Production of ethylene interpolymer products at higher productivity
阅读说明：本技术 以更高的生产率制造乙烯互聚物产品 (Production of ethylene interpolymer products at higher productivity ) 是由 N.卡泽米 M.克拉切克 V.科纳甘迪 B.吉伦 S.戈亚尔 F.锡布廷 S.卡西里 于 2018-10-18 设计创作，主要内容包括：本公开涉及一种改进的连续溶液聚合方法,其中提高了生产率。将过程溶剂,乙烯,任选的共聚单体,任选的氢和桥联茂金属催化剂制剂注入第一反应器中以形成第一乙烯互聚物。任选地,将过程溶剂,乙烯,任选的共聚单体,任选的氢和桥联茂金属催化剂制剂注入第二反应器中,形成第二乙烯互聚物。第一和第二反应器可以串联或并联操作模式配置。任选地,在第三反应器中形成第三乙烯互聚物,其中采用均相催化剂制剂或非均相催化剂制剂。在溶液中,合并第一,任选的第二和任选的第三乙烯互聚物,使催化剂减活,溶液任选地被钝化,并且在相分离过程之后,回收乙烯互聚物产品。(The present disclosure relates to an improved continuous solution polymerization process in which productivity is increased. A process solvent, ethylene, optional comonomer, optional hydrogen, and a bridged metallocene catalyst formulation are injected into a first reactor to form a first ethylene interpolymer. Optionally, a process solvent, ethylene, optional comonomer, optional hydrogen, and a bridged metallocene catalyst formulation are injected into a second reactor to form a second ethylene interpolymer. The first and second reactors may be configured in series or parallel operating modes. Optionally, a third ethylene interpolymer is formed in a third reactor, wherein a homogeneous catalyst formulation or a heterogeneous catalyst formulation is employed. Combining the first, optional second and optional third ethylene interpolymers in solution, deactivating the catalyst, optionally deactivating the solution, and recovering the ethylene interpolymer product after a phase separation process.)
1. An improved continuous solution polymerization process, wherein said improved process comprises the following:
polymerizing ethylene and optionally at least one alpha-olefin in a process solvent in one or more reactors and using at least one bridged metallocene catalyst formulation to form an ethylene interpolymer product;
wherein the improved process has an increased productivity PRIDefined by the formula;
PRI= 100 x (PRA- PRC) / PRC≥ 10%
Wherein PRAIs the productivity of the improved process, and PRCIs a comparative productivity of a comparative process in which the one or more bridged metallocene catalyst formulations have been replaced by non-bridged single site catalyst formulations.
2. The improved process according to claim 1, wherein the bridged metallocene catalyst formulation comprises:
a) component A, defined by formula (I);
wherein M is a metal selected from the group consisting of titanium, hafnium and zirconium; g is the element carbon, silicon, germanium, tin or lead; x represents a halogen atom, R6The radicals being independently selected from hydrogen atoms, C1-20Hydrocarbyl radical, C1-20Alkoxy or C6-10Aryl ether radicals, which may be linear, branched or cyclic or further substituted by halogen atoms, C1-10Alkyl radical, C1-10Alkoxy radical, C6-10Aryl or aryloxy substituted; r1Represents a hydrogen atom, C1-20Hydrocarbyl radical, C1-20Alkoxy radical, C6-10Aryl ether radicals or containing at least one silicon atom and C3-30Alkylsilyl group of carbon atom; r2And R3Independently selected from hydrogen atoms, C1-20Hydrocarbyl radical, C1-20Alkoxy radical, C6-10Aryl ether radicals or containing at least one silicon atom and C3-30Alkylsilyl group of carbon atom; and R4And R5Independently selected from hydrogen atoms, C1-20Hydrocarbyl radical, C1-20Alkoxy radical, C6-10Aryl ether radicals or containing at least one silicon atom and C 3-30Alkylsilyl group of carbon atom;
b) a component M comprising an aluminoxane cocatalyst;
c) component B comprising a boron ion activator, and;
d) optionally, component P, which comprises a hindered phenol.
3. The improved process according to claim 2, having the following molar ratios: the molar ratio of the component B to the component A is 0.3: 1 to 10: 1; the molar ratio of the component M to the component A is from 1: 1 to 300: 1, and; the molar ratio of the optional component P to the component M is from 0.0: 1 to 1: 1.
4. The improved process according to claim 2 wherein component M is methylalumoxane (MMAO-7), component B is triphenylcarbenium tetrakis (pentafluorophenyl) borate, and component P is 2, 6-di-tert-butyl-4-ethylphenol.
5. The improved method of claim 2, further comprisingStep (b) comprises injecting the bridged metallocene catalyst formulation into the one or more reactors at a catalyst inlet temperature of 20 ℃ to 70 ℃; optionally, the component M and the component P may be deleted from the bridged metallocene catalyst formulation and used in the formula Al (R)1)n(OR2)oA defined component J, wherein (R)1) The groups may be the same or different hydrocarbyl groups having from 1 to 10 carbon atoms; (OR) 2) The radicals may be identical or different alkoxy or aryloxy radicals, in which R2Is an oxygen-bonded hydrocarbon group having 1 to 10 carbon atoms; and (n + o) =3, provided that n is greater than 0.
6. The improved process according to claim 1, further comprising injecting the bridged metallocene catalyst formulation into the one or more reactors at a catalyst inlet temperature of from 80 ℃ to 180 ℃.
7. The improved process according to claim 1, wherein the process solvent is one or more C5-C12An alkane.
8. The improved process according to claim 1, wherein the one or more reactors are operated at a temperature of from 80 ℃ to 300 ℃ and a pressure of from 3MPag to 45 MPag.
9. The improved process of claim 1, wherein the average reactor residence time of the process solvent in the one or more reactors is from 10 seconds to 720 seconds.
10. The improved process according to claim 1, wherein said at least one α -olefin is selected from the group consisting of C3-C10α -one or more of olefins.
11. The improved process according to claim 1, wherein the at least one α -olefin is 1-hexene or 1-octene or a mixture of 1-hexene and 1-octene.
12. The improved process according to claim 1, wherein said ethylene interpolymer product has:
a) a dimensionless long chain branching factor, LCBF, of greater than or equal to 0.001;
b) a residual catalytic metal of hafnium from 0.03 to 5 ppm, wherein the residual catalytic metal is measured using neutron activation;
c) a dimensionless unsaturation ratio UR of from ≥ 0.40 to ≤ 0.06, wherein UR is defined by the following relationship;
UR = (SCU-TU)/TU
wherein, SCUIs the amount of pendant unsaturation per 100 carbons in the ethylene interpolymer product, and TUIs the amount of terminal unsaturation per 100 carbons in the ethylene interpolymer product, as determined by ASTM D3124-98 and ASTM D6248-98.
13. The improved process according to claim 1, wherein the ethylene interpolymer product has a melt index from 0.3 to 500 dg/min and a density from 0.855 to 0.975 g/cc; wherein the melt index is measured according to ASTM D1238 (2.16 kg load and 190 ℃) and the density is measured according to ASTM D792.
14. The improved process according to claim 1, wherein the ethylene interpolymer product comprises a first ethylene interpolymer, a second ethylene interpolymer, and optionally a third ethylene interpolymer.
15. The improved process according to claim 1, wherein said ethylene interpolymer product has a polydispersity M from 1.7 to 25 w/MnAnd 1% to 98% of CDBI50Wherein CDBI50Using CTREF measurements; wherein the weight average molecular weight MwAnd number average molecular weight MnMeasured using conventional size exclusion chromatography, and CDBI50CTREF measurements were used.
16. The improved process according to claim 1, wherein the ethylene interpolymer product comprises from 0 to 25 mole percent of one or more alpha-olefins.
Background
The solution polymerization process is generally carried out at a temperature above the melting point of the ethylene homopolymer or copolymer produced. In a typical solution polymerization process, the catalyst components, solvent, monomers and hydrogen are fed under pressure to one or more reactors.
For ethylene polymerization or ethylene copolymerization, the reactor temperature may be in the range of 80 ℃ to 300 ℃ and the pressure is typically in the range of 3MPag to 45 MPag. The resulting ethylene homopolymer or copolymer remains dissolved in the solvent under reactor conditions. The residence time of the solvent in the reactor is relatively short, for example from 1 second to 20 minutes. The solution process can be carried out under a wide range of process conditions that allow the production of a variety of ethylene polymers. After the reactor, the polymerization reaction is quenched by the addition of a catalyst deactivator to prevent further polymerization. Optionally, the deactivation solution may be deactivated by the addition of an acid scavenger. The deactivated solution or optional deactivated solution is then passed to polymer recovery where the ethylene homopolymer or copolymer is separated from the process solvent, unreacted residual ethylene and unreacted optional alpha-olefin.
In solution polymerization, there is a need for improved processes to produce ethylene interpolymers at higher production rates, i.e., an increase in pounds of ethylene interpolymer produced per hour. Higher production rates increase profitability of the solution polymerization plant. The catalyst formulations and solution polymerization processes disclosed herein meet this need.
