olefin polymerization process to produce an ethylene copolymer, ethylene copolymer and ethylene copo

专利摘要:
ETHYLENE COPOLYMERS, FILM AND POLYMERIZATION PROCESS. Ethylene copolymers having a relatively high melt flow rate and a multimodal profile in a temperature rise elution fractionation (TREF) batch are disclosed. Copolymers can be made into film having good dart impact values and good stiffness properties under decreased extrusion pressures.
公开号:BR112014031920B1
申请号:R112014031920-0
申请日:2013-05-24
公开日:2021-04-20
发明作者:Victoria Ker；Patrick Lam；Yan Jiang；Peter Phung Minh Hoang；Charles Ashton Garret Carter；Darryl J. Morrison
申请人:Nova Chemicals (International) S.A；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention is directed to the preparation of polyethylene copolymers, the films made from them, as well as a polyethylene polymerization process. A phosphinimine type catalyst is used to make ethylene copolymers having a relatively high melt flow ratio (I21/I2) and a multimodal TREF profile. Ethylene copolymers have a width distribution index of the CDBI50 composition between 35% by weight and 70% by weight and can be made into film with good physical properties while exhibiting improved processability. FUNDAMENTALS OF THE TECHNIQUE
[002] The demand for polyethylene products having an improved balance of physical properties and processability has led to the development of products having improved output capability and increasingly improved end-use properties, such as tear or dart impact properties of the film improved. Particularly useful is the development of polymer architectures so that polymer blending strategies can be avoided to improve polymer properties as they increase the cost of these strategies.
[003] US Patent Application No. 2011/0003099 discusses linear polyethylene of low melt flow rate (MFR) and linear polyethylene of high melt flow rate (MFR), which are distinguished by an I21/I2 less than 30 and an I21/I2 greater than 30, respectively.
[004] Resins having both a narrow molecular weight distribution and a low melt flow rate are well known and include resins produced with metallocene catalysts and phosphinimine catalysts. Such resins include, for example, Exceed 1018ATM from ExxonMobil and those described in Pat. No. 5,420,220 and US Pat. Canadian No. 2,734,167. These resins can be made into films having a good balance of physical and optical properties, but can be difficult to process in the absence of processing aids, as indicated, for example, by relatively low production capacity on a film production line. blow molded.
[005] Resins having a higher melt flow rate are more attractive to film manufacturers because they are generally easier to process. Pat. U.S. Nos. 6,255,426 and 6,476,171 and U.S. Patent Application No. 2011/0003099 each describe the production and use of resins having melt flow ratios that are in excess of 30 and that have moderately broad molecular weight distributions. Resins are thought to contain long chain branching. The polymers disclosed in U.S. Pat. U.S. Nos. 6,255,426 and 6,476,171 are made with a bridged bis-indenyl zirconocene catalyst and have a composition width distribution index (CDBI) greater than 75%. The resins have been referred to as EnableTM polymers (ExxonMobil) in the patent literature (see, for example, Example Polymers disclosed in US Patent Application No. 2011/0003099), and although the resins are relatively easy to process, they also have a good balance of strength and stiffness properties when blow molded to film. For example, the films had physical properties that were comparable to Exceed 1018A materials despite their better pseudoplastic behavior. The polymers disclosed in US Patent Application No. 2011/0003099 include a novel "Enable" type resin having a low melt index (I2 = 0.3), a relatively high melt flow rate (I21/I2 is 46 to 58) and a moderately broad molecular weight distribution (eg Mw/Mn is 3.4). Polymers also have a single peak in a TREF profile, with a T(75)-T(25) less than 4 °C.
[006]The manipulation of the comonomer distribution profile also provided new ethylene copolymer architectures in an effort to improve the balance between physical properties and polymer processability.
[007] It is generally the case that metallocene catalysts and other so-called "single-site catalysts" typically incorporate comonomer more uniformly than traditional Ziegler-Natta catalysts when used for the copolymerization of catalytic ethylene with alpha olefins. This fact is often demonstrated by measuring the composition width distribution index (CDBI) for corresponding ethylene copolymers. The definition of the composition distribution width index (CDBI50) can be found in PCT publication WO 93/03093 and in U.S. Pat. U.S. No. 5,206,075. The CDBI50 is conveniently determined using techniques that isolated polymer fractions based on their solubility (and hence their comonomer content). For example, fractionation by increasing temperature elution (TREF) as described by Wild et al. J. Poly. Sci., Poly. Phys. Ed. Vol. 20, page 441, 1982 can be used. From the weight fraction versus composition distribution curve, the CDBI50 is determined by establishing the percentage by weight of a copolymer sample that has a comonomer content within 50% of the average comonomer content on each side of the median. Generally, Ziegler-Natta catalysts produce ethylene copolymers with a CDBI50 lower than that of a single-site catalyst at a similar density compatible with a heterogeneously branched copolymer. Typically, a plurality of prominent peaks is observed for such polymers in a TREF (Temperature Elution Fractionation) analysis. Such peaks are compatible with the presence of heterogeneously branched material which generally includes a highly branched fraction, a medium branched fraction and a higher density fraction having little or no short chain branching. In contrast, metallocenes and other single-site catalysts will most often produce ethylene copolymers having a CDBI50 higher than that of a Ziegler-Natta catalyst of similar density and which often contain a single prominent peak in a TREF analysis, compatible with a homogeneously branched copolymer.
[008] Despite the above, methods have been developed to access polyethylene copolymer compositions having an expanded comonomer distribution (ie, more Ziegler-Natta type) while otherwise maintaining typical product characteristics of metallocene resin and single site catalyst such as high dart impact strength for blow molded film. Such resins can be made, for example, using a mixture of metallocene catalysts in a single reactor, using a plurality of polymerization reactors under different polymerization conditions, or by blending the metallocene-produced ethylene copolymers.
[009] U.S. Patent Nos. 5,382,630, 5,382,631 and WO 93/03093 describe polyethylene copolymer blend compositions having broad or narrow molecular weight distributions, and broad or narrow comonomer distributions. For example, a mixture may have a narrow molecular weight distribution while simultaneously having a bimodal composition distribution. Alternatively, a mixture can have a broad molecular weight distribution while simultaneously having a unimodal composition distribution. Blends are made by melt blending two polyethylene resins with similar or different molecular weights and similar or different comonomer contents, where each resin is formed using a metallocene catalyst in a gas phase reactor.
[010] No. 7,018,710 discloses mixtures comprising a high molecular weight component having a high comonomer content and a low molecular weight component having a low comonomer content. The ethylene copolymer blend, which arises from the use of a metallocene catalyst in a double-cascade reactor process where each reactor is operated under different conditions (eg, a suspension-cascade-gas-phase reactor) , shows two distinct maxima in a TREF fratogram. The polymers were applied as a sealing layer on a thermo-adhesive film.
[011] A mixed catalyst system containing a "poor comonomer incorporater" and a "good comonomer incorporater" is disclosed in U.S. Pat. U.S. Nos. 6,828,394 and 7,141,632. The catalyst incorporating the defective comonomer can be a metallocene having at least one fused-ring cyclopentadienyl binder, such as an indenyl binder, with appropriate substitution (e.g., 1-alkyl substitution). The catalyst incorporating the good comonomer was selected from an order of well-known metallocenes and was generally less sterically hindered to the front end of the molecule than the poor comonomer incorporating. These mixed catalyst systems produced polyethylene copolymers having a bimodal TREF distribution, in which two elution peaks are well separated from each other, compatible with the presence of higher and lower density components. The mixed catalysts also produced ethylene copolymer having an expanded molecular weight distribution relative to ethylene copolymer made with one of the single metallocene component catalysts.
[012] A mixed catalyst system comprising three distinct metallocene catalysts is disclosed in U.S. Pat. U.S. No. 6,384,158. Ethylene copolymers having broad molecular weight distributions were obtained using these catalyst systems to polymerize ethylene with an alpha olefin, such as 1-hexene.
