Polyethylene copolymer with broad short chain branching distribution

Abstract

1. A polyethylene copolymer comprising ethylene units and C4-C8 α-olefin comonomer units, having the following characteristics: a melt index of about 0.1 to about 15 g / 10 min at 190° C. as determined by ASTM D1238 under 2.16 kg and at 190° C.; a density of 0.905 to 0.930 g / cc; a molecular weight distribution of about 1.5 to about 2.7; and a molecular weight distribution of about 0.5 to about 2.7 as determined by ASTM D1238 under 2.16 kg and at 190° C. ... * (density [g / cc]) + 863 temperature scale excluding the first 10% and last 1% of the polymer, and the formula: F% ≧ 510 * (density [g / cc]-0.905), where F% is the percentage of lamellar thickness greater than 12 nm.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 188,027, filed May 13, 2021, the contents of which are incorporated by reference in their entirety herein. [Background technology]

[0002] Polyethylene is an olefin polymer with many different end uses. One type of polyethylene that is particularly useful for making films is linear low-density polyethylene (LLDPE), which is formed by copolymerizing ethylene with other olefin monomers, resulting in a copolymer that contains a polyethylene backbone with short branches extending therefrom. The distribution of branches strongly influences the properties of the resulting polymer and its desirability for certain applications, such as forming packaging films. Examples of such properties include dart impact strength, tear resistance, heat seal initiation, hot tack initiation, optical properties, and processability. However, improving some of these properties often makes other properties less desirable.

[0003] Metallocene catalyzed LLDPE (mLLDPE) polymers tend to have a relatively uniform or narrow short chain branching distribution, resulting in polymers with some good and some undesirable characteristics, e.g., high toughness, but poor processability and optical properties. It is therefore desirable to produce polyethylene polymers with more diverse branching or a broader short chain branching distribution that can provide further improvements in toughness without sacrificing processability and optical properties. Attempts to form mLLDPE polymers with a broad short chain branching distribution have been made, for example, by using mixtures of different catalysts or a series of reactors with different conditions, but further improvements are needed. Summary of the Invention

[0004] The present disclosure generally relates to polyethylenes comprising ethylene units and α-olefin comonomer units, the polyethylenes having the following characteristics: a melt index of about 0.1 to about 15 g / 10 min at 2.16 kg and 190° C. as determined by ASTM D1238, a density of 0.905 to 0.930 g / ml as determined by ASTM D1505, a molecular weight distribution (Mw / Mn) of about 1.5 to about 2.7, and a molecular weight distribution (Mw / Mn) of about 1.5 to about 2.7 as determined by the formula: ΔT [° C.]≧−909 * The crystallization elution fractionation temperature range excluding the first 10% and the last 1% of the polymer on the temperature scale according to density [g / cc] + 863 and the formula: F% ≧ 510 * (d[g / cc]-0.905), where F% is the percentage of lamellar thickness greater than 12 nm.

[0005] The present disclosure also provides a cellulose acylate copolymer having the following characteristics: a melt index of about 0.1 to about 15 g / 10 min as determined by ASTM D1238 at 2.16 kg and 190° C., a density of 0.905 to 0.935 g / ml as determined by ASTM D1505, a molecular weight distribution (Mw / Mn) of about 1.5 to about 2.7, and a molecular weight distribution (Mw / Mn) of about 1.5 to about 2.7 as determined by the formula: ΔT [° C.]≧−909 * The crystallization elution fractionation temperature range excluding the first 10% and the last 1% of the polymer on the temperature scale according to density [g / cc] + 863 and the formula: F% ≧ 510 * (d[g / cc]-0.905), where F% is the percentage of lamellar thickness greater than 12 nm. The copolymer comprises (I) an intermediate composition derived from at least (a) a carrier, (b) an organoaluminum compound, and (c) an oxygen source, and (II) an (A)R 2 2AlY (in the formula, each R 2independently comprise a hydrocarbyl group having from 1 to about 20 carbons, and Y comprises a halide radical, a pseudohalide radical, an alkoxide radical, an aryloxide radical, an alkyl substituted amido radical, an aryl substituted amido radical, a siloxy radical, a boronoxy radical, a diarylboronoxy radical, or a halogenated diarylboronoxy radical, or (B) a combination of (i) and (ii), wherein (i) is a group represented by the formula R 1 (X) n wherein R 1 is a hydrocarbyl group having from about 1 to about 20 carbon atoms, n is from 1 to the number of possible substitutions on the hydrocarbyl group, and each X is R 1 and optionally substituted on the above, independently selected from halogen, -OSi(R 3 )3, -N(Si(R 3 )3)2, -N(R 3 )2, -SR 3 , -P(R 3 )2, -CN, or -OR 4 (In the formula, each R 3 are independently hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms, and each R 4 are independently hydrocarbyl having 1 to 20 carbon atoms, and at least one R 3 When R is a hydrocarbyl group, 1 and R 3 Or R 1 and R 4 are optionally linked together to form a cyclic group, with the proviso that at least one X is not directly bonded to an aryl group, and with the proviso that if X is not a halogen, then X is bonded to a secondary or tertiary carbon, or to a -CH-aryl group; (ii) is a group of formula AlR, where each R is independently a C1-C 20 (III) a transition metal component; and (IV) a trihydrocarbylaluminum compound having a hydrocarbyl group therein; and (V) a transition metal component.

[0006] Other features and aspects of the disclosure are discussed in more detail below. [Brief description of the drawings]

[0007] The present disclosure may be better understood with reference to the following figures. [Figure 1] 1 is a CEF profile of the polyethylene copolymer produced in Example 2. [Diagram 2] 1 is a chart showing the cumulative CEF curve for the polyethylene copolymer produced in Example 2 superimposed on the m-SSA curve for the polyethylene copolymer produced in Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Before describing some exemplary embodiments, it is to be understood that the invention is not limited to the details of construction or process steps set forth in the following description as the invention is capable of other embodiments and of being practiced or carried out in various ways.

[0009] In general, the present disclosure relates to polyethylenes with broad short chain branching distributions that have a unique blend of characteristics. Methods for producing the polyethylenes are also disclosed. As a result of their chemical composition distribution, the polyethylenes have characteristics that are particularly beneficial for forming films. For example, films formed from polyethylene polymers have good dart impact strength and tear resistance, as well as low heat seal initiation and hot tack initiation, without sacrificing optical properties and processability.

[0010] 1) Polyethylene copolymer Polyethylene polymers according to the present disclosure are generally copolymers composed of ethylene-based units and α-olefin-based comonomer units, e.g., C4-C8 α-olefin-based comonomer units. Copolymers can include two or more comonomer species, such as a combination of 1-hexene and 1-octene. Thus, the term copolymer is not limited to polymers containing only two monomer species. The comonomer content is typically about 0.5 mol% to about 4 mol%. Preferably, the comonomer includes 1-hexene.

[0011] The density of the polyethylene copolymer is generally about 0.905 g / cc to about 0.935 g / cc. For example, the density is preferably greater than about 0.910 g / cc, for example, greater than about 0.915 g / cc. In addition, the density is preferably less than about 0.930 g / cc, for example, less than about 0.925 g / cc, for example, less than about 0.920 g / cc. The melt index of the copolymer is generally about 0.1 g / 10 min to about 15 g / 10 min, as measured according to ASTM D1238 (2.16 kg, 190° C.). For example, the melt index is preferably greater than about 0.25 g / 10 min, for example, greater than about 0.5 g / 10 min, for example, greater than about 0.75 g / 10 min, for example, greater than about 0.9 g / 10 min, as measured according to ASTM D1238 (2.16 kg, 190° C.). In addition, the melt index, measured according to ASTM D1238 (2.16 kg, 190° C.), is preferably less than about 10 g / 10 min, such as less than about 5 g / 10 min, such as less than about 2.5 g / 10 min. The molecular weight distribution MWD (Mw / Mn) is typically from about 1.5 to about 2.7.

[0012] Polyethylene copolymers have a broad short chain branching distribution in metallocene-catalyzed LLDPE. One way to measure the short chain branching distribution is to analyze the crystallization elution fractionation (CEF) profile of the polymer and / or its successive self-nucleation and annealing (SSA) profile. The breadth of the CEF profile can be quantified by measuring the difference (ΔT) between the temperature below which 10% of the area under the elution profile falls and the temperature above which 1% of the area under the elution profile falls. Figure 1 illustrates a CEF profile including ΔT for a polyethylene copolymer according to the present disclosure. This temperature difference is generally larger for copolymers with a broader short chain branching distribution. The polyethylene copolymers described herein generally have a ΔT [°C] ≥ -909°C. * (density [g / cc]) + 863. For example, ΔT is preferably greater than about 13°C, such as greater than about 15°C, such as greater than about 20°C, such as greater than about 25°C, such as greater than about 30°C. Generally, polyethylene copolymers have a ΔT [°C] ≦ -909 * (density [g / cc]) + 873. For example, ΔT is preferably less than about 50°C, such as less than about 45°C, such as less than about 40°C, for example less than about 35°C.