In solution polymerization, it is also desirable to increase the molecular weight of the ethylene interpolymer produced at a given reactor temperature. Given a particular catalyst formulation, it is well known to those of ordinary skill in the art that as reactor temperature decreases, polymer molecular weight increases. However, lowering the reactor temperature may cause problems when the viscosity of the solution becomes too high. As a result, in solution polymerization, catalyst formulations are needed that produce high molecular weight ethylene interpolymers at high reactor temperatures (or lower reactor viscosities). The catalyst formulations and solution polymerization processes disclosed herein meet this need.
There is also a need for a catalyst formulation that is very efficient in incorporating one or more alpha-olefins into a growing macromolecular chain in a solution polymerization process. In other words, at a given [ alpha-olefin/ethylene ] weight ratio in a solution polymerization reactor, a catalyst formulation is needed that produces a lower density ethylene/alpha-olefin copolymer. In other words, there is a need for a catalyst formulation that produces ethylene/alpha-olefin copolymers having a particular density at a lower [ alpha-olefin/ethylene ] weight ratio in the reactor feed. Such catalyst formulations effectively utilize the available alpha-olefins and reduce the amount of alpha-olefins in the solution process recycle stream.
The catalyst formulations and solution processes disclosed herein produce a unique ethylene interpolymer product having desirable properties in a variety of end-use applications. One non-limiting end-use application includes packaging films comprising the disclosed ethylene interpolymer products. Non-limiting examples of desirable film properties include improved optical properties, lower seal initiation temperatures, and improved hot tack performance. Films prepared from the ethylene interpolymer products disclosed herein have improved properties.
Summary of The Invention
One embodiment of the present disclosure is an ethylene interpolymer product comprising at least one ethylene interpolymer, wherein the ethylene interpolymer product has: a dimensionless long chain branching factor, LCBF, of greater than or equal to 0.001; a residual catalytic metal of hafnium of not less than 0.03 to not more than 5 ppm and a dimensionless unsaturation ratio UR of not less than-0.40 to not more than 0.06. The ethylene interpolymer product can have a melt index (I) from 0.3 to 500 dg/min 2) Density of 0.855 to 0.975g/cc and 0 to 25 mole percent of one or more α -olefins suitable α -olefins include one or more C3-C10α -olefin ethylene interpolymer products in other embodiments having a polydispersity M of from 1.7 to 25w/MnWherein M iswAnd MnWeight average molecular weight and number average molecular weight, respectively, as determined by conventional Size Exclusion Chromatography (SEC). Additional embodiments of the ethylene interpolymer product have a CDBI from 1% to 98%50Wherein CDBI50CTREF measurements were used.
Additional embodiments include producing the ethylene interpolymer product in a continuous solution polymerization process using at least one homogeneous catalyst formulation. One embodiment of a suitable homogeneous catalyst formulation is a bridged metallocene catalyst formulation comprising component A as defined by formula (I)
Wherein M is a metal selected from the group consisting of titanium, hafnium and zirconium; g is the element carbon, silicon, germanium, tin or lead; x represents a halogen atom, R6The radicals being independently selected from hydrogen atoms, C1-20Hydrocarbyl radical, C1-20Alkoxy or C6-10Aryl ether radicals, which may be linear, branched or cyclic or further substituted by halogen atoms, C 1-10Alkyl radical, C1-10Alkoxy radical, C6-10Aryl or aryloxy substituted; r1Represents a hydrogen atom, C1-20Hydrocarbyl radical, C1-20Alkoxy radical, C6-10Aryl ether radicals or containing at least one silicon atom and C3-30Alkylsilyl group of carbon atom; r2And R3Independently selected from hydrogen atoms, C1-20Hydrocarbyl radical, C1-20Alkoxy radical, C6-10Aryl ether radicals or containing at least one silicon atom and C3-30Alkylsilyl group of carbon atom; and R4And R5Independently selected from hydrogen atoms, C1-20Hydrocarbyl radical, C1-20Alkoxy radical, C6-10Aryl ether radicals or containing at least one silicon atom and C3-30Alkylsilyl group of carbon atom.
Other embodiments include an improved continuous solution polymerization process, wherein the improved process comprises polymerizing ethylene and optionally at least one α -olefin in a process solvent in one or more reactors using a bridged metallocene catalyst to form an ethylene interpolymer product, wherein the improved process has an increased productivity PRIDefined by the formula;
PRI=100 x (PRA- PRC) / PRC≥ 10%
wherein PRAIs an improved process productivity, PRCIs a comparative productivity of a comparative continuous solution polymerization process in which a bridged metallocene catalyst formulation has been replaced by a non-bridged single site catalyst formulation.
Additional embodiments include bridged metallocene catalyst formulations comprising: an aluminoxane cocatalyst (component M); a boron ion activator (component B), and optionally, a hindered phenol (component P). Non-limiting examples of components M, B and P include, respectively: methylaluminoxane (MMAO-7), triphenylcarbenium tetrakis (pentafluorophenyl) borate and 2, 6-di-tert-butyl-4-ethylphenol.
Additional embodiments include improved methods employing: comprising one or more C5To C12A process solvent for an alkane and one or more reactors operated at a temperature of from 80 ℃ to 300 ℃ and a pressure of from 3MPag to 45 MPag. Embodiments may include reactor conditions such that the process solvent in one or more reactors has an average reactor residence time of from 10 seconds to 720 seconds. Other embodiments may include reactor conditions such that the catalyst inlet temperature employed in one or more reactors may vary between 20 ℃ and 180 ℃.
Other embodiments include an improved continuous solution polymerization process wherein an ethylene interpolymer product is formed by polymerizing ethylene and optionally at least one alpha-olefin in a process solvent in one or more reactors using a bridged metallocene catalyst formulation, and the improved process is characterized by (a) and/or (b):
(a) the ethylene interpolymer product has at least 10% improved (higher) weight average molecular weight MwIs defined by the following formula
% improved Mw= 100 x (Mw A-Mw C)/Mw C≥ 10%
Wherein M isw AIs the weight average molecular weight, M, of the ethylene interpolymer product produced using the improved processw CIs a comparative weight average molecular weight of a comparative ethylene interpolymer product; wherein the comparative ethylene interpolymer product is produced in a comparative process by replacing a bridged metallocene catalyst formulation with a non-bridged single site catalyst formulation;
(b) The weight ratio of [ alpha-olefin/ethylene ] used in the improved process is reduced (improved) by at least 70%, as defined by the formula
Wherein (α -olefin/ethylene)AShow addingThe weight of α -olefin added to the improved process divided by the weight of ethylene added to the improved process, wherein an ethylene interpolymer product having a target density is produced by bridging a metallocene catalyst formulation, and (α -olefin/ethylene)CRepresenting the comparative weight ratios required to produce a comparative ethylene interpolymer product having a target density, wherein the comparative ethylene interpolymer product was synthesized in the comparative process by replacing the bridged metallocene catalyst formulation with the non-bridged single site catalyst formulation.
Embodiments of the ethylene interpolymer product may comprise a first ethylene interpolymer. Other embodiments of the ethylene interpolymer product can comprise a first ethylene interpolymer and a third ethylene interpolymer. Other embodiments of the ethylene interpolymer product can comprise a first ethylene interpolymer and a second ethylene interpolymer. Other embodiments of the ethylene interpolymer product can comprise a first ethylene interpolymer, a second ethylene interpolymer, and a third ethylene interpolymer.
The first ethylene interpolymer has a melt index from 0.01 to 200 dg/min, a density from 0.855g/cc to 0.975 g/cc; the first ethylene interpolymer may comprise from 5 to 100 weight percent of the ethylene interpolymer product. The second ethylene interpolymer can comprise from 0 to 95 weight percent of the ethylene interpolymer product, have a melt index from 0.3 to 1000 dg/min, and a density from 0.855g/cc to 0.975 g/cc. The third ethylene interpolymer can comprise from 0 to 30 weight percent of the ethylene interpolymer product, have a melt index from 0.4 to 2000 dg/min, and a density from 0.855g/cc to 0.975 g/cc. Weight percent wt% is the weight of the first, second, or optional third ethylene interpolymer, respectively, divided by the total weight of the ethylene interpolymer product, and the melt index is measured according to ASTM D1238(2.16kg load and 190 ℃) and the density is measured according to ASTM D792.
In further embodiments, the CDBI of the first and second ethylene interpolymers50The upper limit of (d) may be 98%, in other cases 95%, and in
In other embodiments, M of the first and second ethylene interpolymersw/MnThe upper limit of (d) may be 2.4, in other cases 2.3, in other cases 2.2; and M of the first and second ethylene interpolymersw/MnThe lower limit of (d) may be 1.7, in other cases may be 1.8, and in other cases may be 1.9. M of a third ethylene interpolymerw/MnThe upper limit of (d) may be 5.0, in other cases 4.8, in other cases 4.5; and optionally a third ethylene interpolymerw/MnThe lower limit of (d) may be 1.7, in other cases may be 1.8, and in other cases may be 1.9.
In the present disclosure, the amount of long chain branching in an ethylene interpolymer is characterized by a dimensionless long chain branching factor, "LCBF". In some embodiments, the LCBF of the first and second ethylene interpolymers may have an upper limit of 0.5, in other cases 0.4, in other cases 0.3 (dimensionless); the LCBF of the first and second ethylene interpolymers may have a lower limit of 0.001, in other cases 0.0015, and in other cases 0.002 (dimensionless). The third ethylene interpolymer may have an upper limit of LCBF of 0.5, in other cases 0.4, in other cases 0.3 (dimensionless); and the third ethylene interpolymer may have a lower limit of LCBF less than 0.001, i.e., no detectable level of long chain branching.