[013] The Application of Pat. No. 2011/0212315 describes a linear ethylene copolymer having a bimodal or multimodal comonomer distribution profile as measured using DSC, TREF or CRYSTAF techniques. The copolymers maintain high dart impact strength when blow molded to film and are relatively easy to process as indicated by a reduced pseudoplasty index, relative to ethylene copolymers having a unimodal comonomer distribution profile. The exemplified ethylene copolymer compositions, which have a melt flow rate less than 30, are made in a single gas phase reactor using a mixed catalyst system comprising a metallocene catalyst and a late transition metal catalyst.
[014] US No. 7,534,847 demonstrates that the use of a chromium-based transition metal catalyst provides an ethylene copolymer having a bimodal comonomer distribution (as indicated by CRYSTAF) with a CDBI of less than 50% by weight (see, Table 1 of US Pat. No. 7,534,847). The patent teaches that copolymers can have a molecular weight distribution of 1 to 8, significant amounts of vinyl group unsaturation, long chain branching and specific amounts of methyl groups as measured by fractionation of CRYSTAF.
[015] U.S. Patent No. 6,932,592 describes very low density (i.e., < 0.916 g/cc) ethylene copolymers produced with a bulky unbridged bis-Cp metallocene catalyst. A preferred metallocene is bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride. The examples show that in the gas phase, sustained versions of this catalyst produce a copolymer of ethylene and 1-hexene that has a CDBI between 60 and 70% and a bimodal comonomer distribution as measured by temperature-increasing elution fractionation (TREF).
[016] U.S. No. 6,420,507 describes a low density ethylene copolymer having a narrow molecular weight distribution (i.e. 1.5 to 3.0) and a bimodal TREF profile. Polymerization is carried out in the gas phase using a so-called "constrained geometry" catalyst having an indenyl binder.
[017] US Patent Nos. 6,248,845, 6,528,597, 7,381,783 and US Patent Application No. 2008/0108768 disclose that a bulky metallocene binder based on hafnium and a small amount of zirconium can be used to provide a copolymer of ethylene/1-hexene which has a bimodal TREF profile. It is taught that the hafnium chloride precursor compounds used to synthesize bulk metallocene catalysts are contaminated with a small amount of zirconium chloride or that zirconium chloride can be deliberately added. The amounts of zirconium chloride present range from 0.1 mol% to 5 mol%. Consequently, the final hafnocene catalysts contain small amounts (ie, 0.1 to 5 mol%) of their zirconocene analogues. Since zirconium-based catalysts may have superior activity relative to their hafnium analogues, it is possible that the products made make a significant contribution from the zirconocene species. If this is the case then it is perhaps not surprising that a bimodal TREF profile works. The patent provides data for blow molded and cast film application that show that compared to Exceed type resins, polymers are more easily extruded, with lower engine load, higher throughput and reduced head pressure. The given resins cast the film with high tear values and the blow molded film with high javelin impact values.
[018] US Patent Nos. 6,956,088, 6,936,675, 7,179,876 and 7,172,816 disclose that the use of a "substantially unique" bulk hafnium catalyst binder provides an ethylene copolymer composition having a CDBI below 55 %, especially below 45% as determined by CRYSTAF. Keeping in mind that hafnocene-derived hafnocene catalysts are expected to have zirconocene contaminants present in low amounts. U.S. Patent Nos. 6,936,675 and 7,179,876 further teach that the CDBI can be altered under different temperature conditions when using hafnocene catalysts. Polymerization at lower temperatures provided ethylene copolymer having a broader composition width distribution index (CDBI) than polymers obtained at higher temperatures. For example, the use of bis(n-propylcyclopentadienyl)hafnium dichloride or bis(n-propylcyclopentadienyl)hafnium difluoride catalysts in a gas phase reactor for the copolymerization of ethylene and 1-hexene at < 80 °C has provided copolymers having a CDBI between 20 and 35%, compared to CDBI values between 40 and 50% for copolymers obtained at 85°C. Disclosed polymers can, under certain down-suction ratios, provide films having a machine direction tear value greater than 500 g/mil, a dart impact strength greater than 500 g/mil, as well as good stiffness . Polymers also have good processability.
[019] No. 5,281,679 describes bis-cyclopentadienyl metallocene catalysts which have secondary or tertiary carbon substituents on a cyclopentadienyl ring. Catalysts provide expanded molecular weight polyethylene materials during gas phase polymerization.
[020] Cyclic bridged bulky binder metallocene catalysts are described in U.S. Pat. U.S. Nos. 6,339,134 and 6,388,115 which provide easier processing ethylene polymers.
[021] A haphnocene catalyst is used in U.S. Pat. No. 7,875,690 to provide an ethylene copolymer in a gas phase fluidized bed reactor. The copolymer has a so-called “wide orthogonal composition distribution” which imparts improved physical properties and low extractables. A broad orthogonal composition distribution is one, in which the comonomer is predominantly incorporated into the high molecular weight chains. The copolymers had a density of at least 0.927 g/cc. Polyethylene copolymers having a similarly broad orthogonal composition distribution but a lower density are disclosed in U.S. Pat. U.S. No. 8,084,560 and U.S. Patent Application No. 2011/0040041A1. Again, a hafnocene catalyst is used in a gas phase reactor to supply the ethylene copolymer.
[022] U.S. No. 5,525,689 also discloses the use of a hafnium-based metallocene catalyst for use in olefin polymerization. The polymers had an I10/I2 ratio of 8 to 50, a density of 0.85 to 0.92 g/cc, a Mw/Mn of up to 4.0, and were made in the gas phase.
[023] No. 8,114,946 discloses ethylene copolymers that have a molecular weight distribution (Mw/Mn) ranging from 3.36 to 4.29, an inverted comonomer incorporation, and contain low levels of long chain branching. Melt flow ratios of the disclosed polymers are generally below about 30. A bridged metallocene cyclopentadienyl/fluorenyl catalyst having an unsaturated pendant group is used to make the ethylene copolymers. The patent application does not mention films or film properties.
[024] U.S. No. 6,469,103 discusses ethylene copolymer compositions comprising a first and second ethylene copolymer component. The individual components are defined using ATREF-DV analytical methods that show a bimodal or multimodal structure with respect to comonomer location. The compositions have an I10/I2 value greater than 6.6 and a relatively narrow molecular weight distribution (i.e. MW/Mn is less than or equal to 3.3) compatible with the presence of long chain branching . Polymers are manufactured using a dual solution reactor system with mixed catalysts.
[025] A process for making ethylene polymer compositions which involves the use of at least two polymerization reactors is described in U.S. Pat. U.S. No. 6,319,989. Ethylene copolymers have a molecular weight distribution greater than 4.0 and show two peaks when subjected to fractionation by crystallization analysis (CRYSTAF).
[026] US No. 6,462,161 describes the use of a constrained geometry type catalyst or a bridged bis-Cp metallocene catalyst to produce, in a single reactor, a polyolefin composition having long chain branching and a maximum molecular weight occurring in the portion of the composition having the highest comonomer content (ie, an inverted comonomer distribution). Compositions made with a constrained geometry catalyst have multimodal TREF profiles and relatively narrow molecular weight distributions (eg exemplified resins have a Mw/Mn of 2.19 to 3.4, see Table 1 in the section on examples of US Pat. No. 6,462,161). Compositions made with a bridged bis-Cp metallocene catalyst have complex TREF profiles and somewhat broader molecular weight distribution (eg resins exemplified have a Mw/Mn of 3.43 or 6.0, see Table 1 in the examples section of US Pat. No. 6,462,161).
[027] Ethylene copolymers are taught in U.S. Pat. US No. 7.968,659 which have a melt index of 1.0 to 2.5, a Mw/Mn of 3.5 to 4.5, an elastic fusion modulus G' (G"=500 Pa) of 40 to 150 Pa and a flux activation energy (Ea) in the range of 28 to 45 kJ/mol Constrained geometry catalysts are used to make the polymer compositions in the gas phase.