[0013] In addition, the copolymers may be characterized by the percentage difference (SC) between a point on the cumulative CEF curve at a particular temperature and a point on the modified cumulative SSA curve at the same temperature. The modified cumulative SSA curve (m-SSA) refers to the cumulative SSA curve minus 32°C, allowing for better comparison with the cumulative CEF curve. Figure 2 shows the cumulative m-SSA curve of a polyethylene copolymer according to the present disclosure, with the corresponding cumulative CEF curve superimposed thereon. The SC percentage difference at 70°C is also shown. Generally, polyethylene copolymers have an SC at 70°C of less than about 15%, preferably less than about 14%. The SC at 70°C is typically greater than about 6%, for example, greater than about 10%.

[0014] Polyethylene copolymers can be characterized by their SSA curves and the well-known equation:

[0015]

number

[0016] 2) Process for making polyethylene copolymers The polyethylene copolymer is produced using a specific combination of activator and transition metal catalyst component. For example, the inventors have discovered that when a specific supported activator composition is used with a specific metallocene catalyst in an ethylene polymerization process, the unique resin properties described herein are obtained. Advantageously, the catalyst described herein also leaves significantly less catalyst residue in the polymer resin as a result of higher catalytic activity compared to conventional catalysts. For example, pellets produced from polyethylene copolymers generally contain less than 0.5 ppm of transition metal components such as Zr. Preferably, the polyethylene copolymer contains less than 0.45 ppm, such as less than 0.4 ppm, such as less than about 0.35 ppm, of transition metal components such as Zr. Pellets containing the copolymer typically contain at least about 10 ppm, such as at least about 20 ppm, such as at least about 25 ppm of transition metal components.

[0017] One advantage of the process disclosed herein is that polyethylene can be produced using only a single reactor, rather than a series of two or more reactors. In addition, polyethylene can be polymerized using a single type of catalyst, rather than using a mixture of different catalysts. The ability to use a single type of catalyst in a single reactor allows for a more efficient production process than other attempts to make mLLDPE with a broad short chain branching distribution.

[0018] Particularly useful activator compositions for producing polyethylene copolymers are described in U.S. Patent Nos. 8,354,485 and 9,090,720, both of which are incorporated herein by reference. For example, activator compositions generally comprise: (I) an intermediate composition derived from at least (a) a carrier, (b) an organoaluminum compound, and (c) an oxygen source; (II) (A) an organoaluminum compound; and (C) an oxygen source. 2 2AlY (in the formula, each R 2independently comprise a hydrocarbyl group having from 1 to about 20 carbons, and Y comprises a halide radical, a pseudohalide radical, an alkoxide radical, an aryloxide radical, an alkyl substituted amido radical, an aryl substituted amido radical, a siloxy radical, a boronoxy radical, a diarylboronoxy radical, or a halogenated diarylboronoxy radical, or (B) a combination of (i) and (ii), wherein (i) is a group represented by the formula R 1 (X) n wherein R 1 is a hydrocarbyl group having from about 1 to about 20 carbon atoms, n is from 1 to the number of possible substitutions on the hydrocarbyl group, and each X is R 1 and optionally substituted on the above, independently selected from halogen, -OSi(R 3 )3, -N(Si(R 3 )3)2, -N(R 3 )2, -SR 3 , -P(R 3 )2, -CN, or -OR 4 (In the formula, each R 3 are independently hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms, and each R 4 are independently hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms, and at least one R 3 When is a hydrocarbyl group, R 1 and R 3 Or R 1 and R 4 are optionally linked together to form a cyclic group, with the proviso that at least one X is not directly bonded to an aryl group, and with the proviso that if X is not a halogen, then X is bonded to a secondary or tertiary carbon, or to a -CH-aryl group; (ii) is a group of formula AlR, where each R is independently a C1-C 20 and wherein the aryl group is a trihydrocarbylaluminum compound having a aryl group,

[0019] I. Intermediate Composition The intermediate composition can be formed by combining at least a carrier, an organoaluminum compound, and an oxygen source. The oxygen source can be any source of oxygen atoms, such as O2 or H2O, including water contained in the carrier. The order of addition when combining the components can vary. For example, it can be [(carrier + oxygen source) + organoaluminum compound] or it can be [(organoaluminum compound + oxygen source) + carrier]. In addition, an oxygenated organoaluminum compound, such as MAO, can be combined with the carrier. As used herein, an oxygenated organoaluminum compound is a compound derived from at least an organoaluminum compound and an oxygen source. The purpose of forming this intermediate composition is to generate Lewis acid sites (i.e., sites suitable for accepting at least one electron pair) to react with the dialkylaluminum cation precursor agent to generate a dialkylaluminum cation precursor on the carrier / support. The carrier source can contain absorbed water, which can function as an oxygen source. A second oxygen source is then optional. The carrier containing water can then be combined with an organoaluminum compound, such as trimethylaluminum (TMA), to form the intermediate composition. The support may be first dried to remove absorbed water, and then a predetermined amount of water may be added back to the support to more precisely control the water content. An oxygen source may be combined with an organoaluminum compound to form a first product (e.g., MAO formed from water and TMA, or from Ph3COH and TMA), and the first product may then be combined with a dried or non-dried support to form a second product (a composition derived from the support and the oxygenated organoaluminum compound).

[0020] a) Carrier Carriers useful in the activator composition can include inorganic or organic carriers. Such carriers may contain water or may have water removed from the carrier by any means known in the art, such as calcination. Such carriers may also have absorbed water completely or incompletely removed, followed by the addition of a certain amount of water. Such carriers may contain a maximum percentage of water such that free water does not leach from the carrier. Carriers containing water can be either uncalcined or low-temperature calcined. As used herein, an "uncalcined" carrier is one that has not been intentionally subjected to a calcination treatment, and a "low-temperature calcined" carrier is one that has been calcined at a temperature below 200°C, e.g., below about 100°C, e.g., below about 50°C. Calcination can be carried out in any atmosphere, e.g., in an air atmosphere, an inert gas atmosphere, or under vacuum.

[0021] A mixture of carriers may be used, and the carrier may contain water as absorbed water or in the form of a hydrate. The carrier is preferably porous and has a total pore volume of 0.1 ml or more per gram of carrier, for example, 0.3 ml or more per gram of carrier. The average particle size of the carrier may be about 5 micrometers to about 1000 micrometers, for example, about 10 micrometers to about 500 micrometers.

[0022] Useful inorganic supports include inorganic oxides, magnesium compounds, clay minerals, and the like. Inorganic oxides can include silica, alumina, silica-alumina, magnesia, titania, zirconia, and clay. Useful inorganic oxides include, but are not limited to, SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, and double oxides thereof, such as SiO2-Al2O3, SiO2-MgO, SiO2-iO2, SiO2-TiO2-MgO. Useful magnesium compounds include MgCl2, MgCl(OEt), and the like. Useful clay minerals include kaolin, bentonite, kibushi clay, geyloam clay, allophane, hisingerite, pyrophylite, talc, mica, montmorillonite, vermiculite, chlorite, palygorskite, kaolinite, nacrite, dickite, halloysite, and the like.

[0023] In one embodiment, a suitable silica support is porous and has a surface area of ​​about 10 μm. 2 / g silica ~ approx. 1000m 2 / g silica, e.g., about 10 m 2 / g silica ~ approx. 700m 2 / g silica, total pore volume in the range of about 0.1 ml / g silica to about 4.0 ml / g silica, and average particle size in the range of about 10 micrometers to about 500 micrometers. 2 / g~about 500m 2 / g, a pore volume in the range of about 0.5 ml / g to about 3.5 ml / g, and an average particle size in the range of about 15 micrometers to about 150 micrometers.

[0024] The average pore diameter of useful porous silica supports typically ranges from about 10 angstroms to about 1000 angstroms, such as from about 50 angstroms to about 500 angstroms, such as from about 175 angstroms to about 350 angstroms. Typical contents of hydroxyl groups are from about 2 mmol OH / g silica to about 10 mmol OH / g silica, such as from about 3 mmol OH / g silica to about 8 mmol OH / g silica, such as from about 3.3 mmol OH / g silica to about 7.2 mmol OH / g silica.