In the present disclosure, the unsaturation ratio "UR" is used to characterize the unsaturation in the ethylene interpolymer. In some embodiments, the upper limit of the UR of the first and second ethylene interpolymers can be 0.06, in other cases 0.04, in other cases 0.02 (dimensionless), and the lower limit of the UR of the first and second ethylene interpolymers can be-0.40, in other cases-0.30, in other cases-0.20 (dimensionless). The upper limit of UR for the third ethylene interpolymer may be 0.06, in other cases 0.04, in other cases 0.02 (dimensionless); and the third ethylene interpolymer may have a UR with a lower limit of-1.0, in other cases-0.95, and in other cases-0.9.
In the present disclosure, the amount of residual catalytic metal in the ethylene interpolymer is characterized by neutron activation analysis "NAA". Metal A in the first ethylene interpolymerR1Can be 5.0ppm, can be 4.0ppm in other cases, can be 3.0ppm in other cases, and the metal a in the first ethylene interpolymerR1The lower limit of ppm (b) may be 0.03ppm, in other cases 0.09ppm, in other cases 0.15 ppm. Metal A in the second ethylene interpolymer R2The upper limit of ppm of (a) may be 5.0ppm, in other cases 4.0ppm, in other cases 3.0 ppm; and metal A in the second ethylene interpolymerR2The lower limit of ppm (b) may be 0.03ppm, in other cases 0.09ppm, in other cases 0.15 ppm. The catalyst residue in the third ethylene interpolymer reflects the catalyst used in its production. Metal A in the third ethylene interpolymer if a bridged metallocene catalyst formulation is usedR3The upper limit of ppm of (a) may be 5.0ppm, in other cases 4.0ppm, in other cases 3.0 ppm; and metal A in a third ethylene interpolymerR3The lower limit of ppm (b) may be 0.03ppm, in other cases 0.09ppm, in other cases 0.15 ppm. Metal C in the third ethylene interpolymer if a non-bridged single site catalyst formulation is usedR3The upper limit of ppm (b) can be 3.0ppm, in other cases can be 2.0ppm, in other cases can be 1.5ppm, and the metal C in the third ethylene interpolymerR3The lower limit of ppm (b) may be 0.03ppm, in other cases 0.09ppm, in other cases 0.15 ppm. In the case of homogeneous catalyst formulations containing bulky ligand-metal complexes which are not members of the class defined by formula (I) or (II), the metal B in the third ethylene interpolymer R3The upper limit of ppm of (a) may be 5.0ppm, in other cases 4.0ppm, in other cases 3.0 ppm; and a third ethylene interpolymerizationMetal B in the materialR3The lower limit of ppm (b) may be 0.03ppm, in other cases 0.09ppm, in other cases 0.15 ppm. The metal Z in the third ethylene interpolymer, if a heterogeneous catalyst formulation is usedR3The upper limit of ppm of (a) may be 12ppm, in other cases 10ppm, in other cases 8 ppm; and metal Z in a third ethylene interpolymerR3The lower limit of ppm (b) may be 0.5ppm, in other cases 1ppm, in
Non-limiting embodiments of the article include a film comprising at least one layer, wherein the layer comprises at least one of the ethylene interpolymer products disclosed herein; wherein the ethylene interpolymer product has 1) a dimensionless long chain branching factor LCBF of greater than or equal to 0.001, 2) a residual catalytic metal of hafnium of greater than or equal to 0.03 to less than or equal to 5ppm, and 3) a dimensionless unsaturation ratio UR of greater than or equal to-0.40 to less than or equal to 0.06. In other embodiments, the film has a film gloss at 45 ° that is 10% to 30% higher relative to the comparative film and/or the film has a film haze that is 30% to 50% lower than the comparative film; wherein the comparative films have the same composition except that the ethylene interpolymer product synthesized with the bridged metallocene catalyst formulation is replaced with the comparative ethylene interpolymer product synthesized with the non-bridged single site catalyst formulation.
Additional film embodiments include films wherein the at least one layer further comprises at least one second polymer; wherein the second polymer may be one or more ethylene polymers, one or more propylene polymers or a mixture of ethylene and propylene polymers. Other embodiments include films having a total thickness of 0.5 mils to 10 mils. Other embodiments include multilayer films having 2 to 11 layers, wherein at least one layer comprises at least one ethylene interpolymer product.
Brief Description of Drawings
To illustrate selected embodiments of the present disclosure, the following figures are provided. It should be understood that embodiments in the present disclosure are not limited to these figures; for example, the precise number of containers or arrangement of containers shown in fig. 3 and 4 is not limiting.
FIG. 1 compares the unsaturation ratio ` UR ` of examples 1 to 6 with respect to comparative examples Q to V and 1 to 5.
FIG. 2 shows the determination of Long Chain Branching Factor (LCBF). The abscissa plotted is the logarithm of the corrected zero shear viscosity (log (ZSV)c) Plotted ordinate is log (IV) of corrected intrinsic viscosityc)). Ethylene polymers without LCB or undetectable LCB fall on the reference line. The ethylene polymer with LCB deviates from the reference line and is characterized by a dimensionless Long Chain Branching Factor (LCBF). LCBF = (S) hx Sv) 2; wherein ShAnd SvHorizontal and vertical displacement factors, respectively.
FIG. 3 shows an embodiment of a continuous solution polymerization process using a CSTR reactor (
FIG. 4 shows an embodiment of a continuous solution polymerization process using two CSTR reactors (vessels 111a and 112a) and one tubular reactor (vessel 117). The two CSTRs can be operated in series or parallel mode.
FIG. 5 is the molecular weight distribution as determined by SEC and the branched content as determined by GPCFTIR (BrF, C) in example 14 and comparative example 146/1000C)。
Figure 6 deconvolutes the ethylene interpolymer product example 15 into first, second and third ethylene interpolymers.
Fig. 7 is a graph of cold seal force (newtons, N) of a multilayer film as a function of sealing temperature.
Fig. 8 is the hot tack (newtons, N) of a multilayer film as a function of sealing temperature.
Definition of terms
Other than in the examples, or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, extrusion conditions, etc., used in the specification and claims are to be understood as modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the various embodiments. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. The numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
It should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10; that is, all subranges having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10. Because the disclosed numerical ranges are continuous, they include every value between the minimum and maximum values. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations.
Indeed, all compositional ranges expressed herein are limited to and do not exceed 100% (volume% or weight%) in total. Where multiple components may be present in the composition, the sum of the maximum amounts of each component may exceed 100%, it being understood and as will be readily appreciated by those skilled in the art, that the amounts of components actually used should correspond to up to 100%.
To form a more complete understanding of the present disclosure, the following terms are defined and should be used in conjunction with the accompanying drawings and the description of all the various embodiments.
As used herein, the term "monomer" refers to a small molecule that can chemically react with itself or other monomers and chemically bond to form a polymer.
As used herein, the term "α -olefin" is used to describe a monomer having a linear hydrocarbon chain containing from 3 to 20 carbon atoms with a double bond at one end of the chain; the equivalent term is "linear alpha-olefin".
As used herein, the term "ethylene polymer" refers to a macromolecule produced from ethylene and optionally one or more additional monomers; regardless of the particular catalyst or the particular process used to prepare the ethylene polymer. In the field of polyethylene, the one or more additional monomers are commonly referred to as "comonomers" and typically include alpha-olefins. The term "homopolymer" refers to a polymer comprising only one type of monomer. Common ethylene polymers include High Density Polyethylene (HDPE), Medium Density Polyethylene (MDPE), Linear Low Density Polyethylene (LLDPE), Very Low Density Polyethylene (VLDPE), Ultra Low Density Polyethylene (ULDPE), plastomers and elastomers. The term ethylene polymer also includes polymers produced in high pressure polymerization processes; non-limiting examples include Low Density Polyethylene (LDPE), ethylene vinyl acetate copolymer (EVA), ethylene alkyl acrylate copolymer, ethylene acrylic acid copolymer and metal salts of ethylene acrylic acid (commonly referred to as ionomers). The term ethylene polymer also includes block copolymers which may comprise from 2 to 4 comonomers. The term ethylene polymer also includes combinations or blends of the above ethylene polymers.
The term "ethylene interpolymer" refers to a subset of polymers in the "ethylene polymer" group, excluding polymers produced in high pressure polymerization processes. Non-limiting examples of polymers produced in high pressure processes include LDPE and EVA (the latter being a copolymer of ethylene and vinyl acetate).
The term "heterogeneous ethylene interpolymer" refers to a subset of the polymers in the ethylene interpolymer group produced using a heterogeneous catalyst formulation; non-limiting examples thereof include Ziegler-Natta or chromium catalysts.