[028] US No. 7,521,518 describes the use of a constrained geometry catalyst to provide an ethylene copolymer composition having an inverted comonomer distribution as determined by various cross-fractionation chromatography (CFC) parameters and a molecular weight distribution of 2 to 10.
[029] No. 5,874,513 discloses that the use of a mixture of components giving rise to a sustained metallocene catalyst can, in a gas phase reactor, provide an ethylene copolymer with reduced comonomer distribution homogeneity. The patent defines a Cb composition distribution parameter that is representative of the comonomer distribution within the polymer composition. TREF analysis of the copolymer composition showed a bimodal distribution.
[030] No. 6,441,116 discloses a film comprising an ethylene copolymer with a TREF-obtained composition distribution curve having four distinct areas including a peak defining area that is assigned to a highly branched component.
[031] An ethylene/alpha olefin copolymer produced with a Ziegler-Natta catalyst and having greater than about 17 percent by weight of a high density fraction, as determined by analytical TREF methods, and a weight distribution molecular (Mw/Mn) less than about 3.6 is disclosed in U.S. Pat. U.S. No. 5,487,938. The high density fraction has short chain branching, while the balance of the copolymer composition is referred to as the fraction containing short chain branching. Consequently, the data are compatible with a bimodal distribution of comonomer incorporation in the ethylene copolymer.
[032] U.S. No. 6,642,340 describes an ethylene copolymer having a specific relationship between a melt flow rate and melt stress. The polymers still comprise between 0.5 and 8% by weight of a component eluting at no lower than 100°C in a TREF analysis.
[033] Use of phosphinimine catalysts for gas phase olefin polymerization is the subject matter of U.S. Patent No. 5,965,677. The phosphinimine catalyst is an organometallic compound having a phosphinimine binder, a cyclopentadienyl type binder and two activatable binders, and which is supported on a suitable particulate support, such as silica. The exemplified catalysts had the formula CpTi(N=P(tBu)3)X2 where X was Cl, Me or Cl and -O-(2,6-iPr-C6H3).
[034] In the Application of Pat. Co-pending CA No. 2,734,167 showed that suitably substituted phosphinimine catalysts provided narrow molecular weight distribution copolymers which when made into film showed a good balance of optical and physical properties.
[035] Polymers and films made in the gas phase using various single-site catalysts, including so-called "phosphinimine" catalysts, were disclosed in Advances in Polyolefins II, Napa, California - October 24 to 27, 1999 ("Development" of NOVA's Single Site Catalyst Technology for use in the Gas Phase Process” - I. Coulter; D. Jeremic; A. Kazakov; I. McKay).
[036] In a disclosure made at the 2002 Canadian Society for Chemistry Conference ("Cyclopentadienyl Phosphinimine Titanium Catalysts - Structure, Activity and Product Relationships in Heterogeneous Olefin Polymerization." RP Spence; I. McKay; C. Carter; L. Koch; D. Jeremic; J. Muir; A. Kazakov. NOVA Research and Technology Center, CIC, 2002), it was shown that phosphinimine catalysts carrying the variously substituted cyclopentadienyl and indenyl ligands were active for the gas phase polymerization of ethylene when in sustained form.
[037] U.S. Patent Application No. 2008/0045406 discloses a sustained phosphinimine catalyst comprising an indenyl ligand substituted by C6F5. The catalyst was activated with an ionic activator having an active proton for use in the polymerization of ethylene with 1-hexene.
[038] U.S. Patent Application No. 2006/0122054 discloses the use of a dual catalyst formulation, one component of which is a phosphinimine catalyst having an n-butyl substituted indenyl ligand. The patent is directed to the formation of bimodal resins suitable for application in tubes. DISCLOSURE OF THE INVENTION
[039]We now report that a polymerization catalyst system comprising a single phosphinimine catalyst can provide an ethylene copolymer having a multimodal comonomer distribution profile and median molecular weight distribution when used in a single reactor. The invention alleviates the need for polymer blends, mixed catalysts, or reactor technologies in forming polyethylene resin that is easy to process and has a good balance of physical properties.
[040] An olefin polymerization process for producing an ethylene copolymer is provided, the process comprising contacting ethylene and at least one alpha olefin having from 3 to 8 carbon atoms with a polymerization catalyst system in a single reactor; ethylene copolymer having a density of 0.916 g/cc to 0.930 g/cc, a melt index (I2) of 0.1 to 1.0 g/10 min, a melt flow rate (I21/I2) of 32 to 50, a molecular weight distribution (Mw/Mn) of 3.6 to 6.5, a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, and a distribution width index of composition CDBI50 from 35 to 70% by weight as determined by TREF; wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, a catalyst activator, and a catalyst modifier; and, wherein the only transition metal catalyst is a group 4 phosphinimine catalyst.
[041] An ethylene copolymer having a density of 0.916 g/cc to 0.930 g/cc, a melt index (I2) of 0.1 to 1.0 g/10 min, a melt flow rate is provided (I21/I2) from 32 to 50, a molecular weight distribution (Mw/Mn) of 3.6 to 6.5, a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, and a CDBI50 composition width distribution index of 35 to 70% by weight as determined by TREF; wherein the ethylene copolymer is made by a process to polymerize ethylene and an alpha olefin having 3 to 8 carbon atoms in a single reactor in the presence of a polymerization catalyst system comprising a single transition metal catalyst, a support, and a catalyst activator; and, wherein the only transition metal catalyst is a group 4 phosphinimine catalyst.
[042] An ethylene copolymer having a density of 0.916 g/cc to 0.930 g/cc, a melt index (I2) of 0.2 to 0.85 g/10 min, a melt flow rate is provided (I21/I2) from 36 to 50, a molecular weight distribution (Mw/Mn) of 4.0 to 6.0, a Z-average molecular weight distribution (Mz/Mw) of 2.0 to 4.0 , a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile defined by three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high) where the T( low) occurs at 62 °C at 82 °C, T(medium) occurs at 76 °C at 89 °C, but is higher than T(low), and T(high) occurs at 90 °C at 100°C, and a composition width distribution index CDBI50 of 35 to 70% by weight as determined by TREF; wherein the ethylene copolymer is made by a process to polymerize ethylene and an alpha olefin having 3 to 8 carbon atoms in a single gas phase reactor in the presence of a polymerization catalyst system comprising a single transition metal catalyst, a support, and a catalyst activator; and, wherein the only transition metal catalyst is a Group 4 organotransition metal catalyst.
[043] A non-blend ethylene copolymer is provided, having a density of 0.916 g/cc to 0.930 g/cc, a melt index (I2) of 0.2 to 0.85 g/10 min, a melt flow ratio (I21/I2) of 36 to 50, a molecular weight distribution (Mw/Mn) of 4.0 to 6.0, a Z-average molecular weight distribution (Mz/Mw) of 2 .0 to 4.0, a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile defined by three intensity peaks occurring at elution temperatures T(low), T(medium) and T( high) where T(low) occurs at 62°C to 82°C, T(medium) occurs at 76°C to 89°C, but higher than T(low), and T(high) occurs at 90°C C to 100°C, and a composition width distribution index CDBI50 of 35 to 70% by weight as determined by TREF.
[044] A film is provided having a per dart impact greater than 500 g/mil, a 1% MD secant modulus greater than 150 MPa, a 1% TD secant modulus greater than 175 MPa, and a MD to TD tear ratio of 0.75 or less; wherein the film comprises an ethylene copolymer having a density of 0.916 g/cc to 0.930 g/cc, a melt index (I2) of 0.1 to 1.0 g/10 min, a melt flow rate ( I21/I2) from 32 to 50, a molecular weight distribution (Mw/Mn) of 3.6 to 6.5, a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF, and an index of distribution width of composition CDBI50 from 35 to 70% by weight as determined by TREF; and, wherein the ethylene copolymer is made by a process to polymerize ethylene and an alpha olefin having 3 to 8 carbon atoms in a single reactor in the presence of a polymerization catalyst system comprising a single transition metal catalyst, a support, a catalyst activator and a catalyst modifier; and, wherein the only transition metal catalyst is a group 4 phosphinimine catalyst.