[0025] Useful organic carriers include acrylic polymers, styrene polymers, ethylene polymers, propylene polymers, etc. Acrylic polymers include polymers of acrylic monomers, such as acrylonitrile, methyl acrylate, methyl methacrylate, methacrylonitrile, etc., and copolymers of monomers and cross-linking polymerizable compounds having at least two unsaturated bonds. Styrene polymers include polymers of styrene monomers, such as styrene, vinyl toluene, ethylvinylbenzene, etc., and copolymers of monomers and cross-linking polymerizable compounds having at least two unsaturated bonds. Cross-linking polymerizable compounds having at least two unsaturated bonds include divinylbenzene, trivinylbenzene, divinyltoluene, divinyl ketone, diallyl phthalate, diallyl maleate, N,N'-methylenebisacrylamide, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, etc.

[0026] Useful organic carriers generally have at least one polar functional group. Suitable polar functional groups include primary amino groups, secondary amino groups, imino groups, amide groups, imide groups, hydrazide groups, amidino groups, hydroxyl groups, hydroperoxy groups, carboxyl groups, formyl groups, methyloxycarbonyl groups, carbamoyl groups, sulfo groups, sulfino groups, sulfeno groups, thiol groups, thiocarboxyl groups, thioformyl groups, pyrrolyl groups, imidazolyl groups, piperidyl groups, indazolyl groups and carbazolyl groups. When the organic carrier originally has at least one polar functional group, the organic carrier can be used as is. One or more polar functional groups can also be introduced by subjecting the organic carrier to a suitable chemical treatment. The chemical treatment can be any method that can introduce one or more polar functional groups into the organic carrier. For example, it can be a reaction between an acrylic polymer and a polyalkylene polyamine such as ethylenediamine, propanediamine, diethylenetriamine, tetraethylenepentamine, dipropylenetriamine, etc. For example, an acrylic polymer (e.g., polyacrylonitrile) can be treated in a slurry state in a mixed solution of ethylenediamine and water at 100° C. or higher. The amount of the polar functional group in the organic carrier having the polar functional group can be 0.01 to 50 mmol / g, or 0.1 to 20 mmol / g.

[0027] b) Organoaluminum Compounds A useful organoaluminum compound is AlR n (XR 1 m ) (3-n) where Al is aluminum, each R is hydrogen or a hydrocarbyl group having up to about 20 carbon atoms, each R may be the same as or different from any other R, and each XR 1 For 1 is an organic group bonded to Al through a heteroatom and having up to about 20 carbon atoms, and each XR 1 Does not match any other XR 1and n is 1, 2, or 3. When X is a halide, m=0, when X is O or S, m=1, and when X is N or P, m=2. Each R can be a linear or branched alkyl group. Non-limiting examples of R include alkyl groups having 1 to about 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, neopentyl, and the like.

[0028] AlR n (XR 1 m ) (3-n) Non-limiting examples of aluminum hydride include, for compounds where n=3, trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diisobutylaluminum hydride, diethylaluminum hydride, dimethylaluminum hydride; for compounds where n=1 or 2 and m=0, AlMe2Cl, AlMeCl2, AlMe2F, AlMeF2; and for compounds where n=1 or 2 and m=1, (2,6-di-tert-butyl -4-methylphenoxy)diisobutylaluminum, bis(2,6-di-tert-butyl-4-methylphenoxy)isobutylaluminum, (2,6-di-tert-butyl-4-methylphenoxy)diethylaluminum, bis(2,6-di-tert-butyl-4-methylphenoxy)ethylaluminum, (2,6-di-tert-butyl-4-methylphenoxy)dimethylaluminum, bis(2,6-di-tert-butyl-4-methylphenoxy)methylaluminum, AlMe2(O t Bu), AlMe(O t Examples of compounds where n=1 or 2 and m=2 include AlMe2(NMe2), AlMe(NMe2)2, AlMe2(NEt2), AlMe(NEt2)2, AlEt2(NMe2), AlEt(NMe2)2, AlEt2(NEt2), AlEt(NEt2)2, Al i Bu2(NMe2), Al iBu(NMe2)2, Al i Bu2(NEt2), Al i These include Bu(NEt2)2, AlMe2(N(SiMe3)2), AlMe(N(SiMe3)2)2 and mixtures thereof.

[0029] The organoaluminum compounds can be prepared by any suitable method, including methods currently known or that may become known, such as those well known to those skilled in the art.

[0030] c) Oxygen source The oxygen source can be any source of oxygen atoms, such as water in a carrier. Alternatively, the oxygen source can be any suitable source of oxygen as would be familiar to one of ordinary skill in the art taught herein. Examples include: 1) free water, either in the gas phase or in a condensed phase (liquid or solid); 2) coordinated forms of water, such as hydrated metal salts (e.g., LiOH(HO) n ) and 3) compounds containing hydroxy groups, including, but not limited to, water absorbed on molecular sieves, etc. In addition, oxygen sources include hydroxy- or carbonyl-containing compounds in which the oxygen atom is directly linked to a tertiary carbon and a hydrogen, such as t The organoaluminum compound may be either BUOH, Ph3COH, etc., or a hydroxy- or carbonyl-containing compound that is directly linked to the tertiary carbon and Al after reaction with trialkylaluminum, such as PhCOMe, PhCOOH, etc. Depending on the organoaluminum compound used, the amount of oxygen source may be adjusted so that the majority (at least about 50 mol%) of the oxygen atoms therein are each in contact with at least two aluminum atoms. The Al:O molar ratio may be from about 100:1 to about 1:1.2, or may be such that the amount of hydroxy or alkoxy residues does not significantly interact with the active catalyst species generated during the process of the present invention.

[0031] Dialkylaluminum Cation Precursor (II-A) Useful dialkylaluminum cation precursors include R 22AlY, wherein each R 2 independently comprise a hydrocarbyl group having up to about 20 carbon atoms, Al is aluminum, and Y comprises a heteroatom or group bonded to Al. Each hydrocarbyl group can comprise one or more heteroatom substituents, but this is not required. Y can comprise, for example, a heteroatom such as O, N, or a group such as a halide radical, a pseudohalide radical, an alkoxide radical, an aryloxide radical, an alkyl-substituted amido radical, an aryl-substituted amido radical, a siloxy radical, a boronoxy radical, a diarylboronoxy radical, a halogenated diarylboronoxy radical, etc.

[0032] For example, dialkylaluminum cation precursor agents include dimethylaluminum fluoride (MeAlF), dimethylaluminum chloride, diethylaluminum fluoride, diethylaluminum chloride, di-n-propylaluminum fluoride, diisobutylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum fluoride, di-n-hexylaluminum chloride, dimethylaluminum methoxide, dimethylaluminum ethoxide, dimethylaluminum isobutoxide, dimethylaluminum phenoxide, dimethylaluminum pentafluorophenoxide (MeAl(OCF)), dimethylaluminum (2,6-di-t-butyl-4-methyl)phenoxide (MeAl(BHT)), dimethylaluminum (2,6-di-isobutyl)phenoxide, dimethylaluminum dimethylamide, dimethylaluminum diethylamide, dimethylaluminum dibutylamide, dimethylaluminum methylphenylamide, diethylaluminum methoxide, diethylaluminum dimethylamide, diethylaluminum methylphenylamide, diethylaluminum methoxide, diethylaluminum methylphenylamide ... diisobutylaluminum ethoxide, dimethylaluminum isobutoxide, diethylaluminum phenoxide, diethylaluminum pentafluorophenoxide, diethylaluminum (2,6-di-t-butyl-4-methyl)phenoxide, diethylaluminum (2,6-di-isobutyl)phenoxide, diethylaluminum dimethylamide, diethylaluminum diethylamide, dimethylaluminum dibutylamide, diethylaluminum methylphenylamide, diisobutylaluminum methoxide, diisobutylaluminum ethoxide, diisobutylaluminum methoxide, diisobutylaluminum phenoxide, diisobutylaluminum pentafluorophenoxide, diisobutylaluminum (2,6-di-t-butyl-4-methyl)phenoxide, diisobutylaluminum (2,6-di-isobutyl)phenoxide, diisobutylaluminum dimethylamide, diisobutylaluminum diethylamide, diisobutylaluminum dibutylamide, and / or diisobutylaluminum methylphenylamide.

[0033] Dialkylaluminum cation precursor is AlR 2 3 (e.g., AlMe3) to AlR 2 It can also be generated in situ by mixing with Y2 (e.g., AlMeF2) or AlY3 (e.g., AlF3). 2 3 may be combined with an intermediate composition derived from at least an organoaluminum compound, a carrier, and an oxygen source, or may be coordinated with the MAO framework or a portion thereof.