The term "homogeneous ethylene interpolymer" refers to a subset of the polymers in the ethylene interpolymer group produced using a homogeneous catalyst formulation. Typically, homogeneous ethylene interpolymers have a narrow molecular weight distribution, such as Size Exclusion Chromatography (SEC) Mw/MnA value of less than 2.8; mwAnd MnRespectively, the weight average molecular weight and the number average molecular weight. In contrast, M of heterogeneous ethylene interpolymersw/MnGenerally greater than M of a homogeneous ethylene interpolymerw/Mn. In general, homogeneous ethylene interpolymers also have a narrow comonomer distribution, i.e., each macromolecule within the molecular weight distribution has a similar comonomer content. In general, the composition distribution breadth index "CDBI" is used to quantify the comonomer How to distribute in the ethylene interpolymer, and to distinguish ethylene interpolymers produced with different catalysts or processes. "CDBI50"is defined as the percentage of ethylene interpolymer having a composition within 50% of the median comonomer composition; this definition is consistent with that described in U.S. patent 5,206,075 assigned to Exxon Chemical Patents Inc. CDBI of ethylene interpolymers50Can be calculated from the TREF curve (temperature rising elution fractionation); the TREF method is described in Wild, et al, J. Polym.Sci., Part B, Polym. Phys., volume 20 (3), page number 441-. In general, CDBI of homogeneous ethylene interpolymers50Greater than about 70%, in contrast to CDBI of a heterogeneous ethylene interpolymer containing α -olefin50CDBI generally lower than homogeneous ethylene interpolymers50. CDBI of blends of two or more homogeneous ethylene interpolymers (differing in comonomer content)50May be less than 70%; in the present disclosure, such blends may be referred to as homogeneous blends or homogeneous compositions. Similarly, two or more homogeneous ethylene interpolymers (weight average molecular weight (M)w) Different) can have Mw/MnNot less than 2.8; in the present disclosure, such blends may be referred to as homogeneous blends or homogeneous compositions.
In the present disclosure, the term "homogeneous ethylene interpolymer" refers to both linear homogeneous ethylene interpolymers and substantially linear homogeneous ethylene interpolymers. Linear homogeneous ethylene interpolymers are generally considered in the art to have no long chain branching or have an undetectable amount of long chain branching; while substantially linear ethylene interpolymers are generally considered to have greater than about 0.01 to about 3.0 long chain branches per 1000 carbon atoms. The long chain branches are macromolecules in nature, i.e., are similar in length to the macromolecule to which the long chain branches are attached.
In the present disclosure, the term "homogeneous catalyst" is defined by the properties of the polymer produced by the homogeneous catalyst. More specifically, if the catalyst is produced with a narrow molecular weight distribution (SEC M)w/MnValue less than 2.8) and narrow Comonomer Distribution (CDBI)50>70%) of a homogeneous ethylene interpolymer, the catalyst is a homogeneous catalyst. Homogeneous catalysts are well known in the art. Two sub-package of homogeneous catalyst speciesIncluding non-bridged metallocene catalysts and bridged metallocene catalysts. Non-bridged metallocene catalysts are characterized by two bulky ligands bonded to the catalytic metal, non-limiting examples include bis (isopropyl-cyclopentadienyl) hafnium dichloride. In bridged metallocene catalysts, two bulky ligands are covalently bonded (bridged) together, non-limiting examples include diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) hafnium dichloride; wherein the diphenylmethylene group bonds or bridges together the cyclopentadienyl and fluorenyl ligands. Two other subsets of homogeneous catalyst classes include non-bridged and bridged single-site catalysts. In the present disclosure, single-site catalysts are characterized by having only one bulky ligand bonded to a catalytic metal. Non-limiting examples of non-bridged single-site catalysts include cyclopentadienyl tris (tert-butyl) phosphinimine titanium dichloride. Non-limiting examples of bridged single site catalysts include [ C 5(CH3)4- Si(CH3)2-N(tBu)]Titanium dichloride of which Si (CH)3)2The group acts as a bridging group.
Herein, the term "polyolefin" includes ethylene polymers and propylene polymers; non-limiting examples of propylene polymers include isotactic, syndiotactic and atactic propylene homopolymers, random propylene copolymers containing at least one comonomer (e.g., an alpha-olefin) and impact or heterophasic polypropylene copolymers.
The term "thermoplastic" refers to a polymer that becomes liquid when heated, will flow under pressure, and solidifies upon cooling. Thermoplastic polymers include ethylene polymers and other polymers used in the plastics industry; non-limiting examples of other polymers commonly used in film applications include barrier resins (EVOH), tie resins, polyethylene terephthalate (PET), polyamides, and the like.
As used herein, the term "monolayer film" refers to a film comprising a single layer of one or more thermoplastics.
The term "hydrocarbyl", "hydrocarbon group" or "hydrocarbyl group" as used herein refers to straight-chain, branched-chain or cyclic aliphatic, olefinic, acetylenic and aryl (aromatic) groups containing hydrogen and carbon, lacking one hydrogen.
As used herein, "alkyl" includes straight, branched and cyclic alkanyl radicals lacking a hydrogen radical; non-limiting examples include methyl (-CH) 3) And ethyl (-CH)2CH3) A group. The term "alkenyl" refers to straight, branched, and cyclic hydrocarbons containing at least one carbon-carbon double bond, lacking one hydrogen group.
The term "aryl" group as used herein includes phenyl, naphthyl, pyridyl and other groups whose molecules have an aromatic ring structure; non-limiting examples include naphthalene, phenanthrene, and anthracene. An "arylalkyl" group is an alkyl group having an aryl group pendant from the alkyl group; non-limiting examples include benzyl, phenethyl and tolylmethyl; "alkylaryl" is an aryl group having one or more alkyl groups pendant from the aryl group; non-limiting examples include tolyl, xylyl, mesityl, and cumyl.
As used herein, the phrase "heteroatom" includes any atom other than carbon and hydrogen that may be bonded to carbon. A "heteroatom-containing group" is a hydrocarbon group that contains a heteroatom and may contain one or more of the same or different heteroatoms. In one embodiment, the heteroatom containing group is a hydrocarbyl group containing 1 to 3 atoms selected from boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen, and sulfur. Non-limiting examples of heteroatom-containing groups include groups of imines, amines, oxides, phosphines, ethers, ketones, oxazoline heterocycles, oxazolines, thioethers, and the like. The term "heterocycle" refers to a ring system having a carbon backbone comprising 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen, and sulfur.
As used herein, the term "unsubstituted" refers to a hydrogen radical bonded to a molecular radical following the term "unsubstituted". The term "substituted" means that the group following the term has one or more moieties that have replaced one or more hydrogen groups anywhere within the group; non-limiting examples of such moieties include halo groups (F, Cl, Br), hydroxy, carbonyl, carboxy, amino, phosphino, alkoxy, phenyl, naphthyl, C1To C10Alkyl radical, C2To C10Alkenyl groups and combinations thereof. Non-limiting examples of substituted alkyl and aryl groups include: acyl, alkylamino, alkoxy, aryloxy, alkylthio, dialkylamino, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, alkylcarbamoyl and dialkylcarbamoyl, acyloxy, acylamino, arylamino and combinations thereof.
The term "R1" and superscript forms thereof "herein"R1"refers to the first reactor in a continuous solution polymerization process; it is understood that R1 is the same as the symbol R1Different; the latter is used for the formula, for example representing a hydrocarbon radical. Similarly, the term "R2" and superscript forms thereof "R2"refers to the second reactor, and the term" R3 "and superscript forms thereof" R3"refers to the third reactor.
As used herein, the term "oligomer" refers to a low molecular weight ethylene polymer, for example, an ethylene polymer having a weight average molecular weight (Mw) of about 2000 to 3000 daltons. Other commonly used terms for oligomers include "wax" or "grease". As used herein, the term "light end impurities" refers to lower boiling compounds that may be present in various vessels and process streams in a continuous solution polymerization process; non-limiting examples include methane, ethane, propane, butane, nitrogen, CO2Ethyl chloride, HCl, etc.
Description of the embodiments
There is a need for improved continuous solution polymerization processes. For example, increasing the molecular weight of the ethylene interpolymer produced at a given reactor temperature. In addition, in solution polymerization, there is a need for catalyst formulations that are very efficient in incorporating one or more alpha-olefins into a growing macromolecular chain. Expressed differently, there is a need for a catalyst formulation that produces an ethylene/α -olefin copolymer having a particular density at a lower (α -olefin/ethylene) ratio in the reactor feed. In addition, there is a need for ethylene interpolymer products having improved properties after conversion to articles.
In embodiments disclosed herein, a "bridged metallocene catalyst formulation" is employed in at least one solution polymerization reactor. The catalyst formulation includes a bulky ligand-metal complex "component a" defined by formula (I):
In formula (I): non-limiting examples of M include
In the art, X (R) as shown in formula (I)6) The common term for a group is a "leaving group", i.e., any ligand that can be extracted from formula (I) to form a catalyst species capable of polymerizing one or more olefins. X (R)6) The equivalent term for a group is "activatable ligand". X (R) shown in formula (I) 6) Other non-limiting examples of groups include weak bases such as amines, phosphines, ethers, carboxylates and dienes. In another embodiment, two R are6The groups may form part of a fused ring or ring system.