[045] A film is provided having an impact per dart greater than 500 g/mil, a MD secant modulus 1% greater than 150 MPa, a TD secant modulus 1% greater than 175 MPa, and a MD to TD tear ratio of 0.75 or less; wherein the film comprises an ethylene copolymer which is not a blend, having a density of 0.916 g/cc to 0.930 g/cc, a melt index (I2) of 0.2 to 0.85 g/10 min, a melt flow ratio (I21/I2) of 36 to 50, a molecular weight distribution (Mw/Mn) of 4.0 to 6.0, a Z-average molecular weight distribution (Mz/Mw) of 2, 0 to 4.0, a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile defined by three intensity peaks occurring at elution temperatures T(low), T(medium) and T(high ) where T(low) occurs at 62 °C to 82 °C, T(medium) occurs at 76 °C to 89 °C, but higher than T(low), and T(high) occurs at 90 °C at 100°C, and a CDBI50 composition width distribution index of 45 to 69% by weight as determined by TREF.
[046] An olefin polymerization process is provided to produce an ethylene copolymer, the process comprising contacting ethylene and at least one alpha olefin having 3 to 8 carbon atoms with a polymerization catalyst system in a single reactor. gas phase to provide an ethylene copolymer having a density of 0.916 g/cc to 0.930 g/cc, a melt index (I2) of 0.2 to 0.85 g/10 min, a melt flow rate (I21 /I2) from 36 to 50, a molecular weight distribution (Mw/Mn) of 4.0 to 6.0, a Z-average molecular weight distribution (Mz/Mw) of 2.0 to 4.0, a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile defined by three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high) where the T(low) occurs at 62 °C to 82 °C, T(medium) occurs at 76 °C to 89 °C, but higher than T(low), and T(high) occurs at 90 °C to 100 °C, and a composition distribution width index tion CDBI50 from 35 to 70% as determined by TREF; wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, and a catalyst activator; and, wherein the only transition metal catalyst is a Group 4 organotransition metal catalyst.
[047] An ethylene copolymer having a density of 0.916 g/cc to 0.930 g/cc, a melt index (I2) of 0.1 to 1.0 g/10 min, a melt flow rate is provided (I21/I2) from 32 to 50, a molecular weight distribution (Mw/Mn) of 3.6 to 6.5, a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, and a distribution width index of the composition CDBI50 of 35 to 70% by weight as determined by TREF, and which satisfies the following relationships: (i) δXO ≤[80 - 1.22 (CDBl50)/(Mw/Mn)]; and (ii) (Mw/Mn) > 68 [(I21/I2)-1 + 10 - 6 (Mn)]; wherein the ethylene copolymer is made by a process to polymerize ethylene and an alpha olefin having 3 to 8 carbon atoms in a single gas phase reactor in the presence of a polymerization catalyst system comprising a single transition metal catalyst, a support, and a catalyst activator and, wherein the only transition metal catalyst is a group 4 organotransition metal catalyst.
[048] In an embodiment of the invention, the ethylene copolymer satisfies the following relationship: δXO ≤96 - 2.14 [(MFR0’5) + 1 x 10 - 4 (Mw - Mn)].
[049] In an embodiment of the invention, the ethylene copolymer has a CDBl50 of 45 to 69% by weight. BRIEF DESCRIPTION OF THE DRAWINGS
[050] Figure 1 shows an analysis of fractionation by elution with increased temperature (TREF) and profile of an ethylene copolymer made according to the present invention.
[051] Figure 2 shows a gel permeation chromatography (GPC) with refractive index detection of an ethylene copolymer made according to the present invention.
[052] Figure 3 shows a gel permeation chromatography with infrared Fourier transform detection (GPC-FTIR) obtained for an ethylene copolymer made according to the present invention. Comonomer content, shown as the number of short chain branches per 1000 carbons (y-axis), is given relative to the copolymer molecular weight (x-axis). The upward sloping line (left to right) is the short-chain branch (in short-chain branches per 1000 carbon atoms) determined by FTIR. As can be seen in the Figure, the number of short chain branches increases at higher molecular weights and, consequently, comonomer incorporation is said to be “reverse”.
[053] Figure 4A shows graphical representation of phase angle vs complex modulus and phase angle vs complex viscosity for comparative ethylene copolymer resins in 1 and 2 as determined by dynamic mechanical analysis (DMA).
[054] Figure 4B shows a graphical representation of the phase angle vs complex modulus and phase angle vs complex viscosity for inventive ethylene copolymer no. 1 and for comparative ethylene copolymer no. 3 and 6, as determined by DMA.
[055]Figure 5 shows a graphical representation of the equation: δXO = 96 - 2.14 [(MFR0’5) + 1 x 10 - 4 (Mw - Mn)]. The value obtained from equation 96 - 2.14 [(MFR0.5) + 1 x 10 - 4 (Mw - Mn)] (the x-axis) is plotted against the corresponding van Gurp-Palmen crossover phase angle , δXO (the y axis) for inventive resin Nos 1 to 5 and comparative resin Nos 1 to 3 and 5 to 7.
[056]Figure 6 shows a graphical representation of the equation: Mw/Mn = 68 [(I21/I2)-1 + 10 - 6 (Mn)]. The values from equation 68 [(I21/I2)-1 + 10 - 6 (Mn)] (the y-axis) are plotted against the corresponding Mw/Mn values (the x-axis) for resins 1 to 8, thus as for various commercially available resins which have a melt index of 1.5 or less and a density between 0.916 and 0.930 g/cm3.
[057]Figure 7 shows a graphical representation of the equation: δXO = [80 - 1.22 (CDBl50/(Mw/Mn)]. The values of the equation [80 - 1.22 (CDBl50/(Mw/Mn)] (the x-axis) are plotted against the corresponding crossover phase angle (δXO) values (the y-axis) for resins 1 through 8, as well as for various commercially available resins that have a melt index of 1.5 or less and a density between 0.916 and 0.930 g/cm3. BEST WAY TO CARRY OUT THE INVENTION
[058] The present invention provides ethylene copolymers having a relatively high melt flow rate and a multimodal profile in a temperature rise elution fractionation (TREF) batch. Copolymers can be made into film having high dart impact values and good stiffness properties under lower extrusion pressures and at good output rates. Polymerization Catalyst System
[059] The polymerization catalyst system used in the present invention will comprise a single transition metal catalyst, but may further comprise components such as, but not limited to, a support(s), catalyst activator(s), and catalyst modifier(s). The term "single transition metal catalyst" and similar terms mean that during preparation of the polymerization catalyst system, only one type of active transition metal catalyst is included, and excludes polymerization catalyst systems comprising two or plus different active transition metal catalysts, such as mixed catalysts and dual catalysts.
[060] Preferably, the transition metal catalyst is an organometallic catalyst based on a group 4 transition metal. By organometallic catalyst, it is meant that the catalyst will have at least one ligand within the transition metal coordination sphere. which is bonded to the metal via at least one carbon-metal bond. Such catalysts may collectively be called "organotransition metal catalysts" or "group 4 organotransition metal catalysts" when based on a group 4 metal.
[061] Preferably, the organotransition metal catalyst is a single site catalyst based on a group 4 metal (where the number refers to the columns in the Periodic Table of the Elements using the IUPAC nomenclature). These include titanium, hafnium and zirconium. The most preferred organotransition metal catalysts are Group 4 metal complexes in their highest oxidation state.