[0034] The Lewis base component is optional. When included, the Lewis base can be chelating or non-chelating. A Lewis base is a reagent that can donate at least one pair of electrons to form a stable dialkylaluminum cation complex derived from a dialkylaluminum cation precursor (including N, O, or halide donors) in the system. For example, suitable Lewis bases include non-chelating Lewis bases such as PhNMe2, PhNEt2, PhNPr2, Ph2NMe, Ph2Net, Ph2NPr, NMe3, NEt3, Me3SiOSiMe3, EtOEt, THF (tetrahydrofuran), PhOMe, t BuOMe, ClPh, FPh, and the like, and chelating Lewis bases such as Me2N(CH2)2NMe2, Et2N(CH2)2NEt2, Ph2N(CH2)2NPh2, Me2N(CH2)3NMe2, Et2N(CH2)3NEt2, Ph2N(CH2)3NPh2, Me3SiOSi(Me)2OSiMe3(OMTS), MeO(CH2)2OMe, EtO(CH2)2OEt, PhO(CH2)2OPh, MeO(CH2)3OMe, EtO(CH2)3OEt, Ph2O(CH2)OPh, and the like.

[0035] The activator composition can be derived from at least a carrier, an oxygen source, an organoaluminum compound, and a dialkylaluminum cation precursor agent. The carrier can be combined with the organoaluminum compound and an oxygen source to form an intermediate composition, and at least a portion of the intermediate composition can be combined with the dialkylaluminum cation precursor agent to form the activator composition. The oxygen source can be water already in the carrier. Also, the organoaluminum and the oxygen source (e.g., water) can be premixed to form an oxygenated organoaluminum compound, which is then combined with the carrier to form the intermediate composition.

[0036] The combination can be carried out in an inert gas atmosphere at a temperature of about -80°C to about 200°C, for example, about 0°C to about 150°C, and the combination time can be about 1 minute to about 36 hours, for example, about 10 minutes to about 24 hours. Treatment after completion of the combination operation can include filtering the supernatant, followed by washing with an inert solvent, and evaporating the solvent under reduced pressure or in an inert gas stream, although these treatments are not required. The resulting activator composition can be used for polymerization in any suitable state, including as a fluid, dry or semi-dry powder, or may be used for polymerization as a suspension in an inert solvent. The combination of the carrier, oxygen source, and organoaluminum compound can be carried out at ambient temperature for a combination time of about 15 minutes to about 48 hours, for example, about 15 minutes to about 6 hours, and the resulting mixture can be used as is or can be subsequently heated to a temperature of about 80°C to about 150°C. Alternatively, the combination of the carrier, oxygen source, and organoaluminum compound can be carried out at a temperature of from about 80° C. to about 150° C. for a combination time of from about 15 minutes to about 6 hours. At least a portion of the resulting intermediate composition is combined with a dialkylaluminum cation precursor agent.

[0037] The amount of aluminum atoms in the product, e.g., solid component, obtained by combining the low-temperature calcined support with the trialkylaluminum compound should be at least about 0.1 mmol of aluminum atoms, e.g., at least about 1 mmol of aluminum atoms, per gram of the solid component in a dry state.

[0038] The activator composition can be prepared by (i) combining a carrier containing water with an organoaluminum compound and then adding a dialkylaluminum cation precursor agent, (ii) combining MAO with a carrier and then adding a dialkylaluminum cation precursor agent, or (iii) combining a carrier with water, then adding an organoaluminum compound, and then adding a dialkylaluminum cation precursor agent.

[0039] Carbocation Precursor (II-B) Alternatively, the activator composition may comprise: (i) a carbocation precursor R 1 (X) n and (ii) a trihydrocarbylaluminum compound.

[0040] Carbocation precursors are compounds containing at least one carbon atom directly linked to a labile electron-rich leaving group X, which readily forms an ion pair when contacted with a supported aluminoxane, with the leaving group X attached to the aluminoxane backbone to form an anion, and the carbon directly linked to the leaving group X becoming a carbocation. Carbocation precursors also include silyl cation precursors containing a silicon atom directly linked to a labile electron-rich leaving group X, which readily forms an ion pair-containing silyl cation when contacted with an aluminoxane, although the derived silyl cation is less stable since silicon atoms have similar chemical properties as carbon atoms with respect to cation formation. Compounds that can be used as carbocation precursors are represented by the formula R 1 (X) n wherein each X is R 1and may be any of the above, independently selected from halogen (fluorine, chlorine, or bromine, preferably fluorine), -OSi(R 3 )3, -N(Si(R 3 )3)2, -N(R 3 )2, -SR 3 , -P(R 3 )2, -CN, or -OR 4 where each R 3 are independently hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms, and each R 4 are independently hydrocarbyl having 1 to 20 carbon atoms, and at least one R 3 When is a hydrocarbyl group, R 1 and R 3 or R 1 and R 4 may be linked together to form a cyclic group, R 1 is a hydrocarbyl group having from about 1 (when X is a halogen) or from about 3 (when X is not a halogen) to about 20 carbon atoms, and n is from 1 to the number of possible substitutions of the hydrocarbyl group, provided that at least one X is not directly bonded to an aryl group, and provided that when X is not a halogen, X is selected from the group consisting of R 1 The aryl group is bonded to a secondary or tertiary carbon of the above formula (I), or to a -CH2-aryl group.

[0041] The term "aryl" disclosed above refers to the case where the labile electron-rich leaving group "X" is directly attached to the aryl group. X in this situation is non-labile, i.e., such groups have been observed to remain attached to the aryl group when contacted with supported or unsupported aluminoxanes and / or organoaluminum compounds. Preferably, R 1 When R contains an aryl group, 1is an aralkyl group (i.e., aryl-alkyl-X, e.g., PhCH2-X) where at least one X is attached to an alkyl group, thereby containing at least one labile leaving group. The "secondary or tertiary carbon" qualification disclosed above also relates to the case where the labile electron-rich leaving group "X" is not a halogen, but is attached to a primary alkyl group. It has also been observed that X in this situation is non-labile, i.e., such groups remain attached to a primary alkyl group when contacted with supported or unsupported aluminoxanes and / or organoaluminum compounds. For example, when X contains oxygen and R 1 is a primary alkyl, for example, diethyl ether (R1=Et and X=OEt) or tetrahydrofuran (THF) (R1=-CH2CH2- and X=OR 3 =-OCH2CH2- and R 1 and R 3 are linked to form a cyclic group), they remain as solvents when mixed with supported or unsupported MAO.

[0042] In one embodiment, n is 1, 2, 3, 4, 5, or 6. In another embodiment, R 1 is C1-C8 alkyl or C7-C 15 In another embodiment, X is -OR 2 and R 2 is C1-C4 alkyl or C6-C 15 It is aralkyl.

[0043] In one embodiment, R 1 (X) n is (R 5 )3C-OR 6 Or (R 5 )3C-N(R 6 ) 2, wherein each R 5 are independently hydrogen or a hydrocarbyl group containing from about to about 20 carbon atoms; R 6 is a hydrocarbyl group having from about 1 to about 20 carbon atoms, or R 5 and R 6may be linked together to form a cyclic group. 5 are independent, C1~C 18 group, more preferably (R 5 ) 3C is independently tert-butyl or trityl; R 6 is a C1 to C6 alkyl group.

[0044] X is R 1 (X) n If R is a halogen 1 can be a primary, secondary or tertiary hydrocarbyl group, and when X is a non-halogen group, R 1 is preferably a tertiary hydrocarbyl group or a saturated carbon-separated aromatic group, and less preferably a secondary hydrocarbyl group, not a primary hydrocarbyl group. The definitions of primary, secondary and tertiary hydrocarbyl groups are as follows: a primary hydrocarbyl group represents a -CH2R group (e.g., ethyl-CH2CH3 or propyl-CH2CH2CH3), a secondary hydrocarbyl group represents a -CH(R)2 group (e.g., isopropyl-CH(Me)2 or sec-butyl-CH(Me)CH2CH3), and a tertiary hydrocarbyl group represents a -CR3 group (e.g., tert-butyl-CMe3 or tritylCPh3), where R is a hydrocarbyl containing at least one carbon. A saturated carbon-separated aromatic group is a -CH2Ar group, where Ar is an aromatic group (e.g., benzyl-CH2Ph).