Other embodiments of component A include the structures, optical or enantiomeric (meso and exo-meso) structures of the formula (I)Rotamers) and mixtures thereof. Although not to be construed as limiting, two of component a include: diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) hafnium dichloride having the molecular formula [ (2, 7-tBu)2Flu)Ph2C(Cp)HfCl2]And diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) hafnium dimethyl having the formula [ (2, 7-tBu)2Flu)Ph2C(Cp)HfMe2]。
In embodiments disclosed herein, a "bridged metallocene catalyst formulation" is used for: (i) a first reactor to produce a first ethylene interpolymer, or (ii) a first and a third reactor to produce a first and a third ethylene interpolymer, or (iii) a first and a second reactor to produce a first and a second ethylene interpolymer, or (iv) a first, a second, and a third solution polymerization reactor to produce a first, a second, and a third ethylene interpolymer. The first and second reactors may be operated in series or parallel mode. In series mode, the effluent from the first reactor flows directly into the second reactor. In contrast, in the parallel mode, the effluent from the first reactor bypasses the second reactor, and the effluents from the first and second reactors are combined downstream of the second reactor.
A variety of catalyst formulations may be used in the optional third reactor. Non-limiting examples of catalyst formulations used in the third reactor include the bridged metallocene catalyst formulations described above, the non-bridged single-site catalyst formulations described below, homogeneous catalyst formulations containing bulky ligand-metal complexes that are not members of the species defined by formula (I) (above) or formula (II) (below), or heterogeneous catalyst formulations. Non-limiting examples of heterogeneous catalyst formulations include Ziegler-Natta or chromium catalyst formulations.
In the comparative example 1 samples disclosed herein, such as comparative examples 1a and 1b, a "non-bridged single site catalyst formulation" was used in at least one solution polymerization reactor. The catalyst formulation includes a bulky ligand-metal complex, hereinafter referred to as "component C", defined by formula (II).
(LA)aM(PI)b(Q)n (II)
In the formula (II): (L)A) Ligands representing large volumes; m represents a metal atom; PI represents a phosphinimine ligand; q represents a leaving group; a is 0 or 1; b is 1 or 2; (a + b) = 2; n is 1 or 2, and the sum of (a + b + n) is equal to the valence of the metal M. Non-limiting examples of M in formula (II) include the
Bulky ligands L in the formula (II) ANon-limiting examples of (a) include unsubstituted or substituted cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom-substituted and/or heteroatom-containing cyclopentadienyl-type ligands. Additional non-limiting examples include cyclopentaphenanthreneyl ligands, unsubstituted or substituted indenyl ligands, benzindenyl ligands, unsubstituted or substituted fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraenediyl ligands, cyclopentacyclododecene ligands, azoenyl ligands, azulene ligands, pentalene ligands, phosphoryl ligands, phosphinimines, pyrrolyl ligands, pyrazolyl ligands, carbazolyl ligands, borabenzene ligands, and the like, including hydrogenated versions thereof, such as tetrahydroindenyl ligands. In other embodiments, LAMay be any other ligand structure capable of η bonding with metal M, such embodiments include η with metal M3Bonding and η5-bonding. In other embodiments, LAMay contain one or more heteroatoms, such as nitrogen, silicon, boron, germanium, sulfur and phosphorus, combined with carbon atoms to form open, acyclic or fused rings, or ring systems, such as heterocyclopentadienyl ancillary ligands. L is AOther non-limiting embodiments of (a) include bulky amides, phosphides, alkoxides, aryl ethers, imides, carbides, borides, porphyrins, phthalocyanines, corrins, and other polyazo macrocycles.
The phosphinimine ligand PI is defined by the formula (III):
(Rp)3P = N - (III)
wherein R ispThe groups are independently selected from: a hydrogen atom; a halogen atom; c unsubstituted or substituted by one or more halogen atoms1-20A hydrocarbyl group; c1-8Alkoxy radicalA group; c6-10An aryl group; c6-10An aryloxy group; an amide group; formula-Si (R)s)3In which R issThe radicals being independently selected from hydrogen atoms, C1-8Alkyl or alkoxy radicals, C6-10Aryl radical, C6-10Aryloxy or of formula-Ge (R)G)3Germyl of (a), wherein RGRadicals like RSAs defined in this paragraph.
Leaving group Q is any ligand that can be extracted from formula (II) to form a catalyst species capable of polymerizing one or more olefins. In some embodiments, Q is a monoanionic labile ligand with a sigma bond to M. Depending on the oxidation state of the metal, n has a value of 1 or 2, so that formula (II) represents a neutral bulky ligand-metal complex. Non-limiting examples of Q ligands include hydrogen, halogen, C1-20Hydrocarbyl radical, C1-20Alkoxy radical, C5-10An aromatic ether group; these radicals may be linear, branched or cyclic, or further substituted by halogen atoms, C 1-10Alkyl radical, C1-10Alkoxy radical, C6-10Aryl or aryloxy substituted. Other non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylic esters, dienes, hydrocarbyl groups having 1 to 20 carbon atoms. In another embodiment, the two Q ligands may form part of a fused ring or ring system.
Other embodiments of component C include the structure of bulky ligand-metal complexes shown in formula (II), optical or enantiomeric isomers (meso and racemic isomers) and mixtures thereof.
Although not to be construed as limiting, two of component C include: the molecular formula is [ Cp [ (t-Bu)3PN]TiCl2]Cyclopentadienyl tris (tert-butyl) phosphinimine titanium dichloride; and the molecular formula [ Cp [ (isopropyl)3PN]TiCl2]Cyclopentadienyl tris (isopropyl) phosphinimine titanium dichloride.
The bridged metallocene catalyst formulation comprises component A (defined above), component MAComponent BAAnd component PA. Components M, B and P are defined below and are superscripted "A"means that the corresponding component is a catalyst containing component AThe fact that the catalyst preparation is part of a bridged metallocene catalyst preparation.
In the present disclosure, comparative ethylene interpolymer products were prepared by using non-bridged single site catalyst formulations. In these comparative samples, the bridged metallocene catalyst formulation was replaced by the non-bridged single-site catalyst formulation in the first polymerization reactor, or the first and second polymerization reactors, or the first, second and third polymerization reactors. The non-bridged single-site catalyst formulation comprises component C (defined above), component M CComponent BCAnd component PC. Components M, B and P are defined below and are superscripted "C"represents the following fact: the corresponding component is part of a catalyst formulation containing component C, i.e. a non-bridged single-site catalyst formulation.
Catalyst components M, B and P were independently selected for each catalyst formulation. More clearly: component MAAnd MCMay or may not be the same compound; component BAAnd BCMay or may not be the same compound, and component PAAnd PCMay or may not be the same compound. In addition, catalyst activity was optimized by independently adjusting the molar ratio of the components in each catalyst formulation.
The components M, B and P are not particularly limited, and a plurality of components may be used as described below.
Component M acts as a co-catalyst that activates component a or component C into a cationic complex that effectively polymerizes ethylene or a mixture of ethylene and alpha-olefins, thereby producing a high molecular weight ethylene interpolymer. In both the bridged metallocene catalyst formulation and the non-bridged single site catalyst formulation, each component M is independently selected from a variety of compounds, and those skilled in the art will appreciate that embodiments of the present disclosure are not limited to the particular compounds disclosed. Suitable compounds of component M include aluminoxane cocatalysts (an equivalent term for aluminoxane is aluminoxane). Although the exact structure of the aluminoxane cocatalyst is not yet certain, the expert of the present subject matter generally agrees that this is an oligomeric species containing recurring units of the general formula (IV):
(R)2AlO-(Al(R)-O)n-Al(R)2 (IV)
Wherein the R groups may be the same or different straight, branched or cyclic hydrocarbon groups containing from 1 to 20 carbon atoms and n is from 0 to about 50. A non-limiting example of an aluminoxane is methylaluminoxane (or MMAO-7) wherein each R group in formula (IV) is a methyl group.
Component B is an ionic activator. Typically, the ionic activator comprises a cation and a bulky anion; wherein the latter is substantially non-coordinating.
In the bridged metallocene catalyst formulations and the non-bridged single site catalyst formulations, each component B is independently selected from a variety of compounds, and those skilled in the art will appreciate that embodiments in the present disclosure are not limited to the particular compounds disclosed. A non-limiting example of component B is a boron ion activator, which is a tetradentate with four ligands bonded to the boron atom. Non-limiting examples of boron ion activators include the following formulas (V) and (VI) shown below:
[R5]+[B(R7)4]- (V)
wherein B represents a boron atom, R5Is an aromatic hydrocarbon radical (e.g., triphenylmethyl onium) and each R7Independently selected from phenyl groups unsubstituted or substituted with 3 to 5 substituents selected from fluorine atoms, C unsubstituted or substituted with fluorine atoms1-4Alkyl or alkoxy; and formula-Si (R) 9)3In which each R is9Independently selected from hydrogen atom and C1-4Alkyl, and
a compound of formula (VI);
[(R8)tZH]+[B(R7)4]- (VI)
wherein B is a boron atom, H is a hydrogen atom, Z is a nitrogen or phosphorus atom, t is 2 or 3, and R is8Is selected from C1-8Alkyl, unsubstituted or substituted by up to three C1-4Alkyl-substituted phenyl, or one R8Together with the nitrogen atom may form an anilinium group, anR7As defined in formula (VI) above.
