maximum operating temperature of the third V / L separator may be about 300°C in some cases, about 250°C in other cases, and about 200°C in yet other cases, and the minimum operating temperature may be about 100°C in some cases, about 125°C in other cases, and about 150°C in yet other cases. The maximum operating pressure of the third V / L separator may be about 500 kPag in some cases, about 150 kPag in other cases, and about 100 kPag in yet other cases, and the minimum operating pressure may be about 1 kPag in some cases, about 10 kPag in other cases, and about 25 kPag in yet other cases.

[0137] The embodiment of the continuous solution-phase polymerization process disclosed in Figure 1 shows three V / L separators. However, the embodiment of the continuous solution-phase polymerization may also include a configuration comprising at least one V / L separator.

[0138] The ethylene polymer products produced in a continuous solution-phase 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.

[0139] In Figure 1, reactor (11a) R1 and reactor (12a) R2 can be any reactor shape or design, and non-limiting examples include unagitated or agitated spherical, cylindrical, or tank-shaped vessels, as well as tubular reactors or recirculating loop reactors.

[0140] On a commercial scale, the maximum capacity of R1 may be approximately 20,000 gallons (approximately 75,710 L) in some cases, approximately 10,000 gallons (approximately 37,850 L) in other cases, and approximately 5,000 gallons (approximately 18,930 L) in yet other cases. On a commercial scale, the minimum capacity of R1 may be approximately 100 gallons (approximately 379 L) in some cases, approximately 500 gallons (approximately 1,893 L) in other cases, and approximately 1,000 gallons (approximately 3,785 L) in yet other cases.

[0141] At pilot plant scale, reactor volumes are typically very small; for example, the volume of R1 at pilot scale may be less than approximately 2 gallons (less than approximately 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 approximately 600% of R1 in some cases, approximately 400% of R1 in other cases, and approximately 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 the volume of R2 is 10,000 gallons. The lower limit of the volume of R2 may be approximately 50% of R1 in some cases, approximately 100% of R1 in other cases, and approximately 150% of R1 in yet other cases.

[0142] In the case of a tank-type reactor with continuous stirring, the stirring speed can vary over a wide range, sometimes ranging from approximately 10 rpm to 2000 rpm, sometimes from approximately 100 to 1500 rpm, and in other cases from approximately 200 to 1300 rpm.

[0143] 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 about 100% of R2 in yet other cases. 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 about 50% of R2 in yet other cases.

[0144] The "mean reactor residence time," a parameter commonly used in the field of chemical engineering, is defined by the first moment of the reactor residence time distribution, which is a probability distribution function describing the amount of time a fluid element spends in the reactor. The mean reactor residence time can vary considerably depending on the process flow rate and the mixing, design, and capacity of the reactor. The upper limit of the mean reactor residence time for solution R1 may be about 600 seconds in some cases, about 360 seconds in other cases, and about 180 seconds in yet other cases. The lower limit of the mean reactor residence time for solution R1 may be about 10 seconds in some cases, about 20 seconds in other cases, and about 40 seconds in yet other cases. The upper limit of the mean reactor residence time for solution R2 may be about 720 seconds in some cases, about 480 seconds in other cases, and about 240 seconds in yet other cases. The lower limit of the mean reactor residence time for solution R2 may be about 10 seconds in some cases, about 30 seconds in other cases, and about 60 seconds in yet other cases. The upper limit of the average reactor residence time for the R3 solution may be approximately 600 seconds in some cases, approximately 360 seconds in other cases, and approximately 180 seconds in yet other cases. The lower limit of the average reactor residence time for the R3 solution may be approximately 1 second in some cases, approximately 5 seconds in other cases, and approximately 10 seconds in yet other cases.

[0145] Optionally, additional reactors (e.g., CSTRs, loops, or tubes) can be added to the embodiment of the continuous solution-phase polymerization process shown in Figure 1. While the number of reactors is not particularly important in this disclosure, the continuous solution polymerization process is provided to include at least two reactors, each using at least one single-site catalyst formulation and at least one heterogeneous catalyst formulation.

[0146] When operating the embodiment of the continuous solution polymerization process shown in Figure 1, the total amount of ethylene supplied to the process can be distributed or split among the three reactors R1, R2, and R3. This operating variable is called the ethylene split (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 The condition is that the ethylene flow rate is 100%. This is achieved by adjusting the ethylene flow rates of the following flows: flow 2 (R1), flow 7 (R2), and flow 14 (R3). 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 sometimes 0%, sometimes about 5%, and in yet another time about 10%.

[0147] This disclosure describes the fresh supply flow RF2 or RF2 * The ethylene concentration inside is further controlled within a defined range. In some cases, fresh supply flow RF2 or RF2 * The ethylene concentration in the mixture is 25% by weight or less, based on the total weight of the fresh feed stream RF2 injected into the second reactor per unit time. In other cases, the fresh feed stream RF2 or RF2 injected into the second reactor R2 *The concentration of ethylene in the mixture is less than 21% by weight and greater than 17.5% by weight, based on the total weight of the second fresh feed stream injected into the second reactor per unit time. In other cases, the fresh feed stream RF2 or RF2 injected into the second reactor R2 is less than 21% by weight. * The concentration of ethylene in the mixture is less than 21% by weight and greater than 15% by weight, based on the total weight of the second fresh feed stream injected into the second reactor per unit time.

[0148] When operating the embodiment of the continuous solution-phase polymerization process shown in Figure 1, 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 the first ethylene polymer by the catalyst compound. Similarly, Q R2 and Q R3 Q represents the percentage of ethylene added to R2 and R3 that was converted to the second and third ethylene polymers in each reactor. The ethylene conversion rate can vary significantly 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 sometimes 0%, sometimes about 5%, and still other times about 10%. T The term "Q" represents the total or overall ethylene conversion rate across the entire continuous solution polymerization plant, i.e., Q T = 100 × [weight of ethylene in polymer product] / ([weight of ethylene in polymer 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, QT The lower limit is approximately 75% in some cases, approximately 80% in others, and approximately 85% in yet another case.

[0149] Optionally, one or more C3~C 10 The α-olefin may be added to the continuous solution-phase polymerization process disclosed herein. If added, the α-olefin may be proportionally distributed or split among R1, R2, and R3. This operational variable is called the comonomer split (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 The condition is that =100%. This is achieved by adjusting the α-olefin flow rates of the following flows: flow 3 (R1), flow 8 (R2), and flow 15 (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 sometimes 0% (ethylene homopolymer produced in R1), sometimes about 5%, and still other times about 10%. CS 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 sometimes 0%, sometimes about 5%, and in yet another time about 10%. CS R3 The upper limit is 100% in some cases, approximately 95% in others, and approximately 90% in yet other cases. CS R3 The lower limit is sometimes 0%, sometimes about 5%, and in yet another time about 10%. Multiple C3-C3 polymerases are used in the continuous solution-phase polymerization process. 10 When adding α-olefin, comonomer resorption is C3~C 10 Each α-olefin is reported separately.

[0150] In some cases, one or more C3~C 10 The α-olefin is in the fresh supply flow RF2 or RF2 * The relative concentration of ethylene is determined through the fresh supply flow RF2 or RF2. * Ethylene weight percentage and one or more C3-C 10 Based on the ratio with the weight percentage of α-olefin, it is injected into the second reactor in a ratio of 0.15 to 2. In other cases, one or more C3-C 10 The α-olefin is in the fresh supply flow RF2 or RF2 * The relative concentration of ethylene is determined through the fresh supply flow RF2 or RF2. * Ethylene weight percentage and one or more C3-C 10 Based on the ratio to the weight percentage of α-olefin, it is injected into the second reactor so that the ratio is between 0.15 and 1.

[0151] In the continuous polymerization process described herein, polymerization is terminated by adding a catalyst deactivator. The embodiment shown in Figure 1 illustrates catalyst deactivation occurring either upstream of the tubular reactor by adding catalyst deactivator A from catalyst deactivator tank (18A), or downstream of the tubular reactor by adding catalyst deactivator B from catalyst deactivator tank 18B. Catalyst deactivator tanks 18A and 18B may contain undiluted (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. Non-limiting examples of suitable solvents include linear or branched C5-C 12Alkanes are included. The method of adding the catalyst deactivator is not particularly important in this disclosure. 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 (e.g., Sibtain et al., U.S. Patent No. 6,180,730). Suitable carboxylic acids as catalyst deactivators include RCO2H (wherein R is a linear or branched hydrocarbyl group containing 5 to 20 carbon atoms).