[0045] R1(X) nNon-limiting examples of when X=F are fluoromethane CH3F, fluoroethane CH3CH2F, tert-butyl fluoride Me3CF, trityl fluoride Ph3CF, trimethylsilyl fluoride Me3SiF, α-fluorotoluene CH5CH2F, α,α-difluorotoluene CH5CHF2, α,α,α-trifluorotoluene CF3Ph, 1,3-bis(trifluoromethyl)benzene 1,3-(CF3)2Ph, etc., when X=O, are isopropyl methyl ether Me2CHOMe, tert-butyl methyl ether Me3COMe, trityl methyl ether Ph3COMe, butene oxide CHOCHCH2CH3, 1,2-di-tert-butylbenzene, 1,2-( t BuO)2C6H41,3-Di-tert-butylbenzene, 1,3-( t BuO)2C6H4, 1,4-( t BuO)2c6H4, t BuO-CH2-CH2-O- t Bu, isobutene oxide CH2OCMe2, 2,3-dimethoxyl-2,3-dimethylbutane Me2C(OMe)C(OMe)Me2, 2,3-dimethoxybutane MeCH(OMe)CH(OMe)Me, tert-butyl trimethylsilyl ether Me3COSiMe3, 1-methyl-tetrahydrofuran, 1,2-dimethyl-tetrahydrofuran, etc., when X=N, triisopropylamine (Me2CH)3N, tert-butyldimethylamine Me3CNMe2, tritylmethyldimethylamine Ph3CNM e2, 2,3-bis(dimethylamino)-2,3-dimethylbutane Me2C(NMe2)C(NMe2)Me2, 2,3-bis(dimethylamino)butane MeCH(NMe)2)CH(NMe2)Me, tert-butyl trimethylsilyl ether Me3COSiMe3, N,N-dimethylbenzylamine, etc., and when X=O and N on a saturated carbon-separated aromatic group, benzyl methyl ether MeOCH2Ph, benzyl dimethylamine Me2NCH2Ph, etc., in which CH4 is a phenylene group; t Bu is a tertiary butyl group.

[0046] R1 (X) n Non-limiting examples of are MeCF, MeSiF, C6H5CH2F, C6H5CF31,3-C6H4(CF3)2, 1,2-( t BuO)2C6H4, 1,3-( t BuO)2C6H4, 1,4-( t BuO)2C6H4, t BuO-CH2-CH2O t Bu, or a mixture thereof, where C6H4 is a phenylene group; t Bu is a tertiary butyl group.

[0047] R 1 X n Other non-limiting examples are tertiary butyl methyl ether, tertiary butyl ethyl ether, tertiary butyl propyl ether, tertiary butyl ether, 1-tert-butoxy-2,6-di-tert-butylbenzene, 1-trimethylsiloxy-2,6-di-tert-butylbenzene, trimethylsiloxybenzene, trimethylmethoxysilane, benzyl methyl ether, benzyl ethyl ether, benzyl propyl ether, benzyl butyl ether or mixtures thereof.

[0048] R 1 X n Further non-limiting examples are propylene oxide, isobutene oxide, 1-butene oxide, styrene oxide, 4-methyl-styrene oxide, trimethylene oxide, 2,2-dimethyl-trimethylene oxide, 2,2-diphenyl-trimethylene oxide, 1-methyl-tetrahydrofuran, 1,1-dimethyl-tetrahydrofuran, 1-methyl-ethyleneimine, 1,1,2-trimethylethyleneimine, 1,1-diphenyl-2-methyl-ethyleneimine, 1-methyl-tetrahydro-pyrrole, 1,1-dimethyl-tetrahydro-pyrrole, 1,1-diphenyl-2-methyl-tetrahydro-pyrrole, 1-methyl-piperidine, 1,1-dimethyl-piperidine, 1,1-diphenyl-2-methyl-piperidine, or mixtures thereof.

[0049] R1 X n Preferred examples are CF3C6H5, isobutene oxide, and N,N-dimethylbenzylamine.

[0050] Trihydrocarbylaluminum compounds generally have the formula AlR3, where Al is aluminum and each R is independently a C1-C 20 is a hydrocarbyl group. Non-limiting examples of R include alkyl groups having from 1 to about 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, neopentyl, benzyl, substituted benzyl, and the like. Preferably, the trihydrocarbylaluminum compound does not contain a β-proton. Non-limiting examples of AlR3 useful in the present invention include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, tri-n-octylaluminum, trineopentylaluminum, tribenzylaluminum, tris(2,6-dimethylbenzyl)aluminum, or mixtures thereof, preferably trimethylaluminum (AlMe3), trineopentylaluminum (Al(CH2C(Me3) 33 ), and tribenzylaluminum (Al(CH2C6H5)3).

[0051] The trihydrocarbylaluminum compounds of the present invention can be prepared by any suitable method, including methods currently known or that may become known, such as those well known to those skilled in the art.

[0052] The supported activator composition can be prepared by combining the components in any order, but preferably the trihydrocarbylaluminum is first combined with the supported aluminoxane intermediate and then the carbocationic agent is introduced.

[0053] Preferably, the supported aluminoxane intermediate may be formed by adding to the support an aluminoxane compound formed by contacting an oxygen source with an organoaluminum compound, for example by contacting a pyrogenic silica free of physically absorbed water with methylaluminum formed by reaction of water with trimethylaluminum. The supported activator composition may then be formed by combining at least a portion of the supported aluminoxane intermediate with a trihydrocarbylaluminum compound and then with a carbocationic agent.

[0054] More preferably, the supported aluminoxane intermediate can be formed "in situ" by adding an organoaluminum compound onto a support containing an oxygen source such as water physically absorbed onto the silica. The supported activator composition of the present invention can then be formed by combining at least a portion of the supported aluminoxane intermediate with a trihydrocarbylaluminum compound and then a carbocationic agent. The oxygen source originally present on the support can be supplemented with an additional oxygen source to allow reaction with more organoaluminum compound and increase the Al loading on the supported aluminoxane intermediate. For example, a non-calcined silica with 5-6% water can be saturated with more water to reach 10-12% to increase the Al loading from about 7% to about 14%. Another example is the addition of a desired amount of water to a silica without physically absorbed water (e.g., silica calcined at 600°C) to control the desired Al loading.

[0055] An alternative route to "in situ" formation of the supported aluminoxane intermediate is to add an excess of the organoaluminum compound, when a trihydrocarbylaluminum compound is used as the organoaluminum compound, onto the oxygen source-containing support, where the excess organoaluminum compound acts as both the organoaluminum compound and the trihydrocarbylaluminum compound. The activator composition of the present invention is then formed by combining at least a portion of the intermediate composition with a carbocationic agent.

[0056] When a trihydrocarbylaluminum compound is used as the organoaluminum compound, yet another alternative route to form the supported aluminoxane intermediate is to add a high trihydrocarbylaluminum-containing aluminoxane to the support. The high trihydrocarbylaluminum-containing aluminoxane is made from a low oxygen source content that allows the desired amount of free trihydrocarbylaluminum compound to be present in the aluminoxane. At least a portion of the intermediate composition having trihydrocarbylaluminum can then be combined with a carbocationic agent to form the activator composition of the present invention.

[0057] The combination can be carried out in an inert gas atmosphere at a temperature of about -80°C to about 200°C, for example, about 0°C to about 150°C, and the combination time can be about 1 minute to about 36 hours, for example, about 10 minutes to about 24 hours. Treatment after completion of the combination operation can include filtering the supernatant, followed by washing with an inert solvent, and evaporating the solvent under reduced pressure or in an inert gas stream, although these treatments are not required. The resulting activator composition can be used for polymerization in any suitable state, including as a fluid, dry or semi-dry powder, or can be used for polymerization in a state suspended in an inert solvent. The combination of the components can be carried out at ambient temperature for a combination time of about 15 minutes to about 48 hours, about 15 minutes to about 6 hours, and the resulting mixture can be used as is or subsequently heated to a temperature of about 80°C to about 150°C.

[0058] In embodiments of the supported aluminoxane, a compound of formula R 1 (X) n The molar ratio of the carbocationic agent compound of formula R to the trihydrocarbylaluminum compound AlR is about 0.01:1 to 2:1, for example, about 0.1:1 to about 1.5:1, for example, about 0.9:1 to 1:1 to 1.1:1, for example, about 1:1, 1 (X) n The molar ratio of X to Al for the compound and the supported aluminoxane is about 0.01:1 to 0.8:1, such as about 0.03:1 to 0.5:1, for example about 0.1:1. The molar ratio of trihydrocarbylaluminum to Al for the supported aluminoxane is about 0.01:1 to 0.8:1, for example about 0.03:1 to 0.5:1, for example about 0.1:1. When generated in situ on the support by reaction of an organoaluminum compound with an oxygen source on the support, such as water absorbed or added on silica, the organoaluminum compound is divided into two parts, the trihydrocarbylaluminum component, R 1 (X) n The reaction loading can be given as the sum of one portion as a stoichiometric portion for reaction with, plus another portion as an organoaluminum compound for in situ formation of the aluminoxane on the support.