In the formulae (V) and (VI), R7A non-limiting example of (a) is a pentafluorophenyl group. In general, boron ion activators may be described as salts of tetrakis (perfluorophenyl) boron; non-limiting examples include anilinium, carbenium, oxonium, phosphonium and sulfonium salts of tetrakis (perfluorophenyl) boron, with anilinium and trityl (or tritylium) groups. Other non-limiting examples of ionic activators include: triethylammoniumtetra (phenyl) boron, tripropylammoniumtetra (phenyl) boron, tri (N-butyl) ammoniumtetra (phenyl) boron, trimethylammonium tetrakis (p-tolyl) boron, trimethylammonium tetrakis (o-tolyl) boron, tributylammoniumtetra (pentafluorophenyl) boron, tripropylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (m, m-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, tributylammoniumtetra (pentafluorophenyl) boron, tri (N-butyl) ammoniumtetra (o-tolyl) boron, N, N-dimethylaniliniumtetrakis (phenyl) boron, N, N-diethylaniliniumtetrakis (phenyl) boron, N, N-2,4, 6-pentamethylaniliniumtetrakis (phenyl) boron, di- (isopropyl) ammoniumtetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) boron, triphenylphosphonium tetra (phenyl) boron, tris (methylphenyl) phosphonium tetra (phenyl) boron, tris (dimethylphenyl) phosphonium tetra (phenyl) boron,
Component P is a hindered phenol and is an optional component in the corresponding catalyst formulation. In both the bridged metallocene catalyst formulation and the non-bridged single site catalyst formulation, each component P is independently selected from a variety of compounds, and those skilled in the art will appreciate that embodiments of the present disclosure are not limited to the particular compounds disclosed. Non-limiting examples of hindered phenols include butylated phenolic antioxidants, butylated hydroxytoluene, 2, 4-di-tert-butyl-6-ethylphenol, 4,4 '-methylenebis (2, 6-di-tert-butylphenol), 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and octadecyl 3- (3',5 '-di-tert-butyl-4' -hydroxyphenyl) propionate.
As described in detail below, four components, component a and component M, in the formulation are optimizedAComponent BAAnd optionally a component PAIn amounts and in molar ratios to produce highly active bridged metallocene catalyst formulations. Where high activity means that a very large amount of ethylene interpolymer is produced from a very small amount of catalyst formulation. Similarly, by optimizing the four components in the formulation, component C, component MCComponent BCAnd optionally a component PCIn a molar ratio to produce a highly active non-bridged single-site catalyst formulation (comparative catalyst formulation).
In the present disclosure, a heterogeneous catalyst formulation can be used in an optional third reactor to synthesize a third ethylene interpolymer. Non-limiting examples of heterogeneous catalyst formulations include: ziegler-natta and chromium catalyst formulations. Non-limiting examples of Ziegler-Natta catalyst formulations include "in-line Ziegler-Natta catalyst formulations" or "batch Ziegler-Natta catalyst formulations". The term "in-line" refers to the continuous synthesis of a small amount of active ziegler-natta catalyst and the immediate injection of the catalyst into the third reactor, where ethylene and one or more optional alpha-olefins are polymerized to form an optional third ethylene interpolymer. The term "batch" refers to the synthesis of significantly greater amounts of catalyst or procatalyst in one or more mixing vessels external to or isolated from a continuously operated solution polymerization process. After preparation, the batch ziegler-natta catalyst formulation or batch ziegler-natta procatalyst is transferred to a catalyst storage tank. The term "procatalyst" refers to an inactive catalyst formulation (inactive for ethylene polymerization); the procatalyst is converted to the active catalyst by the addition of an aluminum alkyl cocatalyst. If desired, the procatalyst is pumped from the storage tank to at least one continuously operated reactor, where the active catalyst polymerizes ethylene and one or more optional α -olefins to form an ethylene interpolymer. The procatalyst may be converted to the active catalyst in the reactor or outside the reactor.
A variety of compounds are useful in the synthesis of active ziegler-natta catalyst formulations. Various compounds that can be combined to produce an active ziegler-natta catalyst formulation are described below. One skilled in the art will appreciate that embodiments in the present disclosure are not limited to the particular compounds disclosed.
The active Ziegler-Natta catalyst formulation may be formed from a magnesium compound, a chloride, a metal compound, an aluminum alkyl co-catalyst, and an aluminum alkyl. In the present disclosure, the term "component (v)" is equivalent to a magnesium compound, the term "component (vi)" is equivalent to a chloride, the term "component (vii)" is equivalent to a metal compound, the term "component (viii)" is equivalent to an alkylaluminum cocatalyst, and the term "component (ix)" is equivalent to an alkylaluminum. As will be appreciated by those skilled in the art, the ziegler-natta catalyst formulation may comprise additional components; non-limiting examples of additional components are electron donors, such as amines or ethers.
Non-limiting examples of active in-line Ziegler-Natta catalyst formulations can be prepared as follows.In the first step, a solution of a magnesium compound (component (v)) is reacted with a solution of a chloride (component (vi)) to form a magnesium chloride support suspended in the solution. Non-limiting examples of magnesium compounds include Mg (R) 1)2(ii) a Wherein R is1The radicals may be identical or different linear, branched or cyclic hydrocarbon radicals having from 1 to 10 carbon atoms. Non-limiting examples of chlorides include R2Cl; wherein R is2Represents a hydrogen atom, or a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms. In the first step, the solution of the magnesium compound may further comprise an aluminum alkyl (component (ix)). Non-limiting examples of aluminum alkyls include Al (R)3)3Wherein R is3The radicals can be identical or different and contain straight-chain, branched or cyclic hydrocarbon radicals having from 1 to 10 carbon atoms. In the second step, a solution of the metal compound (component (vii)) is added to a magnesium chloride solution, and the metal compound is supported on magnesium chloride. Non-limiting examples of suitable metal compounds include M (X)nOr MO (X)n(ii) a Wherein M represents a metal selected from
Al(R4)p(OR5)q(X)r (VII)
Wherein R is4The groups may be the same or different hydrocarbyl groups having 1 to 10 carbon atoms; OR (OR)5The radicals may be identical or different alkoxy or aryloxy radicals, in which R5Is a hydrocarbon group having 1 to 10 carbon atoms bonded to oxygen; x is chlorine or bromine, and (p + q + r) =3, provided that p is greater than 0. Commonly used aluminum alkyl cocatalystsNon-limiting examples of agents include trimethylaluminum, triethylaluminum, tributylaluminum, dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide, dimethylaluminum chloride or bromide, diethylaluminum chloride or bromide, dibutylaluminum chloride or bromide, and ethylaluminum dichloride or dibromide.
The process for synthesizing the active in-line Ziegler-Natta catalyst formulation described in the preceding paragraph may be carried out in a variety of solvents. Non-limiting examples of solvents include straight or branched C5To C12Alkanes or mixtures thereof.
To produce an active in-line ziegler-natta catalyst formulation, the amounts and molar ratios of the five components (v) to (ix) are optimized as described below.
Additional embodiments of heterogeneous catalyst formulations include those wherein the "metal compound" is a chromium compound; non-limiting examples include silyl chromates, chromium oxides and chromocene. In some embodiments, the chromium compound is supported on a metal oxide, such as silica or alumina. The chromium-containing heterogeneous catalyst formulation may further comprise a cocatalyst; non-limiting examples of cocatalysts include trialkylaluminums, alkylaluminoxanes and dialkoxyalkylaluminum compounds and the like.
In the present disclosure, the bridged metallocene catalyst formulation produces a solution process ethylene interpolymer product having a unique unsaturation ratio UR.
Table 1 discloses the amounts of internal, pendant and terminal unsaturation per 100 carbons (100C), i.e., the amounts of trans vinylidene, vinylidene and terminal vinyl groups, as measured according to ASTM D3124-98 and ASTM D6248-98, in the examples of the present disclosure relative to the comparative examples. Table 1 also discloses a dimensionless "unsaturation ratio" "UR", defined by the following equation
UR = (SCU-TU)/TUEquation (UR)
Wherein, SCUIs a degree of side chain unsaturation, TUIs the terminal unsaturation. Graphically, fig. 1 compares the average UR values of the examples and comparative examples. Statistically, the results are compared with all comparative examplesThe examples (examples 1 to 6) had significantly different average UR values. For example, examples 1 to 6 had an average UR value of-0.116. + -. 0.087, and comparative examples Q1 to Q4 had an average UR value of 0.085. + -. 0.014; these mean UR values differ significantly according to the t-test assuming equal variance, i.e. the t statistic of 4.51 exceeds the two-tailed t threshold of 2.31 and the two-tailed P value of 0.00197 is less than 0.05. Comparative example Q is a commercial product known as Queo available from Borealis, Vienna, Austria; specifically, comparative example Q1 is Queo 0201, comparative example Q2 is Queo8201, comparative example Q3 is Queo 0203, and comparative example Q4 is Queo 1001. The Queo product is an ethylene/1-octene copolymer believed to be produced by a solution polymerization process using one reactor and a metallocene catalyst formulation.