[062] A particular organotransition metal catalyst that is especially useful in the present invention is a group 4 organotransition metal catalyst, further comprising a phosphinimine binder. Any organometallic/compound/complex catalyst having a phosphinimine binder and which can be used to make the copolymer compositions further defined and described below (in the section entitled "The ethylene copolymer composition") is considered for use in the present invention . In the present invention, organotransition metal catalysts having at least one phosphinimine binder and which are active in polymerizing olefins to polymers are termed "phosphinimine catalysts".
[063] Transition metal catalysts usually require activation by one or more species of cocatalytic activator or catalyst in order to provide polymer. Consequently, transition metal polymerization catalysts are sometimes called "precatalysts".
[064] In a preferred embodiment of the invention, the phosphinimine catalyst is defined by the formula: L(PI)MX2 where M is a group 4 transition metal selected from Ti, Hf, Zr; PI is a phosphinimine linker; L is a substituted or unsubstituted cyclopentadienyl type linker; and X is an activatable ligand.
[065] In a preferred embodiment of the invention, the phosphinimine catalyst will have a phosphinimine ligand that is not bridged to, or does not bridge to, another ligand within the metal coordination sphere of the phosphinimine catalyst, such as, for example, a linker of the cyclopentadienyl type.
[066] In a preferred embodiment of the invention, the phosphinimine catalyst will have a cyclopentadienyl type ligand that is not bridged to, or does not bridge to, another ligand within the metal coordination sphere of the phosphinimine catalyst , such as, for example, a phosphinimine linker.
[067]The phosphinimine ligand is defined by the formula: R13P=N- wherein each R1 is independently selected from the group consisting of a hydrogen atom; a halogen atom; a C1-20 hydrocarbyl radical which is unsubstituted or further substituted by one or more halogen atom; a C1-20 alkyl radical; a C1-8 alkoxy radical; a C6-10 aryl or aryloxy radical; an amido radical; a silyl radical; and a germanyl radical; P is phosphorus and N is nitrogen (which binds to metal M).
[068] In an embodiment of the invention, the phosphinimine linker is chosen so that each R1 is a hydrocarbyl radical. In a particular embodiment of the invention, the phosphinimine linker is tri-(tertiary-butyl)phosphinimine (i.e. where each R1 is a tertiary butyl group or t-Bu group for abbreviated).
[069] As used herein, the term "cyclopentadienyl-type" binder is intended to include binders that contain at least one five carbon rings that are bonded to the metal via an eta-5 (or in some cases eta-3) bond . Thus, the term "of the cyclopentadienyl type" includes, for example, unsubstituted cyclopentadienyl, mono- or poly-substituted cyclopentadienyl, unsubstituted indenyl, mono- or poly-substituted indenyl, unsubstituted fluorenyl and mono- or poly-substituted fluorenyl. Hydrogenated versions of indenyl and fluorenyl binders are also considered for use in the present invention, provided that the five carbon rings, which bind to the metal via an eta-5 (or in some cases eta-3) bond, remain intact. An exemplary list of substituents for a cyclopentadienyl linker, an indenyl linker (or hydrogenated version thereof) and a fluorenyl linker (or hydrogenated version thereof) includes the group consisting of a C1-20 hydrocarbyl radical (which hydrocarbyl radical may be unsubstituted or further substituted, for example, by a halide and/or a hydrocarbyl group, for example a suitable substituted C1-20 hydrocarbyl radical is a pentafluorobenzyl group such as -CH2C6F5); a halogen atom; a C1-8 alkoxy radical; a C6-10 aryl or aryloxy radical (each of which may be further substituted, for example, by a halide and/or a hydrocarbyl group); an amido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals; a phosphide radical which is unsubstituted or substituted by up to two C1-6 alkyl radicals; a silyl radical of the formula -Si(R')3 wherein each R' is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals; and a germanyl radical of the formula -Ge(R')3 where R' is as defined directly above.
[070] The term "perfluorinated aryl group" means that each hydrogen atom bonded to a carbon atom in an aryl group has been replaced with a fluorine atom as is well understood in the art (eg a perfluorinated phenyl group or substituent has the formula -C6F5).
[071] In one embodiment of the invention, the phosphinimine catalyst will have a mono- or poly-substituted indenyl linker and a phosphinimine linker that is substituted by three tertiary butyl substituents.
[072]Unless otherwise stated, the term "indenyl" (or "Ind" for short) connotes a fully aromatic bicyclic ring structure.
[073] An indenyl linker (or abbreviated "Ind") as defined in the present invention will have carbon atoms in the structure with the numbering scheme given below, so that the location of a substituent can be easily identified.

[074] In one embodiment of the invention, the phosphinimine catalyst will have a mono-substituted indenyl linker and a phosphinimine linker that is replaced by three tertiary butyl substituents.
[075] In one embodiment of the invention, the phosphinimine catalyst will have a mono- or poly-substituted indenyl linker where the substituent is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted aryl group or an unsubstituted one, and a substituted or unsubstituted benzyl group (eg, C6H5CH2-). Suitable substituents for the alkyl, aryl or benzyl group can be selected from the group consisting of alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylaryl groups (for example a benzyl group), arylalkyl groups and halide groups.
[076] In one embodiment of the invention, the phosphinimine catalyst will have a mono-substituted indenyl ligand, R2-Indenyl, where the R2 substituent is a substituted or unsubstituted alkyl group, a substituted aryl group or an unsubstituted one, or a substituted or unsubstituted benzyl group. Suitable substituents for an alkyl R2 group, aryl R2 or benzyl R2 can be selected from the group consisting of alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylaryl groups (for example, a benzyl group), arylalkyl groups and halide groups.
[077] In one embodiment of the invention, the phosphinimine catalyst will have an indenyl linker having at least one 1-position substituent (1-R2) where the R2 substituent is a substituted or unsubstituted alkyl group, a substituted aryl group or an unsubstituted, or a substituted or unsubstituted benzyl group. Suitable substituents for an alkyl R2 group, aryl R2 or benzyl R2 can be selected from the group consisting of alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylaryl groups (for example, a benzyl group), arylalkyl groups and halide groups.
[078] In one embodiment of the invention, the phosphinimine catalyst will have a mono-substituted indenyl linker, 1-R2-Indenyl where the R 2 substituent is in the 1-position of the indenyl linker and is a substituted or unsubstituted alkyl group , a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group. Suitable substituents for an alkyl R2 group, aryl R2 or benzyl R2 can be selected from the group consisting of alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylaryl groups (for example, a benzyl group), arylalkyl groups and halide groups.
[079] In one embodiment of the invention, the phosphinimine catalyst will have a mono-substituted indenyl ligand, 1-R2-Indenyl, where the R2 substituent is an alkyl group substituted (partially/completely) by halide, a benzyl group substituted (partially/completely) by halide, or an aryl group substituted (partially/completely) by halide.
[080] In one embodiment of the invention, the phosphinimine catalyst will have a mono-substituted indenyl linker, 1-R2-Indenyl, where the R2 substituent is a benzyl group substituted (partially/completely) by halide.
[081] When present in an indenyl ligand, a benzyl group may be partially or completely replaced by halide atoms, preferably fluoride atoms. The aryl group of the benzyl group may be a perfluorinated aryl group, a 2,6-fluoro-substituted phenyl group (i.e., ortho), 2,4,6-fluoro-substituted phenyl group (i.e., ortho/para) or a group fluoro substituted phenyl 2,3,5,6 (i.e., ortho/meta), respectively. The benzyl group is, in one embodiment of the invention, located at position 1 of the indenyl ligand.
[082] In one embodiment of the invention, the phosphinimine catalyst will have a mono-substituted indenyl linker, 1-R2-Indenyl, where the R2 substituent is a pentafluorobenzyl group (C6F5CH2-).
[083] In one embodiment of the invention, the phosphinimine catalyst has the formula: (1-R2-(Ind))M(N=P(t-Bu)3)X2 where R2 is a substituted or unsubstituted alkyl group substituted, a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group, wherein the substituents for the alkyl, aryl or benzyl group are selected from the group consisting of alkyl, aryl, alkoxy, aryloxy substituents , alkylaryl, arylalkyl and halide; M is Ti, Zr or Hf; and X is an activatable ligand.