[0152] In this disclosure, the amount of catalyst deactivator added was determined by the following catalyst deactivator molar ratio: 0.3 ≤ (catalyst deactivator) / ((total catalyst metal) + (alkylaluminum cocatalyst) + (aluminum alkyl)) ≤ 2.0; where the catalyst metal is the total number of moles of metal A derived from the crosslinked metallocene catalyst formulation, metal B derived from the first heterogeneous catalyst formulation, and any metal C derived from the second heterogeneous catalyst formulation. The upper limit of the catalyst deactivator molar ratio may be about 2, in some cases about 1.5, and in other cases about 0.75. The lower limit of the catalyst deactivator molar ratio may be about 0.3, in some cases about 0.35, and in yet other cases about 0.4. In general, the catalyst deactivator is added in the minimum amount necessary to deactivate the catalyst and halt the polymerization reaction.

[0153] Referring to the embodiment shown in Figure 1, before entering the first V / L separator, a passivator or acid scavenger is added to the deactivation solution A or B to form a passivation solution, i.e., a passivation solution stream 23. The passivator tank 22 may contain undiluted (100%) passivator, a solution of passivator in a solvent, or a slurry of passivator in a solvent. Non-limiting examples of suitable solvents include linear or branched C5-C 12Alkanes are included. The method of adding the passivator is not particularly important in this disclosure. Suitable passivators are well known in the art, and non-limiting examples include alkali metal salts or alkaline earth metal salts of carboxylic acids or hydrotalcite. The amount of passivator added may vary over a wide range. In this disclosure, the molar amount of added passivator was determined by the total number of moles of chloride compounds added to the solution process, i.e., chloride compound "component (vi)" and metal compound "component (vii)". Optionally, first and second chloride compounds, and first and second metal compounds may be used, i.e., to form first and second heterogeneous catalyst formulations, in which case the amount of passivator added is determined by the total number of moles of all chloride-containing compounds. The upper limit of the passivator molar ratio (moles of passivator) / (moles of total chloride) may be 20, possibly 15, or otherwise 10. The lower limit of the (passivator) / (total chloride) molar ratio may be about 0.2, possibly about 0.4, and in other cases about 0.8. In general, the deactivator is added in the minimum amount necessary to substantially passivate the deactivation solution.

[0154] <First Ethylene Polymer> The first ethylene polymer is produced using a crosslinked metallocene catalyst formulation. Referring to the embodiment shown in Figure 1, if no α-olefin is added to reactor 1 (R1), the ethylene polymer produced in R1 is an ethylene homopolymer. When an α-olefin is added, the weight ratio of the α-olefin to ethylene added to the first reactor is one parameter for controlling the density of the first ethylene polymer. This weight ratio (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, or in other cases about 0.25, and in yet other cases about 0.5. Hereafter, the symbol "σ" 1 " refers to the density of the first ethylene polymer produced in R1. σ 1 The upper limit is approximately 0.975 g / cm³.3 In some cases, approximately 0.965 g / cm³ 3 In other cases, approximately 0.955 g / cm³ 3 That's fine. 1 The lower limit is approximately 0.855 g / cm³. 3 In some cases, approximately 0.865 g / cm³ 3 In other cases, approximately 0.875 g / cm³ 3 That's fine.

[0155] CDBI of ethylene polymers 50 Methods for determining the (composition distribution branching index) are well known to those skilled in the art. CDBI is expressed as a percentage. 50 CDBI of ethylene polymers produced using metallocene catalyst formulations is defined as the percentage of ethylene polymers in which the comonomer composition is within 50% of the central comonomer composition. 50 CDBI of α-olefin-containing ethylene polymer produced using heterogeneous catalyst formulations 50 It is also well known to those skilled in the art that it is higher than the CDBI of the first ethylene polymer (produced using a crosslinked metallocene catalyst formulation as described above herein). 50 The upper limit may be approximately 98%, approximately 95% in other cases, and approximately 90% in yet other cases. CDBI of the first ethylene polymer 50 The lower limit may be approximately 70%, approximately 75% in other cases, and approximately 80% in yet other cases.

[0156] As is well known to those skilled in the art, the M of ethylene polymer produced using a crosslinked metallocene catalyst formulation w / M n This is lower than that of ethylene polymers produced using heterogeneous catalyst formulations. Therefore, in the disclosed embodiments, the first ethylene polymer has a lower M than the second ethylene polymer. w / M n The first ethylene polymer has the following properties, where the second ethylene polymer is produced using a heterogeneous catalyst formulation. w / M nThe upper limit may be about 2.8, about 2.5 in other cases, and about 2.2 in yet other cases. M of the first ethylene polymer w / M n The lower limit may be approximately 1.7, approximately 1.8 in other cases, and approximately 1.9 in yet other cases.

[0157] The first ethylene polymer contains catalyst residues that reflect the chemical composition of the crosslinked metallocene catalyst formulation used in its synthesis. Those skilled in the art will understand that the catalyst residues are typically quantified in parts per million (ppm) of metal in the first ethylene polymer. Hereinafter, metal refers to the metal in component (a) or component (A), and this metal is referred to as "metal A". As previously stated in this disclosure, non-limiting examples of metal A include group IV metals, titanium, zirconium, and hafnium. The upper limit of the ppm of metal A in the first ethylene polymer may be about 1.0 ppm, in other cases about 0.9 ppm, and in yet other cases about 0.8 ppm. The lower limit of the ppm of metal A in the first ethylene polymer may be about 0.01 ppm, in other cases about 0.1 ppm, and in yet other cases about 0.2 ppm.

[0158] The amount of hydrogen added to R1 can be varied over a wide range, thereby enabling a continuous solution phase process to achieve a melt index (hereinafter referred to as I2). 1 (denoted as H2) can produce a first ethylene polymer that is significantly different (the melt index is measured using a load of 2.16 kg at 190°C, following the procedure outlined in ASTM D1238). This is achieved by adjusting the hydrogen flow rate in flow 4 (shown in Figure 1). The amount of hydrogen added to R1 is expressed as parts per million (ppm) of hydrogen in R1 relative to the total mass in reactor R1, and is hereafter referred to as H2 R1 (ppm) is used. In some cases, H2 R1 (ppm) is in the range of approximately 50 ppm to 0 ppm, approximately 25 ppm to 0 ppm in other cases, approximately 10 ppm to 0 ppm in yet other cases, and approximately 2 ppm to 0 ppm in yet other cases.

[0159] I21 The upper limit may be approximately 200 dg / min, in some cases approximately 100 dg / min, in other cases approximately 50 dg / min, and in yet other cases approximately 1 dg / min. 1 The lower limit is approximately 0.01 dg / min, sometimes approximately 0.05 dg / min, and otherwise approximately 0.1 dg / min. In yet other cases, it may be approximately 0.5 dg / min.

[0160] The upper limit of the weight percentage (wt%) of the first ethylene polymer in the ethylene polymer product may be about 60 wt%, about 55 wt%, or about 50 wt% in other cases. The lower limit of the weight percentage of the first ethylene polymer in the ethylene polymer product may be about 15 wt%, about 25 wt%, or about 30 wt% in other cases.

[0161] <Second Ethylene Polymer> Referring to the embodiment shown in Figure 1, if no α-olefin is added to reactor 12a(R2) by either the fresh α-olefin flow 8 or the flow 11e introduced from reactor 11a(R1) (in series mode), then the ethylene polymer produced in reactor 12a(R2) is ethylene polymer. If any α-olefin is present in R2, the weight ratio of α-olefin to ethylene in the second reactor is one parameter for controlling the density of the second ethylene polymer produced in R2, i.e., (α-olefin / ethylene). R2 (α-olefin / ethylene) R2 The upper limit may be approximately 3, approximately 2 in other cases, and approximately 1 in yet other cases. (α-olefin / ethylene) R2The lower limit may be 0, or in other cases about 0.25, and in yet other cases about 0.5. Note that this ratio is different from the relative concentration of α-olefin to ethylene, which is defined based on the ratio of ethylene weight percent to α-olefin weight percent in the fresh feed stream RF2 injected into the second reactor, for example, by passing from the first outlet to the second reactor. Hereinafter, the symbol "σ" 2 " refers to the density of the ethylene polymer produced in R2. σ 2 The upper limit is approximately 0.975 g / cm³. 3 In some cases, approximately 0.965 g / cm³ 3 In other cases, approximately 0.955 g / cm³ 3 This may also be the case. Depending on the formulation of the heterogeneous catalyst used, σ 2 The lower limit is approximately 0.89 g / cm³. 3 In some cases, approximately 0.90 g / cm³ 3 In other cases, approximately 0.91 g / cm³ 3 That's fine.