[0059] In an embodiment of the unsupported solution aluminoxane, a compound of formula R 1 (X) n The molar ratio of the carbocationic agent compound of formula R to the trihydrocarbylaluminum compound AlR is about 0.01:1 to 0.1:1, for example, about 0.05:1 to about 0.08:1, for example, about 1:1. 1 (X) n The molar ratio of X to Al for this compound is about 0.01:1 to 0.15:1, such as about 0.03:1 to 0.08:1, for example about 0.04:1. The molar ratio of trihydrocarbylaluminum to Al for the unsupported solution aluminoxane is about 0.01:1 to 0.15:1, for example about 0.03:1 to 0.08:1, for example about 0.04:1.

[0060] The amount of aluminum in the activator composition should be about 0.1 mmol or more, for example, about 1 mmol or more, per 1 g of the solid component in the dry state. The aluminum loading in the final catalyst composition is generally about 5 wt% to about 25 wt%, preferably about 15 wt% to about 20 wt%.

[0061] III. Transition Metal Component To form an ethylene copolymer, the above activator composition and transition metal component can be added to the monomer independently but substantially simultaneously to catalyze the polymerization. Alternatively, the activator composition and transition metal component may be combined to form a catalyst product, and at least a part of the product may be added to the monomer to catalyze the polymerization. The ratio of Al to the transition metal can be about 1:1 to about 1000:1, for example, about 200:1 to about 300:1.

[0062] The transition metal component can include any transition metal component having olefin polymerization ability. For example, but not limited to, the transition metal component can include one or more metallocene transition metal components.

[0063] The transition metal component can include a catalyst precursor ML a Q q-a wherein M represents a Group 4 transition metal atom of the Periodic Table (1993, IUPAC) or a lanthanide series transition metal, such as titanium, zirconium, or hafnium and lanthanide series transition metals, such as samarium, L represents a group having a cyclopentadienyl structure or a group having at least one heteroatom, at least one L is a group having a cyclopentadienyl structure, each L may be the same or different, and may be cross-linked to each other. Q represents a halide radical, an alkoxide radical, an amide radical, and a hydrocarbyl radical having 1 to about 20 carbon atoms, a represents a number satisfying the formula 0 < a ≦ q, and q represents the valence of the transition metal atom M.

[0064] L may include, for example, a cyclopentadienyl group, a substituted cyclopentadienyl group, or a polycyclic group having a cyclopentadienyl structure. Examples of the substituted cyclopentadienyl group include a hydrocarbon group having 1 to about 20 carbon atoms, a halogenated hydrocarbon group having 1 to about 20 carbon atoms, and a silyl group having 1 to about 20 carbon atoms. Examples of the silyl group according to the present invention include SiMe3. Examples of the polycyclic group having a cyclopentadienyl structure include an indenyl group and a fluorenyl group. Examples of the heteroatom of the group having at least one heteroatom include nitrogen, oxygen, phosphorus, and sulfur.

[0065] Examples of the substituted cyclopentadienyl group include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n-propylcyclopentadienyl group, an n-butylcyclopentadienyl group, an isopropylcyclopentadienyl group, an isobutylcyclopentadienyl group, a sec-butylcyclopentadienyl group, a tert-butylcyclopentadienyl group, a 1,2-dimethylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group, a 1,2,3-trimethylcyclopentadienyl group, a 1,2,4-trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.

[0066] Examples of polycyclic groups having a cyclopentadienyl group include an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group.

[0067] Examples of groups having at least one heteroatom include a methylamino group, a tert-butylamino group, a benzylamino group, a methoxy group, a tert-butoxy group, a phenoxy group, a pyrrolyl group, and a thiomethoxy group.

[0068] One or more of the groups having a cyclopentadienyl structure, or one or more of the groups having a cyclopentadienyl structure and one or more of the groups having at least one heteroatom, may be bridged with (i) an alkylene group, such as ethylene, propylene, (ii) a substituted alkylene group, such as isopropylidene, diphenylmethylene, or (iii) a silylene group or a substituted silylene group, such as a dimethylsilylene group, a diphenylsilylene group, or a methylsilylsilylene group.

[0069] Q includes a halide radical, an alkoxide radical, an amido radical, a hydrogen radical, or a hydrocarbyl radical having 1 to about 20 carbon atoms. Examples of Q include Cl, F, Br, MeO, EtO, PhO, C6F5O, BHT, Me2N, Et2N, Ph2N, (Me3Si)2N, an alkyl group having 1 to about 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a benzyl group, and a silyl group, such as Me3Si and Ph3Si.

[0070] Transition metal component ML a Q q~a(wherein M includes zirconium) examples thereof include bis(cyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(indenyl)zirconium dichloride, bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, bis(fluorenyl)zirconium dichloride, ethylene bis(indenyl)zirconium dichloride, dimethylsilylene(cyclopentadienylfluorenyl)zirconium dichloride, diphenylsilylene bis(indenyl)zirconium dichloride, cyclopentadienyl dimethylamino zirconium dichloride, cyclopentadienyl phenoxy zirconium dichloride, tert dimethyl(tert-butylamino)(tetramethylcyclopentadienyl)silane zirconium dichloride, isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)zirconium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)zirconium dichloride dimethylsilylene(cyclopentadienylfluorenyl)zirconium dichloride, bis(cyclopentadienyl)zirconium dimethyl, bis(methylcyclopentadienyl)zirconium dimethyl, bis(pentamethylcyclopentadienyl)zirconium dimethyl, bis(indenyl)zirconium dimethyl, bis(4,5,6,7-tetrahydroindenyl)zirconium dimethyl, bis(fluorenyl)zirconium dimethyl, ethylene bis(indenyl)zirconium dimethyl, dimethylsilylene(cyclopentadienylfluorenyl)zirconium dimethyl, diphenylsilylene bis Examples of such compounds include (indenyl)zirconium dimethyl, cyclopentadienyldimethylaminozirconium dimethyl, cyclopentadienylphenoxyzirconium dimethyl, dimethyl(tert-butylamino)(tetramethylcyclopentadienyl)silane zirconium dimethyl, isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)zirconium dimethyl, and dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)zirconium dimethyl.

[0071] Further exemplary transition metal components ML a Q q~a Examples of such zirconium components include those in which the zirconium in the above zirconium components is replaced with titanium or hafnium.

[0072] Further exemplary transition metal components ML a Q q~a includes moieties where Q can be the same or different within a molecule.

[0073] Other catalyst precursors useful in the present invention are rac-dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium dimethyl (M1), rac-dimethylsilylbis(2-methyl-4-phenyl-indenyl)zirconium dichloride, rac-dimethylsilylbis(2-methyl-1-indenyl)zirconium dimethyl, rac-dimethylsilylbis(2-methyl-4,5-benzoindenyl)zirconium dimethyl, rac-ethylenebis(tetrahydroindenyl)zirconium dimethyl, rac-ethylenebis-(tetrahydroindenyl)zirconium dichloride, and rac-ethylenebis(indenyl)zirconium dimethyl, bis(1-butyl-3-methylcyclopentadienyl)zirconium dimethyl, bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride. Bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride is preferred.

[0074] The polymerization method is not limited, and either liquid phase polymerization or gas phase polymerization can be used. Examples of the solvent used in the liquid phase polymerization include aliphatic hydrocarbons such as butane, isobutane, pentane, heptane, octane, etc., aromatic hydrocarbons such as benzene, toluene, etc., and halogenated hydrocarbons such as methylene chloride. It is also possible to use at least a part of the olefin to be polymerized as a solvent. The polymerization can be carried out in a batch, semi-batch or continuous manner, and the polymerization may be carried out in two or more stages with different reaction conditions. The polymerization temperature can be about -50°C to about 200°C, for example, 0°C to about 100°C. The polymerization pressure can be atmospheric pressure to about 100 kg / cm. 2 For example, atmospheric pressure to about 50 kg / cm 2 The suitable polymerization time can be determined by means known to those skilled in the art according to the desired olefin polymer and the reaction apparatus, and is typically within the range of about 1 minute to about 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the olefin polymer obtained during polymerization. Preferably, the polyethylene copolymer is formed using only one catalyst species including a metallocene component and one of the above activator compositions. In addition, the copolymer is preferably formed in a single reactor. The ability to form a copolymer with a broad short chain branching distribution using only one catalyst species and in only one reactor is a significant advantage over previous attempts to form polymers with a broad short chain branching distribution.