[084] In an embodiment of the invention, the phosphinimine catalyst has the formula: (1-R2-(Ind))M(N=P(t-Bu)3)X2 where R2 is an alkyl group, a group aryl or a benzyl group and, wherein each of the alkyl group, the aryl group, and the benzyl group can be unsubstituted or substituted by at least one fluoride atom; M is Ti, Zr or Hf; and X is an activatable ligand.
[085] In an embodiment of the invention, the phosphinimine catalyst has the formula: (1-R2-(Ind))M(N=P(t-Bu)3)X2 where R2 is an alkyl group, a group aryl or a benzyl group and, wherein each of the alkyl group, the aryl group, and the benzyl group may be unsubstituted or substituted by at least one halide atom; M is Ti, Zr or Hf; and X is an activatable ligand.
[086] In an embodiment of the invention, the phosphinimine catalyst has the formula: (1-R2-(Ind))Ti(N=P(t-Bu)3)X2 where R2 is an alkyl group, a group aryl or a benzyl group and, wherein each of the alkyl group, the aryl group, and the benzyl group can be unsubstituted or substituted by at least one fluoride atom; and X is an activatable ligand.
[087] In an embodiment of the invention, the phosphinimine catalyst has the formula: (1-C6F5CH2-Ind)M(N=P(t-Bu)3)X2, where M is Ti, Zr or Hf; and X is an activatable ligand.
[088] In an embodiment of the invention, the phosphinimine catalyst has the formula: (1-C6F5CH2-Ind)Ti(N=P(t-Bu)3)X2, where X is an activatable ligand.
[089]Although not preferred, other organotransition metal catalysts that may also be considered for use in the present invention include metallocene catalysts (which have two cyclopentadienyl type ligands), and constrained geometry catalysts (which have a ligand of the starch type and a cyclopentadienyl type binder). Some non-limiting examples of metallocene catalysts, which may or may not be useful, can be found in U.S. Pat. U.S. No. 4,808,561; 4,701,432; 4,937,301; 5,324,800; 5,633,394; 4,935,397; 6,002,033 and 6,489,413, which are incorporated herein by reference. Some non-limiting examples of constrained geometry catalysts, which may or may not be useful, can be found in U.S. Pat. U.S. No. 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5,703,187 and 6,034,021, all of which are incorporated herein by reference in their entirety.
[090] In the present invention, the term "activatable" means that the ligand X can be cleaved from the center of the metal M through a protonolysis reaction or separated from the center of the metal M by acidic catalyst activating compounds or suitable electrophilic (also known as "co-catalyst" compounds) respectively, examples of which are described below. The activatable linker X can also be transformed into another linker that is cleaved or separated from the center of the metal M (for example, a halide can be converted to an alkyl group). Without wishing to be bound by any single theory, protonolysis or separation reactions generate an active “cationic” metal center that can polymerize the olefins.
[091] In embodiments of the present invention, the activatable ligand, X is independently selected from the group consisting of a hydrogen atom; a halogen atom, a C1-10 hydrocarbyl radical; a C1-10 alkoxy radical; and a C6-10 aryl or aryloxy radical, wherein each of the hydrocarbyl, alkoxy, aryl, or aryl oxide radicals may be unsubstituted or further substituted by one or more halogen or other group; a C1-8 alkyl radical; a C1-8 alkoxy, a C6-10 aryl or aryloxy; a starch or a phosphide, but where X is not a cyclopentadienyl. Two linkers X can also be joined together to form, for example, a substituted or unsubstituted diene linker (i.e., 1,3-butadiene); or a delocalized heteroatom containing group, such as an acetate or acetamidinate group. In a convenient embodiment of the invention, each X is independently selected from the group consisting of a halide atom, a C1-4 alkyl radical and a benzyl radical.
[092] Particularly suitable activatable ligands are monoanionics such as a halide (eg chloride) or a hydrocarbyl (eg methyl, benzyl).
[093] The catalyst activator (or simply the abbreviated "activator") used to activate the transition metal polymerization catalyst can be any suitable activator including one or more activators selected from the group consisting of alkylaluminoxanes and ionic activators, optionally together with an alkylating agent.
[094] Without wishing to be bound by theory, alkylaluminoxanes are thought to be complex aluminum compounds of the formula: R32Al1O(R3Al1O)mAl1R32, wherein each R3 is independently selected from the group consisting of C1-20 hydrocarbyl radicals and is 3 to 50. Optionally, a hindered phenol can be added to the alkylaluminoxane to provide an Al1:hindered phenol molar ratio of 2:1 to 5:1 when the hindered phenol is present.
[095] In one embodiment of the invention, R3 of the alkylaluminoxane is a methyl radical and m is from 10 to 40.
[096] Alkylaluminoxanes are typically used in substantial molar excess compared to the amount of group 4 transition metal in the organometallic compound/complex. The Al1:group 4 transition metal molar ratios can be from about 10:1 to about 10,000:1, preferably from about 30:1 to about 500:1.
[097] In one embodiment of the invention, the catalyst activator is methylaluminoxane (MAO).
[098] In one embodiment of the invention, the catalyst activator is modified methylaluminoxane (MMAO).
[099] It is well known in the art that alkylaluminoxane can serve two functions as both an alkylator and an activator. Consequently, an alkylaluminoxane activator is often used in combination with activatable binders such as halogens.
[0100] Alternatively, the catalyst activator of the present invention may be a combination of an alkylating agent (which can also serve as a decontaminant) with an activator capable of ionizing the group 4 of the transition metal catalyst (i.e., a ionic activator). In this context, the activator can be chosen from one or more alkylaluminoxane and/or an ionic activator, whereas an alkylaluminoxane can serve as both an activator and an alkylating agent.
[0101] When present, the alkylating agent may be selected from the group consisting of (R4)p MgX22-p wherein X2 is a halide and each R4 is independently selected from the group consisting of C1-alkyl radicals 10 ep is 1 or 2; R4Li wherein in R4 is as defined above, (R4)qZnX22-q wherein R4 is as defined above, X2 is halogen and q is 1 or 2; (R4)s Al2X23-s wherein R4 is as defined above, X2 is halogen and s is an integer from 1 to 3. Preferably, in the above compounds R4 is a C1-4 alkyl radical, and X2 is chlorine. Commercially available compounds include triethyl aluminum (TEAL), diethyl aluminum chloride (DEAC), dibutyl magnesium ((Bu)2Mg), and butyl ethyl magnesium (BuEtMg or BuMgEt).
[0102]The ionic activator can be selected from the group consisting of: (i) compounds of the formula [R5]+ [B(R6)4]- where B is a boron atom, R5 is a C5 aromatic cation -7 cyclic or a triphenyl methyl cation and each R6 is independently selected from the group consisting of phenyl radicals which are unsubstituted or substituted with 3 to 5 substituents selected from the group consisting of a fluorine atom, a radical C1-4 alkyl or alkoxy which is unsubstituted or substituted by a fluorine atom; and a silyl radical of the formula --Si-- (R7)3; wherein each R7 is independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical; and (ii) compounds of the formula [(R8)t ZH]+ [B(R6)4]- wherein B is a boron atom, H is a hydrogen atom, Z is a nitrogen atom or phosphorus atom, t is 2 or 3 and R8 is selected from the group consisting of C1-8 alkyl radicals, a phenyl radical that is unsubstituted or substituted by up to three C1-4 alkyl radicals, or an R8 taken together with the nitrogen atom can form an aninium radical and R6 is as defined above; and (iii) compounds of the formula B(R6)3 wherein R6 is as defined above. Alkylaluminoxanes can also be used as alkylating agents.
[0103] In the above compounds, preferably, R6 is a pentafluorophenyl radical, and R5 is a triphenylmethyl cation, Z is a nitrogen atom and R8 is a C1-4 alkyl radical or R8 taken together with the nitrogen atom form an aninium radical which is substituted by two C1-4 alkyl radicals.