[0162] A heterogeneous catalyst formulation is used to produce the second ethylene polymer. If the second ethylene polymer contains α-olefin, the CDBI of the second ethylene polymer 50 CDBI of the first ethylene polymer produced using a cross-linked metallocene catalyst formulation. 50 It becomes lower than. In one embodiment of the present disclosure, the CDBI of a second ethylene polymer (containing α-olefin) 50 The upper limit may be about 70%, about 65% in other cases, and about 60% in yet other cases. In one embodiment of the present disclosure, the CDBI of the second ethylene polymer (including α-olefin) 50 The lower limit may be about 45%, about 50% in other cases, and about 55% in yet other cases. If α-olefins are not added to the continuous solution-phase polymerization process, the second ethylene polymer is an ethylene homopolymer. Even in the case of homopolymers that do not contain α-olefins, CDBI can be performed using TREF. 50 It can measure the CDBI of the second ethylene polymer. In the case of homopolymers, the CDBI of the second ethylene polymer can be measured. 50The upper limit may be approximately 98%, approximately 96% in other cases, and approximately 95% in yet other cases, CDBI 50 The lower limit may be about 88%, about 89% in other cases, and about 90% in yet other cases. As is well known to those skilled in the art, as the α-olefin content in the second ethylene polymer approaches zero, the CDBI described for the second ethylene polymer (containing α-olefin) 50 CDBI describes the limit values ​​and the second ethylene polymer, which is an ethylene homopolymer. 50 A smooth transition is observed between the threshold and the limit. Typically, the CDBI of the first ethylene polymer. 50 CDBI is the second ethylene polymer. 50 It's higher than that.

[0163] The second ethylene polymer M w / M n M of the first ethylene polymer w / M n Higher than the second ethylene polymer M w / M n The upper limit may be about 4.4, about 4.2 in other cases, and about 4.0 in yet other cases. M of the second ethylene polymer w / M n The lower limit may be approximately 2.2. w / M n The value becomes 2.2 when the melt index of the second ethylene polymer is high, or when the melt index of the ethylene polymer product is high (for example, more than 10 dg / min). In other cases, the M of the second ethylene polymer w / M n The lower limit may be approximately 2.4, and in other cases, approximately 2.6.

[0164] The second ethylene polymer contains catalyst residues that reflect the chemical composition of the heterogeneous catalyst formulation. Those skilled in the art will understand that the heterogeneous catalyst residues are typically quantified in parts per million (ppm) of metal in the second ethylene polymer. Here, metal refers to a metal derived from component (vii), i.e., a “metallic compound,” which will hereafter be referred to as “metal B.” As previously stated in this disclosure, non-limiting examples of metal B include metals selected from groups 4 through 8 of the periodic table, or mixtures of metals selected from groups 4 through 8. The upper limit of the ppm of metal B in the second ethylene polymer may be about 12 ppm, in other cases about 10 ppm, and in yet other cases about 8 ppm. The lower limit of the ppm of metal B in the second ethylene polymer may be about 1 ppm, in other cases about 2 ppm, and in yet other cases about 3 ppm. While we do not wish to be bound by any particular theory, in series mode operation, the chemical environment in the second reactor is thought to deactivate the crosslinked metallocene catalyst compound, and in parallel mode operation, the chemical environment in flow (12d) is thought to deactivate the crosslinked metallocene catalyst compound.

[0165] Referring to the embodiment shown in Figure 1, the amount of hydrogen added to R2 can be varied over a wide range, thereby enabling a continuous dissolution process to achieve a melt index (hereinafter referred to as I2). 2 (denoted as H2) can produce a second ethylene polymer that is significantly different. This is achieved by adjusting the hydrogen flow rate in flow 9. 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 (ppm) is used. In some cases, H2 R2 (ppm) is in the range of approximately 100 ppm to 0 ppm, sometimes approximately 50 ppm to 0 ppm, sometimes approximately 20 ppm to 0 ppm, and still other times approximately 2 ppm to 0 ppm. 2 The upper limit may be approximately 1000 dg / min, in some cases approximately 750 dg / min, in other cases approximately 500 dg / min, and in yet other cases approximately 200 dg / min. 2The lower limit may be about 0.3 dg / min, in some cases about 0.4 dg / min, in other cases about 0.5 dg / min, and in still other cases about 0.6 dg / min.

[0166] The upper limit of the weight percentage (wt%) of the second ethylene polymer in the ethylene polymer product may be about 85 wt%, in other cases about 80 wt%, and in still other cases about 70 wt%. The lower limit of the wt% of the second ethylene polymer in the ethylene polymer product may be about 30 wt%, in other cases about 40 wt%, and in still other cases about 50 wt%.

[0167] <The third ethylene polymer> Referring to the embodiment shown in FIG. 1, when the catalyst deactivator A is added upstream of the reactor 17 via the catalyst deactivator tank 18A, no third ethylene polymer is produced in the reactor 17 (R3). When the catalyst deactivator A is not added and no alpha-olefin is added to the reactor 17 via any of the paths of the fresh alpha-olefin stream 15 or the stream 12c from the reactor 12a (R2) in the series mode or the stream 12d in the parallel mode, the ethylene polymer produced in the reactor 17 is an ethylene homopolymer. When the catalyst deactivator A is not added and any alpha-olefin is present in R3, the density of the third ethylene polymer is determined by the following weight ratio: (alpha-olefin / ethylene) R3 . In the continuous solution polymerization process, (alpha-olefin / ethylene) R3 is one of the control parameters used to produce a third ethylene polymer having a desired density. (alpha-olefin / ethylene) R3 The upper limit may be about 3, in other cases about 2, and in still other cases about 1. (alpha-olefin) / (ethylene) R3 The lower limit may be 0, in other cases about 0.25, and in still other cases about 0.5. Hereinafter, the symbol "σ" 3 refers to the density of the ethylene polymer produced in R3. σ 3The upper limit is about 0.975 g / cm 3 , in some cases about 0.965 g / cm 3 , and in other cases about 0.955 g / cm 3 and may be. Depending on the heterogeneous catalyst formulation used, the lower limit of σ 3 is about 0.89 g / cm 3 , in some cases about 0.90 g / cm 3 , and in other cases about 0.91 g / cm 3 and may be. Optionally, a second heterogeneous catalyst formulation may be added to σ 3 .

[0168] Typically, the upper limit of the CDBI of any third ethylene polymer (including α-olefin) is about 65%, in other cases about 60%, and in still other cases about 55%. The CDBI of any third ethylene polymer including α-olefin 50 is lower than the CDBI of the first ethylene polymer produced using a single-site catalyst formulation. Typically, the lower limit of the CDBI of any third ethylene polymer (including α-olefin) is about 35%, in other cases about 40%, and in still other cases about 45%. If α-olefin is not added to the continuous solution polymerization process, any third ethylene polymer is an ethylene homopolymer. In the case of an ethylene homopolymer, the upper limit of the CDBI 50 is about 98%, in other cases about 96%, and in still other cases about 95%, and the lower limit of the CDBI 50 is about 88%, in other cases about 89%, and in still other cases about 90%. Typically, the CDBI of the first ethylene polymer 50 is higher than the CDBIs of the third ethylene polymer and the second ethylene polymer 50 . 50 50 The M of any third ethylene polymer 50 / M

[0169] w / M n ​​The upper limit may be about 5.0, about 4.8 in other cases, and about 4.5 in yet other cases. M of any third ethylene polymer w / M n The lower limit may be about 2.2, about 2.4 in other cases, and about 2.6 in yet other cases. M of any third ethylene polymer w / M n M of the first ethylene polymer w / M n It is higher than. When blended together, the second and third ethylene polymers are higher than the second ethylene polymer. w / M n The fourth M is not as wide as w / M n It has.

[0170] The catalyst residue in any third ethylene polymer reflects the chemical composition of the heterogeneous catalyst formulation used, namely the first heterogeneous catalyst formulation and optionally the second heterogeneous catalyst formulation. The chemical compositions of the first and second heterogeneous catalyst formulations may be the same or different. For example, the first and second heterogeneous catalyst formulations can be synthesized using the first component (vii) and the second component (vii). As stated above, "metal B" refers to the metal derived from the first component (vii). Hereinafter, "metal C" refers to the metal derived from the second component (vii). Metal B and any metal C may be the same or different. Non-limiting examples of metal B and metal C include metals selected from groups 4 through 8 of the periodic table, or mixtures of metals selected from groups 4 through 8. The upper limit of the ppm of (metal B + metal C) in any third ethylene polymer may be about 12 ppm, about 10 ppm in other cases, and about 8 ppm in yet other cases. The lower limit of ppm for (metal B + metal C) in any third ethylene polymer may be about 0.5 ppm, about 1 ppm in other cases, and about 3 ppm in yet other cases.