Statistically, the average UR values of examples 1 to 6 are also significantly different from those of comparative example R, comparative example S, comparative example T, comparative example U, comparative example V, comparative example 1, comparative example 2, comparative example 3, comparative example 4 and comparative example 5. As shown in Table 1 and FIG. 1, comparative example R has an average UR of 1.349. + -. 0.907, which is The average of 7 samples of a commercially available product known as Affinity available from The Dow Chemical Company, Midland, Michigan; specifically, Affinity PL1880 (3 samples), Affinity PF1140, Affinity PF1142, and Affinity PL 1881. The Affinity sample was an ethylene/1-octene copolymer, believed to be produced in a solution polymerization process using one reactor and a single site catalyst formulation. Comparative example S has an average UR of 0.1833. + -. 0.0550, the average of 5 samples of a commercially available product known as Enable, available from ExxonMobil Chemical Company, Spring, Texas; specifically, Enable 27-03CH (3 samples) and Enable 20-05 (2 samples). The Enable product is an ethylene/1-hexene copolymer believed to be produced in a gas phase process using one reactor and a metallocene catalyst formulation. Comparative example T has an average UR of-0.6600. + -. 0.1306, the average of 48 samples from a commercial product available from ExxonMobil Chemical Company, Spring, Texas; specifically, it is exceced 1018 (26 samples), exceced 1023 (4 samples), exceced 1015(3 samples), exceced 4518 (3 samples), exceced 3518(4 samples), exceced 1012 (3 samples), exceced 1318CA (2 samples), exceced 3812, exceced 1023DA and Exc DA eed 2718 CB. The exceted product is an ethylene/1-hexene copolymer believed to be produced in a gas phase process using one reactor and a metallocene catalyst formulation. Comparative example U, having a UR value of-0.667, is a commercially available product designated Elite AT 6202 from The Dow Chemical Company, Midland, Michigan. Elite AT 6202 is an ethylene/1-hexene copolymer believed to be produced in a two reactor solution process employing AT least one homogeneous catalyst formulation. Comparative example V had an average UR of-0.8737. + -. 0.0663, an average of 25 samples of a commercially available product known as Elite from The Dow Chemical Company, Midland, Michigan; specifically Elite 5400 (12 samples), Elite 5100 (4 samples), Elite 5110 (2 samples), Elite 5230 (2 samples), Elite 5101 and Elite 5500. The Elite product is an ethylene/1-octene copolymer believed to be produced in a solution polymerization process using a single-site catalyst formulation in the first reactor and a batch Ziegler-Natta catalyst formulation in the second reactor. Comparative example 1 has an average UR of-0.4374 + -0.1698, an average of 61 samples of a commercially available product designated SURPASS FPs117 from NOVA Chemicals Corporation, Calgary, Alberta. SURPASS FPs117 is an ethylene/1-octene copolymer produced in a solution polymerization process employing a single-site catalyst formulation. Comparative example 2 has an average UR of-0.5000. + -. 0.1000, which is the average of 3 samples of the experimental product manufactured by NOVA Chemicals Corporation, Calgary, Alberta. Comparative examples 2a, 2b and 2c are ethylene/1-octene copolymers (about 0.917g/cc and about 1.0I) produced in a solution polymerization process using a bridged metallocene catalyst formulation in a first reactor and a non-bridged single site catalyst formulation in a second reactor 2). Comparative example 3 has an average UR of-0.8548. + -. 0.0427, which is the average of 4 samples of the experimental product manufactured by NOVA Chemicals Corporation, Calgary, Alberta. Comparative examples 3a, 3b, 3c and 3d are ethylene/1-octene copolymers (about 0.917g/cc and about 1.0I) produced in a solution polymerization process using a bridged metallocene catalyst formulation in a first reactor and an in-line Ziegler-Natta catalyst formulation in a second reactor2). Comparative example 4 has an average UR of-0.8633. + -. 0.0470, known as SU from NOVA Chemicals Corporation, Calgary, AlbertaAverage of 21 samples of a commercial product of RPASS; specifically, SURPASS SPs116 (6 samples), SURPASS SPsK919 (5 samples), SURPASS VPsK114 (3 samples) and SURPASS VPsK914 (7 samples) are ethylene/1-octene copolymers produced in a solution polymerization process using a single-site catalyst formulation in a first reactor and an in-line Ziegler-Natta catalyst formulation in a second reactor. Comparative example 5 has an average UR of-0.8687 + -0.0296, known as SCLAIR from NOVA Chemicals Corporation, Calgary, Alberta®Average of 137 samples of commercial product of FP 120. FP120 is an ethylene/1-octene copolymer produced in a solution polymerization process employing an in-line Ziegler-Natta catalyst formulation.
As demonstrated in FIG. 1 and Table 1, there was no significant difference in UR values for comparative examples 3 to 5 and comparative example V (UR values ranging from-0.8548 to-0.8737), which is believed to reflect the fact that Ziegler-Natta catalysts are used to produce at least a portion of these copolymers.
In the present disclosure, the bridged metallocene catalyst formulation produces an ethylene interpolymer product having long chain branching (hereinafter "LCB").
LCB is a structural feature in polyethylene well known to those of ordinary skill in the art. Traditionally, there are three methods of quantifying the amount of LCB, namely nuclear magnetic resonance spectroscopy (NMR), see, for example, j.c. Randall, J macromol. sci, rev. macromol. chem. phys. 1989, 29, 201; triple detection SEC equipped with DRI, viscometer and low angle laser light scattering detector see, for example, W.W. Yau and D.R. Hill, int. J. Polymer. anal. Charact.1996; 2: 151; and rheology, see, for example, W.W. Graessley, Acc. chem. Res. 1977, 10, 332-. The long chain branches are macromolecular in nature, i.e., long enough to be visible in the NMR spectrum, triple detector SEC experiments, or rheology experiments.
The limitation of LCB analysis by NMR is that it cannot distinguish branch lengths equal to or longer than branches of six carbon atoms (therefore, NMR cannot be used to characterize LCB in ethylene/1-octene copolymers having hexyl as a side branch).
Intrinsic viscosity measurement by triple assay SEC method ([ η)]) (see, e.g., W.W. Yau, D.Gillespie, Analytical and Polymer Science, TAPPI Polymers, Laminations, and coatings conference Proceedings, Chicago 2000; 2: 699 or F. Beer, G. Capaccio, L.J.Rose, J.appl.Polymer, Sci.1999, 73: 2807 or P.M. Wood-Adams, J.M. Dealy, A.W.degroot, O.D. Redwine, Macromolecules 2000; 33: 7489.) by mixing the intrinsic viscosities of the branched Polymers ([ η. RTM. Polymers]b) Intrinsic viscosity of the same molecular weight linear polymer ([ η)]1) For reference, the viscosity branching index factor g '(g' = [ η ]]b/[η]l) However, both Short Chain Branching (SCB) and Long Chain Branching (LCB) are intrinsic viscosity ([ η)]) There has been a contribution, therefore, to the isolation of SCB contributions to ethylene/1-butene and ethylene/1-hexene copolymers, but not to ethylene/1-octene copolymers (see Lue et al, US 6,870,010B 1). In the present disclosure, systematic studies were conducted to observe the effect of SCB on the Mark-Houwink constant K for three types of ethylene/1-olefin copolymers, namely octene, hexene and butene copolymers. After subtracting the contribution of SCB, a viscosity LCB index was introduced to characterize the LCB containing ethylene/1-olefin copolymer. The viscosity LCB index is defined as the Mark-Houwink constant (K) of the sample measured in 1,2, 4-Trichlorobenzene (TCB) at 140 ℃ m) SCB-corrected Mark-Houwink constant (K) divided by linear ethylene/1-olefin copolymerCO) Equation (1).
Wherein [ η]Is the intrinsic viscosity (dL/g), M, determined by 3D-SECvIs the viscosity average molar mass (g/mol) determined using 3D-SEC; SCB is the short chain branching Content (CH) determined using FTIR3#/1000C) and a is a constant, depending on the α -olefin present in the ethylene/α -olefin interpolymer tested, specifically 2.1626, 1.9772 and 1.1398 for 1-octene, 1-hexene and 1-butene, respectively, in the case of ethylene homopolymer, no correction for Mark-Houwink constants is required, i.e. SCB is zero.
Rheology is also an effective method in the art to measure the amount of LCB or lack thereof in ethylene interpolymers. Several streams of quantitative LCB have been disclosedOne common method is based on zero shear viscosity (η)0) And weight average molar mass (M)w) A power of 3.41 dependence on monodisperse polyethylene consisting of linear chains only has been established (η) 0= K×Mw 3.41) See, for example, R.L. Arnett and C.P. Thomas, J. Phys. chem. 1980, 84, 649-0More than having the same MwExpected η for linear ethylene polymers0The ethylene polymer of (a) is believed to contain long chain branches. However, there is a need in the art for polydispersities such as Mw/MnThe controversy of the effects of (c). Polydispersity dependence is observed in some cases (see M. Ansari et al, Rheol. Acta, 2011, 5017-27), but not in others (see T.P. Karjala et al, Journal of Applied Polymer Science 2011, 636-.
Another example of analyzing LCB by rheology is based on zero shear viscosity (η)0) And intrinsic viscosity ([ η)]) See, for example, R.N. Shroff and H. Mavridis,
In the present disclosure, systematic studies were conducted to observe the effects of both SCB and molar mass distribution. After subtracting the contribution of SCB and molar mass distribution (polydispersity), a "long chain branching factor" (hereinafter "LCBF") was introduced to characterize the amount of LCB in the ethylene/α -olefin copolymer, as detailed below.