[0104]Examples of compounds capable of ionizing the transition metal catalyst include the following compounds: triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron , trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tetra(m,m-dimethylphenyl)boron of tributylammonium, tetra(p-trifluoromethylphenyl)boron of tributylammonium, tetra(pentafluorophenyl)boron of tributylammonium, tetra(o-tolyl)boron of tri(n-butyl)ammonium, tetra(phenyl)boron of N,N-dimethylanilinium, tetra N,N-diethylanilinium (phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron, N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron, dihydrogen tetra(pentafluorophenyl)boron - (isopropyl)ammonium, dicyclohexylammonium tetra(phenyl)boron, triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropil io tetracispentafluorophenyl borate, triphenylmethyl tetracispentafluorophenyl borate, benzene (diazonium) tetracispentafluorophenyl borate, tropylium phenyltris-pentafluorophenyl borate, triphenylmethyl phenyl-trispentafluorophenyl borate, benzene (diazonium) phenyltrispentafluorophenyl borate, tropylium tetramethyl-triphenyl(2,3,) tetracis (2,3,5,6-tetrafluorophenyl) borate, benzene (diazonium) tetracis (3,4,5-trifluorophenyl) borate, tropylium tetracis (3,4,5-trifluorophenyl) borate, benzene (diazonium) tetracis (3 ,4,5-trifluorophenyl) borate, tropylium tetracis (1,2,2-trifluoroethenyl) borate, trophenylmethyl tetracis (1,2,2-trifluoroethenyl) borate, benzene (diazonium) tetracis (1,2,2-trifluoroethenyl) borate , tropylium tetracis (2,3,4,5-tetrafluorophenyl) borate, triphenylmethyl tetracis (2,3,4,5-tetrafluorophenyl) borate, and benzene (diazonium) tetracis (2,3,4,5-tetrafluorophenyl) borate.
[0105]Commercially available activators that are capable of ionizing the transition metal catalyst include: N,N-dimethylaniliniumtetracispentafluorophenyl borate ("[Me2NHPh][B(C6F5)4]"); triphenylmethyl tetracispentafluorophenyl borate ("[Ph3C][B(C6F5) 4]"); and tripentafluorophenyl boron.
[0106] In one embodiment of the invention, the ionic activator compounds can be used in amounts that provide a molar ratio of Group 4 transition metal to boron that will be from 1:1 to 1:6.
[0107]Optionally, mixtures of alkylaluminoxanes and ionic activators can be used as activators for the organometallic complex.
[0108] In the present invention, the polymerization catalyst system will preferably comprise an inert support (note: the terms "support" and "inert support" are used interchangeably in the present invention). In a particular embodiment of the invention, the polymerization catalyst system comprises a phosphinimine catalyst which is supported on an inert support. The inert support used in the present invention can be any support known in the art suitable for use with polymerization catalysts. For example, the support can be any porous or non-porous support material, such as talc, inorganic oxides, inorganic chlorides, aluminophosphates (i.e., AlPO4), and polymer supports (e.g., polystyrene, etc.). Accordingly, supports include Group 2, 3, 4, 5, 13 and 14 metal oxides generally such as silica, alumina, silica-alumina, magnesium oxide, magnesium chloride, zirconia, titania, clay (e.g. , montmorillonite) and mixtures thereof.
[0109] Agglomerated supports such as silica and clay agglomerates can also be used as a support in the present invention.
[0110]Supports are generally used in calcined form. An inorganic oxide support, for example, will contain acidic surface hydroxyl groups which will react with a polymerization catalyst. Before use, the inorganic oxide can be dehydrated to remove water and to reduce the concentration of surface hydroxyl groups. Calcination or dehydration of a support is well known in the art. In one embodiment of the invention, the support is calcined at temperatures above 200°C, or above 300°C, or above 400°C, or above 500°C. In other embodiments, the support is calcined at about 500°C to about 1000°C, or from about 600°C to about 900°C. The resulting support may be free of adsorbed water and may have a surface hydroxyl content of about 0.1 to 5 mmols/g of support, or 0.5 to 3 mmols/g. The amount of hydroxyl groups on a silica support can be determined according to the method disclosed by J.B. Peri and A.L. Hensley Jr., in J. Phys. Chem., 72(8), 1968, page 2926.
[0111] The support material, especially an inorganic oxide, typically has a surface area of about 10 to about 700 m2/g, a pore volume in the range of about 0.1 to about 4.0 cc/g and an average particle size of about 5 to about 500 µm. In a more specific embodiment, the support material has a surface area of about 50 to about 500 m 2 /g, a pore volume in the range of about 0.5 to about 3.5 cc/g and an average particle size of about 10 to about 200 µm. In another more specific embodiment, the support material has a surface area of about 100 to about 400 m 2 /g, a pore volume in the range of about 0.8 to about 3.0 cc/ g and an average particle size of about 5 to about 100 µm.
[0112] The support material, especially an inorganic oxide, typically has an average pore size (i.e., pore diameter) of about 10 to about 1000 Angstroms(A). In a more specific embodiment, the carrier material has an average pore size of from about 50 to about 500A. In another more specific embodiment, the carrier material has an average pore size of from about 75 to about 350A.
[0113] The surface area and pore volume of a support can be determined by nitrogen adsorption according to BET techniques, which are well known in the art and are described in Journal of the American Chemical Society, 1938, v 60, pages 309 to 319.
[0114] A silica support that is suitable for use in the present invention has a high surface area and is amorphous. By way of example only, useful silicas are commercially available under the trademark Sylopol® 958, 955 and 2408 by Davison Catalysts, a Division of W.R. Grace and Company and ES-70W by Ineos Silica.
[0115] Agglomerated supports comprising a mineral clay and an inorganic oxide, can be prepared using a number of techniques well known in the art including pelletizing, extrusion, drying or precipitation, spray drying, molding into granules in a rotating coating drum, and the like. A nodulation technique can also be used. Methods for making agglomerated supports comprising a mineral clay and an inorganic oxide include spray drying a suspension of a mineral clay and an inorganic oxide. Methods for making agglomerated supports comprising a mineral clay and an inorganic oxide are disclosed in U.S. Patent Nos. 6,686,306; 6,399,535; 6,734,131; 6,559,090 and 6,958,375.
[0116] An inorganic oxide clay agglomerate which is useful in the present invention may have the following properties: a surface area of from about 20 to about 800 m2/g, preferably from 50 to about 600 m2/g; particles having a bulk density of from about 0.15 to about 1 g/ml, preferably from about 0.20 to about 0.75 g/ml; an average pore diameter of from about 30 to about 300 Angstroms (A), preferably from about 60 to about 150 A; a total pore volume of from about 0.10 to about 2.0 cc/g, preferably from about 0.5 to about 1.8 cc/g; and an average particle size of from about 4 to 250 microns (µm), preferably from about 8 to 100 microns.
[0117] Alternatively, a support, for example a silica support, can be treated with one or more salts of the type: Zr(SO4)2-4H2O, ZrO(NO3)2, and Fe(NO3)3 as taught in Co-pending Canadian Patent Application No. 2,716,772. Supports that have been otherwise chemically treated are also contemplated for use with the catalysts and processes of the present invention.