[0171] Referring to the embodiment shown in Figure 1, any hydrogen can be added to the tubular reactor (R3) via flow 16. The amount of hydrogen added to R3 can vary over a wide range. The amount of hydrogen in R3 (hereinafter referred to as H2) R3 By adjusting the melt index (hereinafter referred to as I2) in the continuous dissolution process, 3 (denoted as ) can produce any third ethylene polymer that is significantly different. The amount of hydrogen added to R3 is in the range of approximately 50 ppm to 0 ppm, sometimes approximately 25 ppm to 0 ppm, sometimes approximately 10 ppm to 0 ppm, and still other times approximately 2 ppm to 0 ppm. I2 3 The upper limit may be approximately 2000 dg / min, in some cases approximately 1500 dg / min, in other cases approximately 1000 dg / min, and in yet other cases approximately 500 dg / min. I2 3 The lower limit may be approximately 0.5 dg / min, in some cases approximately 0.6 dg / min, in other cases approximately 0.7 dg / min, and in yet other cases approximately 0.8 dg / min.

[0172] The upper limit of the weight percentage (wt%) of any third ethylene polymer in the ethylene polymer product may be about 30 wt%, about 25 wt%, and about 20 wt% in other cases. The lower limit of the weight percentage of any third ethylene polymer in the ethylene polymer product may be 0 wt%, about 5 wt%, and about 10 wt% in other cases.

[0173] <Ethylene polymer products> The upper limit of the density of ethylene polymer products is approximately 0.975 g / cm³. 3 In some cases, approximately 0.965 g / cm³ 3 In other cases, approximately 0.955 g / cm³ 3 This may also be the case. The lower limit of the density of the ethylene polymer product is approximately 0.869 g / cm³. 3 In some cases, approximately 0.879 g / cm³ 3 In other cases, approximately 0.889 g / cm³ 3 That's fine.

[0174] CDBI of ethylene polymer products 50 The upper limit may be approximately 97%, approximately 90% in other cases, and approximately 85% in yet other cases. If α-olefins are not added to the continuous solution polymerization process, CDBI 50 This can yield an ethylene polymer product with 97% purity, in which case the ethylene polymer product is an ethylene homopolymer. CDBI of ethylene polymers 50 The lower limit may be approximately 20%, approximately 40% in other cases, and approximately 60% in yet other cases.

[0175] M of ethylene polymer products w / M n The upper limit may be about 25, about 15 in other cases, and about 9 in yet other cases. M of the ethylene polymer product w / M n The lower limit may be 2.0, or in other cases about 2.2, and in yet other cases about 2.4.

[0176] The catalyst residue in the ethylene polymer product reflects the chemical composition of the crosslinked metallocene catalyst formulation used in R1, the first heterogeneous catalyst formulation used in R2, and optionally the first heterogeneous catalyst formulation used in R3, or optionally the first and second heterogeneous catalyst formulations used in R3. In this disclosure, the catalyst residue was quantified by measuring the ppm of catalyst metal in the ethylene polymer product. In addition, the elemental amounts (ppm) of magnesium, chlorine, and aluminum were quantified. The catalyst metal originates from two or optionally three sources, specifically: (1) "metal A" derived from component (i) used to form a single-site catalyst formulation, (2) "metal B" derived from a first component (vii) used to form a first heterogeneous catalyst formulation, and (3) optionally "metal C" derived from a second component (vii) used to form any second heterogeneous catalyst formulation. Metals A, B, and C may be the same or different. In this disclosure, the term “total catalyst metal” is synonymous with the sum of catalyst metals A + B + C. Furthermore, in this disclosure, the terms “first total catalyst metal” and “second total catalyst metal” are used to distinguish the first ethylene polymer product of this disclosure from comparative “polyethylene compositions” produced using different catalyst formulations.

[0177] The upper limit of the ppm of metal A in the ethylene polymer product may be about 0.6 ppm, about 0.5 ppm in other cases, and about 0.4 ppm in yet other cases. The lower limit of the ppm of metal A in the ethylene polymer product may be about 0.001 ppm, about 0.01 ppm in other cases, and about 0.03 ppm in yet other cases. The upper limit of the ppm of (metal B + metal C) in the ethylene polymer product may be about 11 ppm, about 9 ppm in other cases, and about 7 ppm in yet other cases. The lower limit of the ppm of (metal B + metal C) in the ethylene polymer product may be about 1 ppm, about 2 ppm in other cases, and about 3 ppm in yet other cases.

[0178] In some embodiments, ethylene polymers can be produced even when the catalyst metals (metal A, metal B, and metal C) are the same metal. A non-limiting example is titanium. In such embodiments, the ppm of (metal B + metal C) in the ethylene polymer product is calculated using equation (VII): Sprawl (B+C) = ((ppm (A+B+C) -(f A ×ppm A )) / (1-f A ) (VII) (In the formula, ppm (B+C) This is the calculated ppm of (metal B + metal C) in the ethylene polymer product, and ppm (A+B+C) This is the total ppm of catalyst residue in the experimentally measured ethylene polymer product, i.e., (metal Appm + metal Bppm + metal Cppm), and f A f represents the weight fraction of the first ethylene polymer in the ethylene polymer product, and A This can vary from approximately 0.15 to approximately 0.6, in ppm. A (where represents the ppm of metal A in the first ethylene polymer). In formula (VII), ppm A Let's assume it is 0.35 ppm.

[0179] The embodiments of the ethylene polymer products disclosed herein have less catalyst residue compared to the polyethylene polymer described in U.S. Patent No. 6,277,931. The increase in catalyst residue in U.S. Patent No. 6,277,931 increases the complexity of the continuous solution polymerization process. This increased complexity includes an additional purification step to remove the catalyst residue from the polymer. In contrast, the catalyst residue is not removed in this disclosure. In this disclosure, the upper limit of the total ppm of catalyst residue (metal A + metal B + any metal C) in the ethylene polymer product may be about 12 ppm, in other cases about 9 ppm, and in yet other cases about 7 ppm, and the lower limit of the total ppm of catalyst residue (metal A + metal B + any metal C) in the ethylene polymer product may be about 1 ppm, in other cases about 2 ppm, and in yet other cases about 3 ppm.

[0180] The upper limit of the melt index of the ethylene polymer product may be approximately 500 dg / min, possibly approximately 400 dg / min, otherwise approximately 300 dg / min, and still otherwise approximately 200 dg / min. The lower limit of the melt index of the ethylene polymer product may be approximately 0.3 dg / min, possibly approximately 0.4 dg / min, otherwise approximately 0.5 dg / min, and still otherwise approximately 0.6 dg / min.

[0181] <Flexible manufactured goods> The ethylene polymer products disclosed herein can be converted into a wide variety of flexible manufactured articles. Non-limiting examples include single-layer films and multi-layer films, such films are well known to those skilled in the art. Non-limiting examples of processes for preparing such films include inflation film processes and cast film processes.

[0182] Depending on the end application, the disclosed ethylene polymer products can be converted into films across a wide range of thicknesses. Non-limiting examples include food packaging films with thicknesses ranging from approximately 0.5 mil (13 μm) to approximately 4 mil (102 μm), and films with thicknesses ranging from approximately 2 mil (51 μm) to approximately 10 mil (254 μm) for use in heavy-duty bags.

[0183] The ethylene polymer products disclosed herein may be used in a single-layer film, which may contain multiple ethylene polymer products and / or additional thermoplastics; non-limiting examples of thermoplastics include ethylene polymers and propylene polymers. The lower limit of the weight percentage of the ethylene polymer product having improved color in the single-layer film may be about 3% by weight, in other cases about 10% by weight, and in yet other cases about 30% by weight. The upper limit of the weight percentage of the ethylene polymer product having improved color in the single-layer film may be 100% by weight, in other cases about 90% by weight, and in yet other cases about 70% by weight.

[0184] The improved color ethylene polymer products disclosed herein may also be used in one or more layers of a multilayer film; non-limiting examples of multilayer films include 3, 5, 7, 9, 11 or more layers. The thickness of a particular layer in the multilayer film (containing the improved color ethylene polymer product) may be about 5% of the total multilayer film thickness, in other cases about 15%, and in yet other cases about 30%. In other embodiments, the thickness of a particular layer in the multilayer film (containing the improved color ethylene polymer product) may be about 95% of the total multilayer film thickness, in other cases about 80%, and in yet other cases about 65%. Each individual layer of the multilayer film may contain multiple ethylene polymer products and / or additional thermoplastics.