In the present disclosure, Long Chain Branching Factor (LCBF) is used to characterize the amount of LCB in the ethylene interpolymer product. The disclosed ethylene interpolymer products employ (i) a first reactor; (ii) first and second reactors; or (iii) bridged metallocene catalyst formulation in the first, second, and third reactors; or (iv) optionally, the bridged metallocene catalyst formulation used in the third reactor may be replaced with an alternative homogeneous catalyst formulation or heterogeneous catalyst formulation.
Fig. 2 illustrates the calculation of the LCBF. The solid "reference line" shown in fig. 2 characterizes an ethylene polymer without LCB (or with undetectable levels of LCB).
The LCB-containing ethylene interpolymer was offset from the reference line. For example, ethylene interpolymer product examples 1-3 (open circles in fig. 2) are offset horizontally and vertically from the reference line.
LCBF calculation Zero Shear Viscosity (ZSV) requiring polydispersity correctionC) And SCB corrected Intrinsic Viscosity (IV) C) As described in equation (2).
As shown in equation (2), for a zero shear viscosity ZSV having a poise dimensionCAnd (3) correcting:
η therein0Zero shear viscosity (poise), as measured by DMA as described in the "test methods" section of this disclosure; pd is the dimensionless polydispersity (M) measured using conventional SEC (see "test methods")w/Mn) And 1.8389 and 2.4110 are dimensionless constants.
For intrinsic viscosity IV having dL/g dimension as shown in equation (3)CAnd (3) correcting:
wherein the intrinsic viscosity is measured using 3D-SEC [ η](dL/g) (see "test methods"); measurement of dimensional (CH) Using FTIR3#/1000C) (see "test methods"); mvFor viscosity average molar mass (g/mol), 3D-SEC was used for determination (see "test methods"), and A is a dimensionless constant, depending on whether the A of the α -olefin, i.e., 1-octene, 1-hexene, and 1-butene α -olefin, in the ethylene/α -olefin interpolymer sample, is 2.1626, 1.9772, or 1.1398, respectively.
The linear ethylene/α -olefin interpolymer (containing no LCB or undetectable LCB levels) falls on the reference line defined by equation (4).
As shown in FIG. 2, the calculation of LCBF is based on a horizontal displacement (S) from a linear reference lineh) And vertical displacement (S)v) As defined by the following equation:
in equations (5) and (6), ZSV is requiredCAnd IVCRespectively having dimensions poise and dL/g. Horizontal displacement (S)h) Is ZSVCAt constant Intrinsic Viscosity (IV)C) The physical meaning of the displacement of (c) is apparent if the Log function is removed, i.e. the ZSV of the sample being measuredCRelative to having the same IVCZSV of linear ethylene polymersCThe ratio of two zero shear viscosities. Horizontal displacement (S)h) Is dimensionless. Vertical displacement (S)v) Is a constant Zero Shear Viscosity (ZSV)C) Lower IVCIf the Log function is removed, its physical meaning is apparent, i.e. having the same ZSVCIV of the linear ethylene polymerCIV relative to the sample to be measuredCThe ratio of the two intrinsic viscosities. Vertical displacement (S)v) Is dimensionless.
The dimensionless Long Chain Branching Factor (LCBF) is defined by equation (7):
the linear ethylene/α -olefin interpolymer (containing no LCB or no detectable LCB level) falls on the reference line defined by equation (4). tables 2A and 2B set forth 37 reference resins containing no LCB (or no detectable LCB). M of the reference resins w/MnThe value is 1.68 to 9.23, the "A" value in Table 2A indicates whether the reference resin contains 1-octene, 1-hexene or 1-butene α -olefin the reference resin includes the use of Ziegler-Natta, homogeneous and mixed (Ziegler-Natta) in solution, gas phase or slurry processesIn the present disclosure, resins without LCB (or with undetectable LCB) are characterized by an LCBF of less than 0.001 (dimensionless) as shown in Table 2B, where the LCBF value for the reference resin is from 0.000426 to 1.47 × 10-9。
Table 3A discloses the LCBF values for the examples and comparative examples. For example, S of Long chain branching example 1hAnd Sv0.646 and 0.136, respectively, and LCBF of 0.044((0.646 × 0.136)/2). in contrast, S of comparative example 1a, which did not contain LCBhAnd Sv-0.022 and-0.0047, respectively, and LCBF 0.0001((-0.022 × -0.047)/2).
In this disclosure, the resin with LCB is characterized by LCBF ≧ 0.001 (dimensionless); in contrast, resins without LCB (or with undetectable LCB) are characterized by an LCBF of less than 0.001 (dimensionless).
The ethylene interpolymer products disclosed herein, i.e., examples 1-3, comprise LCB, as shown in table 3A and fig. 2. More specifically, as shown in table 3A, the LCBFs of examples 1 to 3 were 0.044, 0.054 and 0.056, respectively, and did not fall on the linear reference line shown in fig. 2. In contrast, comparative example 1a had an LCBF of 0.0001 (table 3A) and fell on the reference line (fig. 2, filled triangle), i.e., contained no LCB or had undetectable levels of LCB. Examples 1-2 are ethylene interpolymer products produced using a bridged metallocene catalyst formulation in a first and second solution polymerization reactor, and example 3 is produced using a bridged metallocene catalyst formulation in the first solution polymerization reactor. Comparative example 1a was produced using a non-bridged single site catalyst formulation in the first and second solution polymerization reactors. Comparative example 1a is a commercial product numbered FPs117-C from NOVA Chemicals Corporation, Calgary, Alberta. From table 3A, it is evident that comparative examples Q1, Q3, and Q4 (open squares in fig. 2) contain long chain branching, i.e., LCBF values of 0.049, 0.018, and 0.067, respectively. Comparative example Q is a commercial product known as Queo from Borealis, Vienna, Austria; specifically, comparative example Q1 is Queo 0201, comparative example Q3 is Queo 0203, and comparative example Q4 is Queo 1001.
Table 3B summarizes the LCB-containing comparative example R1 (open diamonds in fig. 2) for an LCBF value of 0.040. Comparative example R1 is a commercially available product designated Affinity PL1880G from The Dow Chemical Company, Midland Mich. As shown in Table 3B, comparative examples S1 and S2 (filled circles in FIG. 2) contained LCB, which had LCBF values of 0.141 and 0.333, respectively. Comparative examples S1 and S2 are commercially available products known as Enable from ExxonMobil Chemical Company, Spring Texas; specifically, Enable 20-05HH and Enable 27-03. Table 3B discloses that comparative example U (cross-x symbol in fig. 2) contains LCB, i.e., the LCBF value is 0.036. Comparative example U is a commercial product available under The reference Elite AT 6202 from The Dow Chemical Company, Midland, Michigan. Two samples (dash-like symbols in FIG. 2) of comparative example V2 summarized in Table 3B (V2a and V2B) had LCBF values of 0.0080 and 0.0088, a commercially available product designated Elite 5100G from The Dow chemical Company, Midland, Michigan. Comparative example T was obtained from ExxonMobil Chemical Company, Spring, Texas, exceeded 1018.
Although comparative examples 4 and 5 are not present in tables 3A-3B or fig. 2, these resins had no LCB or undetectable levels of LCB, i.e., LCBF < 0.001. Comparative examples 2 and 3 are also not shown in tables 3A-3B or fig. 2. Comparative example 2 contains LCB, i.e., the average LCBF of the three samples of comparative example 2 (i.e., comparative examples 2a to 2c) is 0.037. Comparative example 3 contains LCB, i.e., the four samples of comparative example 3 (i.e., comparative examples 3a-3d) had an average LCBF of 0.016.
Solution polymerization process
Embodiments of the continuous solution polymerization process are shown in fig. 3 and 4. Fig. 3 and 4 should not be construed as limiting, it being understood that embodiments are not limited to the precise arrangement or number of containers shown. Briefly, FIG. 3 shows one Continuous Stirred Tank Reactor (CSTR) followed by an optional tubular reactor, and FIG. 4 shows two CSTRs followed by an optional tubular reactor. The dashed lines in fig. 3 and 4 illustrate optional features of the continuous polymerization process. In the present disclosure, the equivalent term for the tubular reactor 117 shown in fig. 4 is "third reactor" or "R3"; optionally producing a third ethylene interpolymer in the reactor. Referring to FIG. 3 with one CSTR, the term "third reactor" or "R3" is also used to describe the
In fig. 3,
The bridged metallocene catalyst formulation is injected into
Optionally, deactivating the first outlet stream,
The term "tubular reactor" is intended to convey its conventional meaning, i.e., simple tubes; wherein the length/diameter (L/D) ratio is at least 10/1. Optionally, one or more of the following reactor feed streams may be injected into the tubular reactor 17: process solvent 13,
In fig. 3, streams 34a to 34h represent "heterogeneous catalyst assemblies". In one embodiment, the in-line ziegler-natta catalyst formulation is produced in a heterogeneous catalyst component. Components comprising the in-line Ziegler-Natta catalyst formulation are introduced via
The amount of the in-line heterogeneous catalyst formulation added to the
Any combination of streams used to prepare and deliver the in-line ziegler-natta catalyst formulation to
In
The optional third ethylene interpolymer produced in
In fig. 3, the deactivated solution a (
The first bottoms stream enters a second V/
The
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