[0075] 3) Film The present disclosure also relates to films formed from polyethylene copolymers. The films have a desirable blend of properties due to the molecular structure of the copolymers. For example, films formed from polyethylene copolymers generally exhibit improved hot seal initiation temperature, hot tack initiation temperature, Elmendorf tear strength, and dart impact strength. They also exhibit good tensile strength, elongation at break, and low haze. The films can be formed from the copolymers alone or in combination with other polymers. For example, in one embodiment, the films are formed from compositions containing the polyethylene copolymers described herein and low density polyethylene. The polyethylene copolymers described herein generally constitute at least about 50% of the film, such as at least about 70% of the film, such as at least about 85% of the film.

[0076] The term "film" refers to a sheet, laminate, web, or the like, or combinations thereof, having a length dimension and a width dimension, having two major surfaces, and having a thickness between the major surfaces. The film can be a monolayer film (having only one layer) or a multilayer film (having two or more layers). In one embodiment, the film is a monolayer film having a thickness of about 12 μm to about 250 μm, e.g., about 20 μm to about 50 μm.

[0077] The term "multilayer film" is a film having two or more layers. The layers of the multilayer film are bonded together by one or more of the following non-limiting processes: coextrusion, extrusion coating, vapor deposition coating, solvent coating, emulsion coating, suspension coating, or adhesive lamination. In one embodiment, the multilayer film has a thickness of about 12 μm to about 250 μm, for example, about 20 μm to about 50 μm.

[0078] The film may be an extruded film. Extrusion is a process for forming a continuous shape by forcing a molten plastic material through a die, optionally followed by cooling or chemical hardening. Just prior to extrusion through the die, a relatively highly viscous polymeric material is fed into a rotating screw, which forces it through the die. The extruder may be a single screw extruder, a multi-screw extruder, a disk extruder, or a ram extruder. The die may be a film die, a blown film die, or a sheet die.

[0079] The film may be a coextruded film. The terms "coextrusion" and "coextruding" refer to a process for extruding two or more materials through a single die having two or more orifices disposed therein, such that the extrudates coalesce or are otherwise fused together into a layered structure. Coextrusion can be used as an embodiment of other processes, such as in film blowing, casting film, and extrusion coating processes.

[0080] The film can be a blown film. The terms "blown film" or "film blowing" are a process for making films in which a polymer or copolymer is extruded to form bubbles filled with air or another gas in order to orient the polymer film. The bubbles are then collapsed and collected into a flat film.

[0081] Films formed from the copolymers described herein generally exhibit a dart impact strength of from about 800 gf to about 1500 gf, e.g., from about 900 gf to about 1300 gf, e.g., from about 1100 gf to about 1200 gf, as determined according to ASTM D1709 at a thickness of 1.6 mils (40.6 μm).

[0082] In addition, films formed from the copolymers described herein typically exhibit a longitudinal Elmendorf tear strength, determined according to ASTM D1922 at a thickness of 1.6 mils (40.6 μm), of about 450 to about 700, e.g., about 500 to about 600, e.g., about 525 to about 575. Films formed from the copolymers described herein typically exhibit a transverse Elmendorf tear strength, determined according to ASTM D1922 at a thickness of 1.6 mils (40.6 μm), of about 600 to about 800, e.g., about 650 to about 700.

[0083] Films formed from the copolymers described herein also exhibit good optical properties. For example, the films generally have a gloss value of about 40 to about 60, e.g., about 45 to about 55, as determined according to ASTM D2457 at a thickness of 1.6 mils (40.6 μm) and at a 45° angle. In addition, films formed from the copolymers described herein generally have a haze value of about 5% to about 15%, e.g., about 8% to about 13%, e.g., about 10% to about 12%, as determined according to ASTM D1003 at a thickness of 1.6 mils (40.6 μm).

[0084] The invention having thus been generally described will be more readily understood with reference to the following examples, which are provided by way of illustration and are not intended to limit the invention. EXAMPLES

[0085] Test Method Crystallization elution fractionation Samples were prepared by dissolving approximately 15 mg of sample in ODBC (o-dichlorobenzene) at 160° C. for 1 hour.

[0086] [Table 1]

[0087] Sequential self-nucleating annealing Approximately 5 mg of PE sample is first heated up to 200°C to remove all thermal history, followed by a series of cooling / heating cycles. The temperature for the cooling cycle is always set at 20°C, while the set temperature for the heating cycle is varied from 128°C to 73°C at 5°C intervals, for a total of 12 self-nucleation and annealing steps. After cooling to 73°C, the sample is heated up to 170°C, and the final melting curve is used for SSA data analysis. The heating / cooling rate is 10°C / min for all cycles. For comparison with CEF, the SSA curve is temperature corrected by subtracting 32°C, and the corrected curve is defined as m-SSA.

[0088] All manipulations were carried out under an inert atmosphere of dry nitrogen using drybox or Schlenk line techniques. Solvents were dried / stored over molecular sieves.

[0089] Catalytic activity Catalyst activity is determined by the amount of polymer produced divided by the amount of catalyst added, normalized to 60 minutes.

[0090] Density was determined according to ASTM D1505.

[0091] Melt index was determined under 2.16 kg and 190° C. according to ASTM D1238.

[0092] Dart drop impact strength was measured according to ASTM D1709.

[0093] Haze was measured according to ASTM D1003.

[0094] Gloss was measured at a 45° angle according to ASTM D2457.

[0095] Elmendorf tear resistance was measured according to ASTM D1922.

[0096] Example 1 - Preparation of Compounds The supported activator compositions were prepared as described in U.S. Patents 8,354,485 and 9,090,720. The activator was then mixed with bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride metallocene in a hydrocarbon solvent for several hours. The resulting mixture was filtered. The recovered solid was washed with fresh hydrocarbon solvent and dried under vacuum. The Zr loading in the final catalyst was 0.35-1.0 wt.% and the residual solvent content was less than 3 wt.%. The Al content in the final catalyst was 15-20 wt.%.

[0097] Example 2 - Polymerization (Autoclave) A clean and purged (inert gas) jacketed autoclave reactor is then charged with the specified amounts of isobutane, hexene, hydrogen, scavengers, and antistatic agents under inert conditions. The reactor pressure and temperature are monitored. The autoclave is heated to the specified temperature and stirred at about 800 RPM using a marine impeller. Once the desired temperature is reached (usually about 5 minutes), the desired amount of ethylene pressure is added. Once the ethylene pressure approaches the desired set point, the desired amount of catalyst prepared by the method of Example 1 is added. Once the catalyst is added, the polymerization time is started. The ethylene pressure (feed) is maintained constant throughout the duration of the polymerization test via a mass flow controller. Once the polymerization time is over, the volatile contents are flushed and the autoclave temperature / pressure is reduced to atmospheric conditions (usually about 5 minutes). The autoclave is then opened. The polymer formed is recovered and dried under vacuum at about 70-80°C to constant weight. After the polymer is removed, the autoclave is cleaned of residual polymer, closed, and subjected to an automatic heating / inert gas purge sequence to prepare the reactor for the next polymerization test.

[0098] Example 3 - Polymerization (gas phase - bench scale) A 5 L Xytel reactor equipped with suitable software capable of controlling the reactor is heated to above 100°C and purged multiple times with dry N2. The reactor is charged with dry NaCl (typically 500-1000 grams) and continuously purged with dry N2 for 15-20 minutes while stirring above 100°C. The pressure is maintained at about 50 psi during the purging. The reactor is cooled to about 80-85°C. Silica-MAO solids (8 grams) are added via a charge bomb using N2 pressure. The reactor is pressurized with 40-50 psi N2 pressure and the reactor is stirred for 25-30 minutes. The pressure is slowly reduced to about 3 psi. The desired gas combination of N2, H2, and ethylene is added and the valves allowing hexene flow are opened so that the pressure is close to the desired set point of 225 psi for the polymerization. The hexene / ethylene and H2 / ethylene ratios are monitored by online GC analysis. H2, ethylene, and hexene are fed on demand to target the desired ratio required for a particular polymerization run. The desired amount of catalyst prepared in the manner of Example 1 is loaded into a charge bomb along with silica-MAO solids (2 grams) and injected into the reactor with stirring. Once the internal temperature has stabilized and reached the desired set point, the reaction is carried out for 1 hour. At the end of the polymerization, the reactor is cooled, vented to about 20°C, and thoroughly purged with low N2 flow to remove residual hydrocarbons. The reactor contents are isolated in air and salts are removed by a water washing / filtration process. The polymer is dried to constant weight and further analyzed as necessary.