[0185] Additional embodiments include lamination and coating, in which a single or multilayer film containing an ethylene polymer product having the disclosed improved color is extruded, adhesively laminated, or extruded coated. In extruded or adhesive lamination, two or more substrates are bonded together with a thermoplastic resin or adhesive. In extruded coating, a thermoplastic material is applied to the surface of the substrate. These processes are well known to those skilled in the art.

[0186] The ethylene polymer products disclosed herein can be used in a wide range of manufactured articles, such as articles comprising one or more films (single-layer or multi-layer). Non-limiting examples of such manufactured articles include: food packaging films (for fresh foods, frozen foods, liquid foods, and granular foods), stand-up pouches, retort packaging, and bag-in-box packaging; barrier films (for oxygen, moisture, fragrance, oil, etc.) and modified atmosphere packaging; lightweight and heavy-duty shrink films and wraps, collated shrink films, pallet shrink films, shrink bags, shrink ties, and shrink shrouds; lightweight and heavy-duty stretched films, hand-stretched wraps, machine-stretched wraps, and stretched food films; high-transparency films; heavy-duty bags; household wraps, overlap films, sandwich bags; industrial and facility films, garbage bags, can liners, magazine overlaps, newspaper bags, mailbags, bags and envelopes, bubble wrap, carpet films, furniture bags, clothing bags, coin bags, automotive panel films; gowns, dresses Medical applications such as trousers and surgical gowns; construction films and sheets, asphalt films, insulation bags, masking films, landscaping films and bags; geomembrane liners for municipal waste treatment and mining applications; bulk sealing bags; agricultural films, mulch films, greenhouse films; in-store packaging, self-service bags, boutique bags, grocery bags, take-out bags, T-shirt bags; oriented films, mechanically oriented and biaxially oriented films, and functional film layers (e.g., sealant and / or toughness layers) of oriented polypropylene (OPP) films. Additional manufactured articles comprising one or more films containing at least one ethylene polymer product having improved color include laminates and / or multilayer films, sealant and tie layers in multilayer films and composite materials, laminations with paper, aluminum foil laminates, or laminates containing vacuum-deposited aluminum, polyamide laminates, polyester laminates, extruded coated laminates, and hot-melt adhesive formulations. The manufactured articles summarized in this paragraph include at least one film (monolayer or multilayer) comprising at least one embodiment of the disclosed ethylene polymer product having improved color.The desired film properties (single-layer or multi-layer) typically depend on the intended application. Non-limiting examples of desired film properties include optical properties (gloss, haze, and clarity), dart impact, Elmendorf tear strength, modulus of elasticity (1% and 2% secant coefficients), puncture-propagation tear resistance, tensile properties (yield strength, breaking strength, elongation at break, toughness, etc.), and heat sealing properties (heat seal initiation temperature and hot tack strength). Specific hot tack and heat sealing properties are desired in high-speed vertical and horizontal pouch-filling processes for filling and sealing commercially available products (liquids, solids, pastes, components, etc.) into pouch-like packaging.

[0187] The films used in the manufactured articles described in this section may optionally contain additives and auxiliaries depending on their intended use. Non-limiting examples of additives and auxiliaries include antiblocking agents, primary antioxidants, secondary antioxidants, heat stabilizers, slip agents, processing aids, antistatic additives, colorants, dyes, fillers, light stabilizers, light absorbers, lubricants, pigments, plasticizers, nucleating agents, and combinations thereof. Non-limiting examples of suitable primary antioxidants include Irganox 1010 [CAS Registry No. 6683-19-8] and Irganox 1076 [CAS Registry No. 2082-79-3], both available from BASF Corporation (Florham Park, New Jersey, USA). Non-exclusive examples of suitable secondary antioxidants include Irgafos 168 [CAS Registry No. 31570-04-4], available from BASF Corporation (Florham Park, New Jersey, USA); Weston 705 [CAS Registry No. 939402-02-5], available from Addivant (Danbury, Connecticut, USA); and Doverphos Igp-11 [CAS Registry No. 1227937-46-3], available from Dover Chemical Corporation (Dover, Ohio, USA). [Examples]

[0188] <Solution-phase polymerization process> The continuous solution-phase polymerizations in Examples 1 and 2 were each carried out in a commercial “in-series” multi-reactor solution polymerization process using a mixed binary catalyst system. In this process, ethylene polymer products were produced by forming a first ethylene polymer in a first reactor (R1), a second ethylene polymer in a second reactor (R2), and a third ethylene polymer in a third reactor (R3), where R1, R2, and R3 were configured in series with each other.

[0189] The pressure in R1 was from about 14 MPa to about 18 MPa, and R2 was operated at a lower pressure to facilitate the continuous flow from R1 to R2. Both R1 and R2 were continuous stirred-tank reactors (CSTRs) and were stirred under conditions where the contents of the reactors were well mixed. The two CSTR reactors (R1 and R2) were configured in series, followed by the connection of a third reactor (R3). The third reactor (R3) was a tubular reactor. This process was continuously operated by feeding fresh process solvent, ethylene, 1-octene, and hydrogen to the first and second reactors (R1 and R2) and removing the product. Methylpentane was used as the process solvent (a commercial blend of methylpentane isomers). The monomer (ethylene) and comonomer (1-octene) were purified using a conventional feed preparation system (such as contact with various absorption media to remove impurities such as water, oxygen, polar contaminants, etc.) before being added to the reactor.

[0190] Methylpentane was used as the process solvent (a commercially available blend of methylpentane isomers). The monomer (ethylene) and comonomer (1-octene) were purified using a conventional feedstock preparation system (e.g., contact with various absorbents to remove impurities such as water, oxygen, and polar contaminants) before being added to the reactor. The ethylene, 1-octene, and process solvent were combined and injected into reactors R1 and R2 in the ratios shown in Table 1. The R1 feed flow temperatures in Examples 1 and 2 were controlled to 24.1°C and 24.0°C, respectively. The R2 feed flow temperatures in Examples 1 and 2 were controlled to 68.9°C and 69.9°C, respectively.

[0191] The ethylene concentration in the R1 feedstream was 13.7 wt% and 12.6 wt%, respectively, in Example 1 and Example 2, based on the total weight of the R1 feedstream injected into R1 per unit time. The ethylene concentration in the R2 feedstream was 15.7 wt% and 15.8 wt%, respectively, in Example 1 and Example 2, based on the total weight of the R2 feedstream injected into R2 per unit time. The relative concentrations of 1-octene to ethylene in the R1 feedstream were 0.294 wt% / wt% and 0.449 wt% / wt%, respectively, in Example 1 and Example 2, based on the ratio of weight percent of ethylene to weight percent of 1-octene in the R1 feedstream. The relative concentrations of 1-octene to ethylene in the R2 feedstream were 0.782 wt% / wt% and 0.903 wt% / wt% in Example 1 and Example 2, respectively, based on the ratio of weight percent of ethylene to weight percent of 1-octene in the R2 feedstream.

[0192] When operating the continuous solution polymerization process shown in Table 1, the total amount of ethylene supplied to the process was distributed or split among the three reactors R1, R2, and R3. In Table 1, this operating variable is referred to as the ethylene split (ES), i.e., ES R1 , ES R2 , and ES R3 These refer to the weight percentage of ethylene injected into R1, R2, and R3, respectively. However, ES R1 +ESR2 +ES R3 The condition is that =100%. 1-Octene was also added to the continuous solution polymerization process and distributed or split among R1, R2, and R3. In Table 1, this operational variable is called the 1-octene split (OS), i.e., OS R1 OS R2 , and OS R3 These refer to the weight percentage of 1-octen comonomer injected into R1, R2, and R3, respectively. However, OS R1 OS R2 +OS R3 The condition is that it equals 100%.

[0193] When operating the continuous solution polymerization process shown in Table 1, the total amount of ethylene converted in each reactor is monitored. R1 The term refers to the percentage of ethylene added to R1 that is converted to the first ethylene polymer by the catalyst compound. Similarly, Q R2 and Q R3 This represents the percentage of ethylene added to R2 and the percentage of residual ethylene that flowed from R1 and R2 into R3 that was converted to the second and third ethylene polymers, respectively.

[0194] In Table 1, Q T The term Q represents the total ethylene conversion rate throughout a continuous solution-phase polymerization plant, i.e., Q T = 100 × [weight of ethylene in the ethylene polymer product] / ([weight of ethylene in the ethylene polymer product] + [weight of unreacted ethylene]).