[0099] Example 4 - Polymerization (gas phase - continuous) Hexene-ethylene copolymer was produced in a continuous flow gas phase polymerization reactor in the presence of hydrogen. The desired resin target was a polymer with a melt index of about 1.0 g / 10 min and a density of about 0.918 g / cc. The reactor temperature was maintained in the range of about 75-85° C. Catalyst, prepared as described in Example 1, was continuously fed to the reactor to maintain the desired polymer production rate. Product was continuously removed to maintain the desired fluidized bed height. The characteristics of the resulting polymer are shown in Table 1, which also lists the same characteristics for Exceed 1018, an ethylene 1-hexene copolymer commercially available from ExxonMobil. Additionally, the CEF profile of the resulting polymer is shown in FIG. 1, with the cumulative CEF and m-SSA profiles overlaid in FIG. 2.

[0100] [Table 2]

[0101] Example 5 - Film Formation Blown films were produced under the following process conditions: a.3 inch die and 100 mil die gap b.Dual lip air ring c. 1.5 inch extruder with straight compression screw d. LDPE was blended at 10% using a gravimetric blender. e. Film samples were run at 35 lbs / hr with the same heat profile for the extruder and die. f. The line speed was varied to obtain two different thicknesses: 1 mil and 1.6 mil. g. All samples were run with 12 inch LF and 9 inch FLH tube targets, air ring temperatures and blower speeds were comparable throughout the runs.

[0102] Films were made under the above conditions using the polymer produced in Example 4 and Exceed 1018. Table 2 lists the properties of the resulting films.

[0103] [Table 3]

[0104] While particular embodiments have been illustrated and described, it is to be understood that changes and modifications can be made in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the appended claims.

[0105] The embodiments illustratively described herein may be suitably practiced in the absence of any element or elements, limitations or limitations not specifically disclosed herein. Thus, for example, terms such as "comprising", "including", "containing" and the like should be read expansively and without limitation. In addition, the terms and expressions used herein are used as terms of description and not of limitation, and in the use of such terms and expressions, there is no intention to exclude any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. In addition, the phrase "consisting essentially of" will be understood to include those elements specifically recited, as well as those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of" excludes any elements not specified.

[0106] The present disclosure is not limited with respect to the specific embodiments described in this application. As will be apparent to those skilled in the art, many modifications and variations can be made without departing from the spirit and scope thereof. In addition to those enumerated herein, functionally equivalent methods and compositions within the scope of the present disclosure will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that the disclosure is not limited to particular methods, reagents, compounds, compositions, or biological systems, which may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0107] Additionally, when features or aspects of the disclosure are described in terms of a Markush group, one of skill in the art will recognize that the disclosure is also thereby described in terms of any individual members or subgroups of members of the Markush group.

[0108] As will be understood by those skilled in the art, for all and all purposes, especially in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations thereof. Any recited range can be readily recognized as fully describing and allowing the same range to be subdivided into at least two, three, four, five, ten, etc. As a non-limiting example, each range discussed herein can be readily subdivided into a lower third, a middle third, an upper third, etc. Also, as will be understood by those skilled in the art, all terms such as "up to," "at least," "greater than," "less than," etc. refer to a range that includes the recited number and can then be subdivided into subranges as discussed above. Finally, as will be understood by those skilled in the art, a range includes each individual member.

[0109] All publications, patent applications, issued patents, and other documents referenced herein are incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions contained in the descriptions incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

[0110] Other embodiments are within the scope of the following claims.

Claims

1. 1. A polyethylene comprising ethylene units and α-olefin comonomer units, said polyethylene having the following characteristics: A melt index of 0.1 to 15 g / 10 min as determined by ASTM D1238 at 190° C. under 2.16 kg; a density of 0.905 to 0.930 g / cc as determined by ASTM D1505; A molecular weight distribution (Mw / Mn) of 1.5 to 2.7; Formula: ΔT[℃]≧-909 ＊ Crystallization elution fractionation temperature range excluding the first 10% and last 1% of the polymer on a temperature scale according to density [g / cc] + 863; Formula: F%≧510 ＊ (density [g / cc]-0.905), where F% is the percentage of lamellar thickness greater than 12 nm.

2. 2. The polyethylene of claim 1, having a cumulative fraction difference (S-C) between the corrected SSA and the CEF at 70° C. of less than 15%.

3. The polyethylene of claim 1, wherein the polyethylene has a density of 0.905 to 0.925 g / cc.

4. 2. The polyethylene of claim 1, wherein the polyethylene has a melt index of 0.5 to 5 g / 10 min as determined by ASTM D1238 at 2.16 kg and 190° C.

5. The polyethylene of claim 1, wherein the α-olefin comonomer comprises hexene.

6. 2. The polyethylene of claim 1, wherein the percentage of lamellar thickness greater than 12 nm (F%) is greater than 10%.

7. 2. The polyethylene of claim 1, wherein the polyethylene has a density of 0.910 to 0.920 g / cc.

8. A film comprising the polyethylene of claim 1.

9. 2. A pellet comprising the polyethylene of claim 1, wherein the pellet contains Zr in an amount less than 0.50 ppm.

10. 10. The pellet of claim 9, wherein the pellet contains Zr in an amount of 0.1 ppm to 0.4 ppm.

11. 1. A polyethylene comprising ethylene units and α-olefin comonomer units, said polyethylene having the following characteristics: A melt index of 0.1 to 15 g / 10 min as determined by ASTM D1238 at 190° C. under 2.16 kg; a density of 0.905 to 0.935 g / cc as determined by ASTM D1505; A molecular weight distribution (Mw / Mn) of 1.5 to 2.7; Formula: CEF ΔT [℃] ≧ -909 ＊ (density [g / cc]) + crystallization elution fractionation temperature range excluding the first 10% and last 1% of the polymer on a temperature scale according to 863; Formula: F%≧510 ＊ (density [g / cc]-0.905), where F% is the percentage of lamellar thickness greater than 12 nm; The polyethylene is an intermediate composition derived from at least a carrier, an organoaluminum compound, and an oxygen source; (A) R ２ ２ AlY (wherein each R ２ independently comprise a hydrocarbyl group having 1 to 20 carbons, and Y comprises a halide radical, a pseudohalide radical, an alkoxide radical, an aryloxide radical, an alkyl substituted amido radical, an aryl substituted amido radical, a siloxy radical, a boronoxy radical, a diarylboronoxy radical, or a halogenated diarylboronoxy radical; or (B) a combination of (i) and (ii), wherein (i) is a group of formula R １ (X) ｎ wherein R １ is a hydrocarbyl group having 1 to 20 carbon atoms, n is from 1 to the number of possible substitutions of said hydrocarbyl group, and each X is R １ Optionally substituted on the above, independently halogen, —OSi(R ３ ) ３ , -N(Si(R ３ ) ３ ) ２ , -N(R ３ ) ２ , -SR ３ , -P(R ３ ) ２ , -CN, or -OR ４ (In the formula, each R ３ are independently hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, and each R ４ is independently a hydrocarbyl having 1 to 20 carbon atoms, and at least one R ３ When R is a hydrocarbyl group, １ and R ３ Or R １ and R ４ are optionally linked together to form a cyclic group, with the proviso that at least one X is not directly attached to an aryl group, and with the proviso that when X is not a halogen, X is a secondary or tertiary carbon, or -CH ２ -aryl group, and (ii) is a group of formula AlR ３ wherein each R is independently C １ ~C ２０ a trihydrocarbylaluminum compound having a cyclic alkyl group, and a transition metal component.

12. The polyethylene of claim 11 , wherein the transition metal component comprises a metallocene component.

13. The polyethylene of claim 12, wherein the metallocene component comprises bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride.

14. 12. The polyethylene of claim 11, having a cumulative fraction difference (SC) between M-SSA and CEF at 70° C. of less than 15%.

15. The polyethylene of claim 11, wherein the polyethylene has a density of 0.905 to 0.925 g / cc.

16. The polyethylene of claim 11, wherein the polyethylene has a melt index of 0.5 to 5 g / 10 min as determined by ASTM D1238 under 2.16 kg and 190° C.

17. The polyethylene of claim 11, wherein the α-olefin comonomer comprises hexene.

18. 12. The polyethylene of claim 11, wherein the percentage (F%) of lamellar thickness greater than 12 nm is greater than 10%.

19. The polyethylene of claim 11, wherein the polyethylene has a density of 0.910 to 0.920 g / cc.

20. A film comprising the polyethylene of claim 11.

21. 12. A pellet comprising the polyethylene of claim 11, wherein the pellet contains Zr in an amount less than 0.50 ppm.

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