[0195] In Examples 1 and 2, a first ethylene polymer was prepared in a first reactor (R1) configured in series with the second reactor (R2) and the third reactor (R3) using the following crosslinked metallocene catalyst components: Component A: diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethide [(2,7-tBu2Flu)Ph2C(Cp)HfMe2]; Component M: methylaluminoxane (MMAO-07); Component B: trityltetrakis(pentafluorophenyl)borate (tritylborate); and Component P: 2,6-di-t-butyl-4-ethylphenol (BHEB). Methylaluminoxane (MMAO-07) and 2,6-di-tert-butyl-4-ethylphenol were pre-mixed inline and then mixed with diphenylmethylene (cyclopentadienyl)(2,7-di-t-butylfluorenyl)hafnium dimethyl and trityltetrakis(pentafluorophenyl) borate immediately before entering the polymerization reactor (R1). Methylpentane was used as the catalyst solvent for components M and P, and xylene was used for components A and B. The efficiency of the crosslinked metallocene catalyst formulation was optimized by adjusting the amount of component A added to R1 (R1 catalyst (ppm) shown in Table 1), the molar ratio of the catalyst components (i.e., [M] / [A], [P] / [M], and [B] / [A] shown in Table 1), and the R1 catalyst inlet temperature (not shown in Table 1). The R1 catalyst inlet temperature was controlled to 20-40°C.

[0196] In Examples 1 and 2, a second ethylene interpolymer was prepared in a second reactor (R2) using an in-line Ziegler-Natta catalyst formulation. The in-line Ziegler-Natta catalyst formulation contained the following components: butylethylmagnesium [component v], tert-butyl chloride [component vi], titanium tetrachloride [component vii], diethylaluminum ethoxide [component viiii], and triethylaluminum [component ix]. Methylpentane was used as the catalyst solvent, and the in-line Ziegler-Natta catalyst formulation was prepared according to the following procedure and then injected into the second reactor (R2). In Step 1, a solution of triethylaluminum and butylethylmagnesium (Mg:Al=20, molars:molars) was combined with a tert-butyl chloride solution and reacted for approximately 30 seconds to produce a MgCl2 support. In Step 2, a titanium tetrachloride solution was added to the mixture produced in Step 1 and reacted for approximately 14 seconds before being injected into the second reactor (R2). The in-line Ziegler-Natta catalyst was activated in the reactor by injecting a diethylaluminum ethoxide solution into R2. The efficiency of the in-line Ziegler-Natta catalyst formulation was optimized by adjusting the amount of titanium tetrachloride added to the reactor (listed as R2 catalyst (ppm) in Table 1), the molar ratio of the catalyst components (shown in Table 1 as [vi] / [v], [viii] / [vii], and [ix] / [vii]), and the R2 catalyst inlet temperature (not shown in Tables 1A-1C). The R2 catalyst inlet temperature was controlled between 20 and 40°C. The catalyst system and feed flow were injected into the second reactor (R2) through separate feed lines, which were located approximately midway between the upper and lower parts of the reactor and opposed to each other.

[0197] In Examples 1 and 2, fresh ethylene, 1-octene, hydrogen, and catalyst were not pumped into the third reactor. Residual ethylene, residual 1-octene, and residual active catalyst that entered the third reactor (R3) from the upstream reactors R1 and R2 formed the third ethylene polymer in these examples.

[0198] Polymerization in the continuous solution polymerization process was stopped by adding a catalyst deactivator to the outlet flow of the third reactor. Using a multi-stage phase separation process, the outlet flow of the third reactor was heated and passed through multiple V / L separators configured in series to recover the ethylene interpolymer product from the process solvent. The polymer-rich flow (containing 94.5–96.5 wt percent of the ethylene polymer product) from the final V / L separator was fed to a twin-screw extruder for additive addition and pelletization.

[0199] The continuous solution-phase polymerization in Examples 3 and 4 was carried out under substantially the same conditions as those disclosed in Examples 1 and 2, except that: a non-crosslinked single-site catalyst represented by the chemical formula Cp(t-Bu)3PNTiCl2 was injected into R1 instead of hafnosene component A; and the composition, temperature, and total dissolution rate of the mixed feed stream injected into R2 were adjusted in Example 3 to an ethylene concentration of 27.5 wt%, a 1-octene to ethylene relative concentration of 0.20 wt% / wt%, a feed stream temperature of 28.0°C, and a total feed stream dissolution rate of 109 Mg / h; and in Example 4 to an ethylene concentration of 20.3 wt%, a 1-octene to ethylene relative concentration of 0.19 wt% / wt%, a feed stream temperature of 70°C, and a total feed stream dissolution rate of 149.5 Mg / h. The catalyst formulation injected into R1 in Examples 3 and 4 contained the same components M, B, and P as those used in Examples 1 and 2. The in-line Zn catalyst formulation injected into R2 in Examples 3 and 4 was the same as the in-line Zn catalyst described herein in Examples 1 and 2. In Examples 3 and 4, the outlet temperatures of the second reactor R2 were set to 188.3°C and 188.0°C, respectively. In Examples 3 and 4, similar polymerization conditions were used in the first reactor R1 to achieve a target density of 0.919 g / cm³. 3 It was produced with a target melt index of 20.85 dg / min.

[0200] Reactors R1, R2, and R3 in Examples 1-4 were operated under adiabatic conditions. The term "adiabatic" means that no heat is added to or removed from the polymerization reaction, and the reactor temperature is not increased during the polymerization process.

[0201] The ethylene polymer products prepared in Examples 1 to 4 contained 750 ppm (by weight) of AO-168, 500 ppm (by weight) of SUMILIZER® GP, and 350 ppm (by weight) of AO-1076.

[0202] [Table 1]

[0203] <Film defect> The absence of defects is a common quality indicator for films prepared from polymer compositions with a thickness of approximately 130 μm or less. These defects are defined herein as inclusions that have a clear phase boundary with the film matrix, exhibit different light transmittance from the surrounding material, and are detectable by an optical scanning system. Those skilled in the art will understand that the presence of these defects can result in visually unacceptable films, film breakage, or rupture, potentially adversely affecting film production equipment.

[0204] These defects in ethylene polymer products prepared according to this disclosure can be evaluated using well-known techniques for extruding film samples and subjecting them to a defect detection system for inspection. The extruder may be configured in at-line operation for continuous quality control during the production of the ethylene polymer product, or in offline operation for supplying the prepared ethylene polymer product to the extruder in small batches.

[0205] This disclosure evaluates defects in the ethylene polymer products prepared in Examples 1 to 4. This evaluation was performed by sampling 90–180 g of the product every 3 minutes and continuously extruding the sampled material into a 50 μm single-layer cast film prepared at a take-up rate of 7 meters / min, a film / winder tension of 6.5 Newtons, and an airflow rate of 6000 liters / hour. The prepared film was passed under a high-resolution line-scan camera (FSA-100 OCS camera). The cast extrusion process consisted of an ME-20 / 2800 V3.4 extruder with five heating zones Z1–Z5 (zone temperatures 210°C / 220°C / 220°C / 220°C / 220°C, feed port temperature 40°C), a CR-9 / G OCS chill roll maintained at 23.0°C, and an FSA-100 OCS camera with a pixel resolution of 25 μm. The OCS extruder was equipped with a 4:1 compression ratio screw and did not have a screen pack. The described extrusion parameters were confirmed not to cause polymer degradation that could result in artificial defects in the tested ethylene polymer product. To detect stepwise changes in the quality of the ethylene polymer product, the number of defects in various size categories was monitored. The size categories were 250–500 μm, 501–750 μm, 751–1000 μm, 1001–1500 μm, 1501–2000 μm, and over 2000 μm. Defect size was calculated by calculating the equivalent circle diameter of the defect. The total number of defects was reported as a total ppm value, defined based on the total area of ​​defects ranging from 250 μm to 2000 μm relative to the total evaluated area of ​​the rolling window of the produced film (width 66.4 mm, length 5.12 m). Specifically, the total number of defects was calculated by multiplying the total area of ​​defects by 10. 6 It was calculated by multiplying by and then dividing the result by the total evaluated area.

[0206] The ethylene polymer product produced in Example 1 showed a stable total defect count during operation, with an average value of 0.16 ppm. Similarly, the ethylene polymer product produced in Example 2 showed a stable total defect count during operation, with an average value of 0.09 ppm. In contrast to Examples 1 and 2, the ethylene polymer product produced in Example 3 was characterized by an unstable total defect count during operation, with intervals where the total defect count reached values ​​exceeding 30 ppm. Compared to Example 3, the ethylene polymer product produced in Example 4 showed a reduced total defect count during operation, consistently below 1.5 ppm.

[0207] In the film samples prepared in Example 3, portions with increased defect levels were labeled, and defects exceeding 750 μm were further analyzed. The analysis was performed using a combination of a BRUKER HYPERION 3000 Fourier transform infrared (FTIR) microscope and a Bruker Tensor 27 spectrometer. The observed defects were classified according to one of the following categories: non-oxidized polyethylene (NOPE) defects, oxidized polyethylene defects, residual catalyst particles, additive particles, undispersed talc or silicate particles, fibers (clothing or cellulose), and other contaminants such as dust, dirt, and oil. Of the 20 defects characterized using FTIR microscopy in the ethylene polymer product produced in Example 3, 18 were classified as NOPE defects based on their FTIR signatures. NOPE defects are defined herein as inclusions characterized by an FTIR spectrum that does not contain additional chemical species other than ethylene and α-olefin monomer units. NOPE defects are ethylene homopolymers or copolymers having a weight-average molecular weight exceeding that of the ethylene polymer product, and may have a different chemical composition from the ethylene polymer product matrix. If the NOPE defect is an ethylene homopolymer, the FTIR spectrum observed for the inclusion will not include peaks known to originate from α-olefin monomer units. For example, the observed FTIR spectrum will include peaks at approximately 1378 and 770 cm⁻¹. -1 (1-Butene), 1377 and 895 cm -1 (1-hexen), and 1377 cm-1 No peak is observed at the (1-octene) wavenumber. Furthermore, the observed second derivative spectrum shows a peak at approximately 780 cm⁻¹. -1 (1-butene and 1-hexene) and approximately 785 cm -1 and 770cm -1 No peak was observed for (1-octene).

[0208] While we do not wish to be bound by any theory, we can assume that the NOPE defect originates in the feed zone of R2, where the feed reactants (ethylene, hydrogen solvent, and optionally 1-octen comonomer) enter the second reactor R2. The degree of polymerization (DPN) in a polymerization reaction is proportional to the total rate of the chain growth reaction and inversely proportional to the total rate of the chain transfer / termination reaction. Conditions under which the total rate of the chain growth reaction increases relative to the total rate of the chain transfer / termination reaction result in higher molecular weights. If the ethylene concentration in the feed stream is high at low temperatures (e.g., below 60°C) (e.g., more than 25% by weight based on the total weight of the fresh feed stream injected into the second reactor per unit time), the first heterogeneous catalyst supplied to the second reactor is temporarily exposed to high ethylene concentrations in the feed zone, resulting in very high and / or extremely high MW (i.e., M) w This may produce trace amounts of catalyst (exceeding 10⁶ g / mol). Those skilled in the art will recognize that the intensity of mixing in the feed zone within the second reactor minimizes the period during which the first heterogeneous catalyst is exposed to high ethylene concentrations. Such feed zone polymers generally do not miscible with the bulk ethylene polymer product and become visible defects in the final film prepared from the ethylene polymer product produced in Example 3. NOPE defects may have melting temperatures that are measurably higher (e.g., using techniques such as hot-stage microscopy) or lower than the bulk ethylene polymer product matrix, and given the large molecular weight mismatch with the bulk ethylene polymer product, they remain undispersed under the deformation fields that occur in conventional thin-film production methods.

[0209] Furthermore, and more importantly, the low defect count observed in the ethylene polymer products produced in Examples 1 and 2 can be analyzed by considering the composition and temperature conditions of the R2 feed stream applied in these examples. While we do not wish to be bound by any theory, in Examples 1 and 2, the high temperature of the R2 feed stream and the low ethylene concentration in the R2 feed stream inhibited the formation of ultra-high MW feed zone polymers, resulting in a lower visual defect content in the films prepared from the ethylene polymer products prepared in Examples 1 and 2.

[0210] The solution-phase polymerization process performed in Example 4 is important in that it further demonstrates the following: a) the active catalytic site that formed the NOPE gel in the final ethylene polymer product is the in-line Zn catalyst added to R2, and b) consistent with the observations in Examples 1 and 2, when the temperature of the R2 feed stream is low and the ethylene concentration in the R2 feed stream is high, there is a greater tendency for ultra-high MW feed zone polymers to form in R2.

Claims

1. A continuous solution phase polymerization process for providing ethylene polymer products, The ethylene polymer product comprises a first ethylene polymer and a second ethylene polymer. The aforementioned process, a) A step of injecting a crosslinked metallocene catalyst mixture, a process solvent, and ethylene into a first reactor to generate a first outlet flow containing a first ethylene polymer in the process solvent, b) A step of passing the first outlet flow through the second reactor, injecting the first heterogeneous catalyst mixture and the second feed flow into the second reactor to generate a second outlet flow containing the second ethylene polymer and the first ethylene polymer in the process solvent, wherein the second feed flow is generated by combining the process solvent and ethylene, and Includes, The process wherein the ethylene concentration in the second feed stream is 25% by weight or less, based on the total weight of the second feed stream injected into the second reactor per unit time, and the temperature of the second feed stream is 60°C or higher and 90°C or lower.

2. A continuous solution phase polymerization process for providing ethylene polymer products, The ethylene polymer product comprises a first ethylene polymer and a second ethylene polymer. The aforementioned process, a) A step of injecting a crosslinked metallocene catalyst mixture, a process solvent, and ethylene into a first reactor to generate a first outlet flow containing a first ethylene polymer in the process solvent, b) A step of injecting the first heterogeneous catalyst mixture and the second feed stream into the second reactor to generate a second outlet stream containing the second ethylene polymer in the process solvent, wherein the second feed stream is generated by combining the process solvent and ethylene. c) A step of combining the first outlet flow and the second outlet flow to form a third outlet flow. Includes, The process wherein the ethylene concentration in the second feed stream is 25% by weight or less based on the total weight of the second feed stream injected into the second reactor per unit time, and the temperature of the second feed stream injected into the second reactor is 60°C or higher and 90°C or lower.

3. Step a) involves adding one or more C to the first reactor. ３ ~C １０ The process according to claim 1 or 2, further comprising injecting an α-olefin.

4. In step b), the second feed stream is injected into the second reactor, and the second feed stream contains ethylene by weight percentage and one or more C ３ ~C １０ Based on the ratio to the weight percentage of α-olefins, one or more C compounds have a relative concentration of 0.15 to 2 relative to ethylene. ３ ~C １０ The process according to any one of claims 1 to 3, further comprising the α-olefin.

5. C ３ ~C １０ The process according to claim 3 or 4, wherein the α-olefin is selected from 1-hexene, 1-octene, or a mixture of 1-hexene and 1-octene.

6. The process according to any one of claims 1 to 5, wherein the second feed stream injected into the second reactor in step b) contains hydrogen at a concentration of 0.1 to 20 ppm based on the total weight of the second feed stream injected into the second reactor per unit time.

7. The aforementioned crosslinked metallocene catalyst formulation is Component A defined by equation (I): 【Chemistry 1】 (In the formula, M is a Group 4 metal selected from titanium, zirconium or hafnium; G is a Group 14 element selected from carbon, silicon, germanium, tin or lead; R １ is a hydrogen atom, C １－２０ hydrocarbyl radical, C １－２０ alkoxy radical, or C ６－１０ aryloxide radical; R ２ and R ３ are independently selected from a hydrogen atom, C １－２０ hydrocarbyl radical, C １－２０ alkoxy radical or C ６－１０ aryloxide radical; R ４ and R ５ are independently selected from a hydrogen atom, unsubstituted C １－２０ hydrocarbyl radical, substituted C １－２０ hydrocarbyl radical, C １－２０ alkoxy radical or C ６－１０ aryloxide radical; Q is independently an activatable leaving group ligand), and Almoxane co-catalyst, Boron ionic surfactants, Optionally, hindered phenol and The process according to any one of claims 1 to 6, including the process described in any one of claims 1 to 6.

8. The aforementioned crosslinked metallocene catalyst formulation is Component A defined by equation (II): 【Chemistry 2】 (wherein G is a Group 14 element selected from carbon, silicon, germanium, tin, or lead; R １ C is a hydrogen atom. １－２０ Hydrocarbyl radical, C １－２０ Alkoxy radicals, or C ６－１０ It is an aryl oxide radical; R ２ and R ３ C is a hydrogen atom. １－２０ Hydrocarbyl radical, C １－２０ Alkoxy radicals or C ６－１０ Selected independently from aryl oxide radicals; R ４ and R ５ This is a hydrogen atom, unsubstituted C １－２０ Hydrocarbyl radical, substituted C １－２０ Hydrocarbyl radical, C １－２０ Alkoxy radicals or C ６－１０ (Selected independently from aryl oxide radicals; Q is independently an activatable leaving ligand), Almoxane co-catalyst, Boron ionic surfactants, Optionally, hindered phenol and The process according to any one of claims 1 to 6, including the process described in any one of claims 1 to 6.

9. The process according to claim 7 or 8, wherein the molar ratio of the boron ionic activator to component A in the first reactor is 0.1:1 to 10:1, the molar ratio of the almoxane cocatalyst to component A in the first reactor is 1:1 to 1000:1, and, if present, the molar ratio of the hindered phenol to the almoxane cocatalyst in the first reactor is 0.0:1 to 10:

1.

10. The process according to any one of claims 7 to 9, wherein the almoxane cocatalyst is methylalmoxane.

11. The process according to any one of claims 7 to 9, wherein the boron ionic surfactant is trityltetrakis(pentafluorophenyl)borate.

12. The process according to any one of claims 1 to 11, wherein the first heterogeneous catalyst formulation is a first in-line Ziegler-Natta catalyst formulation.

13. The first in-line Ziegler-Natta catalyst compound is formed by an in-line process, and the in-line process is A first step of a first heterogeneous catalyst assembly is to combine flow S1 and flow S2 to form a first product mixture, and to equilibrate the first product mixture for HUT-1 second; wherein flow S1 contains a magnesium compound and an aluminum alkyl in the process solvent, and flow S2 contains a chloride compound in the process solvent. A second step of a first heterogeneous catalyst assembly, comprising: combining the first product mixture with flow S3 to form a second product mixture; and equilibrating the second product mixture for HUT-2 seconds; wherein flow S3 contains a metal compound in the process solvent; A third step of the first heterogeneous catalyst assembly, comprising: combining a second product mixture with flow S4 to form a first in-line Ziegler-Natta catalyst formulation; and equilibrating the in-line Ziegler-Natta catalyst formulation for HUT-3 seconds before injection into the second reactor; wherein flow S4 contains an alkylaluminum co-catalyst in the process solvent; The process according to claim 12, including the process described in claim 12.

14. The process according to claim 13, wherein HUT-1 is approximately 5 seconds to approximately 70 seconds, HUT-2 is approximately 2 seconds to approximately 50 seconds, and HUT-3 is approximately 0.5 seconds to approximately 15 seconds.

15. The process according to claim 13, wherein the molar ratio of aluminum alkyl to magnesium compound in the second reactor is about 3.0:1 to about 70:1, the molar ratio of chloride compound to magnesium compound in the second reactor is about 1.0:1 to about 4.0:1, the molar ratio of alkylaluminum cocatalyst to metal compound in the second reactor is about 0:1 to about 10:1, and the molar ratio of aluminum alkyl to metal compound in the second reactor is about 0.05:1 to about 2:

1.

16. Magnesium compounds are given by formula Mg(R １ ) ２ Defined by (where R １ The base may be the same or different.) Aluminum alkyl is of the formula Al(R ３ ) ３ Defined by (in the formula, R ３ The base may be the same or different.) Chloride compounds, formula R ２ Defined in Cl, Metal compounds, formula M ＊ (X) ｎ or M ＊ O(X) ｎ Defined by (where M ＊ is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, or mixtures thereof, O is oxygen, X is chloride or bromide, and n is metal M ＊ (An integer that satisfies the oxidation state of) Alkylaluminum cocatalysts are of the formula Al(R ４ ) ｐ (OR ５ ) ｑ (X) ｒ Defined by (in the formula, R ４ The bases may be the same or different, OR ５ The bases may be the same or different, and (p + q + r) = 3, provided that p is greater than 0. In the formula, R １ , R ２ , R ３ , R ４ , and R ５ The process according to claim 13, wherein the hydrocarbyl group having 1 to 10 carbon atoms is represented.

17. M in metal compounds ＊ The process according to claim 16, wherein the material is titanium, zirconium, hafnium, vanadium, chromium, or a mixture thereof.

18. The first in-line Ziegler-Natta catalyst compound is formed by an in-line process, and the in-line process is A first step of a first heterogeneous catalyst assembly is to combine flow S1 and flow S2 to form a first product mixture, and to equilibrate the first product mixture for HUT-1 second, wherein flow S1 contains a magnesium compound and an aluminum alkyl in the process solvent, and flow S2 contains a chloride compound in the process solvent. A second step of the first heterogeneous catalyst assembly, comprising the steps of forming a second product mixture by combining the first product mixture with flow S3, and equilibrating the second product mixture for HUT-2 seconds, wherein flow S3 contains a metal compound in the process solvent. A step of forming a first in-line Ziegler-Natta catalyst compound in a second reactor, wherein the second product mixture is further equilibrated for HUT-3 seconds in the third step of the first heterogeneous catalyst assembly and injected into the second reactor, and a flow S4 containing alkylaluminum co-catalyst in the process solvent is independently injected into the second reactor. The process according to claim 12, including the process described in claim 12.

19. The process according to claim 18, wherein HUT-1 is approximately 5 seconds to approximately 70 seconds, HUT-2 is approximately 2 seconds to approximately 50 seconds, and HUT-3 is approximately 0.5 seconds to approximately 15 seconds.

20. The process according to claim 18, wherein the molar ratio of aluminum alkyl to magnesium compound in the second reactor is about 3.0:1 to about 70:1, the molar ratio of chloride compound to magnesium compound in the second reactor is about 1.0:1 to about 4.0:1, the molar ratio of alkylaluminum cocatalyst to metal compound in the second reactor is about 0:1 to about 10:1, and the molar ratio of aluminum alkyl to metal compound in the second reactor is about 0.05:1 to about 2:

1.

21. Magnesium compounds are given by formula Mg(R １ ) ２ Defined by (where R １ The base may be the same or different.) Aluminum alkyl is of the formula Al(R ３ ) ３ Defined by (in the formula, R ３ The base may be the same or different.) Chloride compounds, formula R ２ Defined in Cl, Metal compounds, formula M ＊ (X) ｎ or M ＊ O(X) ｎ Defined by (where M ＊ is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, or mixtures thereof, O is oxygen, X is chloride or bromide, and n is metal M ＊ (An integer that satisfies the oxidation state of) Alkylaluminum cocatalysts are of the formula Al(R ４ ) ｐ (OR ５ ) ｑ (X) ｒ Defined by (in the formula, R ４ The bases may be the same or different, OR ５ The bases may be the same or different, and (p + q + r) = 3, provided that p is greater than 0. In the formula, R １ , R ２ , R ３ , R ４ , and R ５ The process according to claim 18, wherein the hydrocarbyl group having 1 to 10 carbon atoms is represented.

22. M in the metal compound ＊ The process according to claim 21, wherein M represents titanium, zirconium, hafnium, vanadium, chromium or a mixture thereof.

23. The process according to any one of claims 1 to 22, wherein the ethylene concentration in the second feed stream injected into the second reactor is less than 21 weight percent and greater than 15 weight percent, based on the total weight of the second feed stream injected into the second reactor per unit time.

24. The first outlet flow is at the first temperature T １ It has a second outlet flow at a second temperature T ２ It has T １ and T ２ However, 45<T ２ -T １ The process according to any one of claims 1 to 23, satisfying inequality 70.

25. A process according to claim 1, further comprising passing a second outlet flow from step b) through a third reactor and optionally injecting ethylene, a process solvent, one or more α-olefins, hydrogen, and a second heterogeneous catalyst mixture into the third reactor to generate a fourth outlet flow containing any third ethylene polymer, a second ethylene polymer, and a first ethylene polymer in the process solvent.

26. A process according to claim 2, further comprising passing a third outlet flow from step c) through a third reactor and optionally injecting ethylene, a process solvent, one or more α-olefins, hydrogen, and a second heterogeneous catalyst mixture into the third reactor to generate a fourth outlet flow containing any third ethylene polymer, a second ethylene polymer, and a first ethylene polymer in the process solvent.

27. The process according to claim 25 or 26, wherein the second heterogeneous catalyst formulation is, if present, the first in-line Ziegler-Natta catalyst.

28. The process according to any one of claims 1 to 24, wherein the first reactor and the second reactor are operated adiabatically.

29. The process according to any one of claims 25 to 27, wherein the third reactor is operated adiabatically.

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