[0118] The present invention is not limited to any particular procedure for supporting a transition metal catalyst or catalyst system components. Processes for depositing such catalysts (eg, a phosphinimine catalyst) as well as a catalyst activator on a support are well known in the art (for some non-limiting examples of catalyst support methods, see "Supported Catalysts" by James H. Clark and Duncan J. Macquarrie, published online November 15, 2002 in Kirk-Othmer Encyclopedia of Chemical Technology Copyright© 2001 by John Wiley & Sons, Inc.; for some non-limiting methods supporting an organotransition metal catalyst, see US Patent No. 5,965,677). For example, a transition metal catalyst (eg, a phosphinimine catalyst) can be added to a support by co-precipitation with the support material. The activator can be added to the support before and/or after the transition metal catalyst or together with the transition metal catalyst. Optionally, the activator can be added to a sustained in situ transition metal catalyst or a transition metal catalyst can be added to the in situ support or a transition metal catalyst can be added to a sustained in situ activator. A transition metal catalyst can be slurried or dissolved in a suitable diluent or solvent and then added to the support. Suitable solvents or diluents include, but are not limited to, hydrocarbons and mineral oil. A transition metal catalyst, for example, can be added to the solid support, in the form of a solid, solution or suspension, followed by addition of the activator in solid form or as a solution or suspension. The transition metal catalyst (eg, phosphinimine catalyst), catalyst activator, and support can be mixed together in the presence or absence of a solvent. Polymerization Process
[0119] The copolymer compositions of the present invention are preferably manufactured using a single reactor, preferably a single gas phase reactor or suspension phase. The use of a polymerization catalyst system comprising a single transition metal catalyst in a single gas phase reactor is especially preferred.
[0120]Detailed descriptions of suspension polymerization processes are widely reported in the patent literature. For example, polymerization in particle form, or a suspension process where the temperature is kept below the temperature at which the polymer is in solution is described in U.S. Patent No. 3,248,179. Other suspension processes include those using a closed loop reactor and those using a plurality of reactors stirred in series, parallel, or combinations thereof. Non-limiting examples of suspension processes include continuous closed loop or stirred tank processes. Other examples of suspension processes are described in U.S. Patent No. 4,613,484.
[0121]Suspension processes are conducted in the presence of a hydrocarbon diluent, such as an alkane (including isoalkanes), an aromatic or a cycloalkane. The diluent can also be the alpha olefin comonomer used in copolymerizations. Alkane diluents include propane, butanes, (i.e., butane and/or normal isobutane), pentanes, hexanes, heptanes and octanes. Monomers can be soluble in (or miscible with) the diluent, but the polymer is not (under polymerization conditions). The polymerization temperature is preferably from about 5°C to about 200°C, most preferably less than about 120°C typically from about 10°C to 100°C. The reaction temperature is selected so that the ethylene copolymer is produced as solid particles. Reaction pressure is influenced by choice of diluent and reaction temperature. For example, pressures can range from 15 to 45 atmospheres (about 220 to 660 psi or about 1500 to about 4600 kPa) when isobutane is used as a diluent (see, for example, US Patent No. 4,325,849) to approximately twice as much (ie, from 30 to 90 atmospheres - about 440 to 1300 psi or about 3000 - 9100 kPa) when propane is used (see, US Patent No. 5,684,097). The pressure in a suspension process must be kept high enough to keep at least some of the ethylene monomer in the liquid phase. The reaction typically takes place in a closed-loop jacketed reactor having an internal stirrer (eg an impeller) and at least one settling leg. Catalyst, monomers and diluents are fed into the reactor as liquids or suspensions. The suspension circulates through the reactor and the jacket is used to control the reactor temperature. Through a series of drop valves, the suspension enters a settling leg and then is pressure lowered to flash the diluent and unreacted monomers and recover the polymer usually in a cyclone. Diluent and unreacted monomers are recovered and recycled back to the reactor.
[0122]A gas phase polymerization process is commonly carried out in a fluidized bed reactor. Such gas phase processes are widely described in the literature (see, for example, US Patent Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453. 471, 5,462,999, 5,616,661 and 5,668,228). In general, a fluidized bed gas phase polymerization reactor employs a "bed" of polymer and catalyst that is fluidized by a stream of monomer, comonomer, and other optional components that are at least partially gaseous. Heat is generated by the enthalpy of polymerization of the monomer (and comonomer) flowing through the bed. Unreacted monomer, comonomer and other optional gaseous components exit the fluidized bed and are provided with a cooling system to remove this heat. The cooled gas stream, including monomer, comonomer, and other optional components (such as condensable liquids) is then recirculated through the polymerization zone, along with make-up monomer (and comonomer) to replace the one that has been polymerized. in the previous passage. Simultaneously, the polymer product is withdrawn from the reactor. As will be appreciated by one skilled in the art, the “fluidized” nature of the polymerization bed helps to evenly distribute/mix the heat of the reaction and thereby minimize the formation of localized temperature gradients.
[0123] Reactor pressure in a gas phase process can range from about atmospheric to about 600 psig. In a more specific embodiment, the pressure can range from about 100 psig (690 kPa) to about 500 psig (3448 kPa). In another more specific embodiment, the pressure can range from about 200 psig (1379 kPa) to about 400 psig (2759 kPa). In yet another more specific embodiment, the pressure can range from about 250 psig (1724 kPa) to about 350 psig (2414 kPa).
[0124] The reactor temperature in a gas phase process can vary according to the heat of polymerization as described above. In a specific embodiment, the reactor temperature can be from about 30°C to about 130°C. In another specific embodiment, the reactor temperature can be from about 60°C to about 120°C. In yet another specific embodiment, the reactor temperature can be from about 70°C to about 110°C. In yet another specific embodiment, the temperature of a gas phase process can be from about 70°C to about 100°C.
[0125]The fluidized bed process described above is well suited for the preparation of polyethylene, but other monomers (ie comonomer) can also be used. The monomers and comonomer include ethylene and C3-12 alpha olefins respectively, where C3-12 alpha olefins are unsubstituted or substituted by up to two C1-6 alkyl radicals, C8-12 vinyl aromatic monomers that are unsubstituted or substituted by up to two substituents selected from the group consisting of C1-4 alkyl radicals, C4-12 straight chain or cyclic diolefins which are unsubstituted or substituted by a C1-4 alkyl radical. Illustrative non-limiting examples of such alpha-olefins are one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene, styrene, alpha methyl styrene, p-tert-butyl styrene, and ring-limited cyclic olefins such as cyclobutene, cyclopentene, dicyclopentadiene norbornene, alkyl substituted norbornenes, alkenyl substituted norbornenes, and the like (for example, 5-methylene-2-norbornene and 5-ethyllidene-2-norbornene, bicyclo- (2,2,1)-hepta-2,5-diene).
[0126] In one embodiment, the invention is directed to a polymerization process involving the polymerization of ethylene with one or more comonomer(s) including linear or branched comonomer(s) having 3 to 30 carbon atoms, preferably 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms.
[0127] The process is particularly well suited to copolymerization reactions involving the polymerization of ethylene in combination with one or more comonomers, for example, alpha-olefin comonomer such as propylene, butene-1, pentene-1,4- methylpentene-1, hexene-1, octene-1, decene-1, styrene, and cyclic and polycyclic olefins such as cyclopentene, norbornene and cyclohexene or a combination thereof. Other comonomer for use with ethylene may include polar vinyl monomers, diolefins such as 1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, norbornadiene, and other unsaturated monomers including ethylene monomers. acetylene and aldehyde. Higher alpha-olefins and polyenes or macromers can also be used.
[0128] Preferably, the comonomer is an alpha-olefin having 3 to 15 carbon atoms, preferably 4 to 12 carbon atoms and most preferably 4 to 10 carbon atoms.
[0129] In one embodiment of the invention, ethylene comprises at least 75% by weight of the total weight of monomer (i.e., ethylene) and comonomer (i.e., alpha olefin) that is fed to a polymerization reactor.
[0130] In one embodiment of the invention, ethylene comprises at least 85% by weight of the total weight of monomer (i.e., ethylene) and comonomer (i.e., alpha olefin) that is fed to a polymerization reactor.
[0131] In one embodiment of the invention, ethylene is polymerized with at least two different comonomers to form a terpolymer and the like, the preferred comonomer is a combination of monomers, alpha-olefin monomers having 3 to 10 carbon atoms, plus preferably 3 to 8 carbon atoms, optionally with at least one diene monomer. Preferred terpolymers include combinations such as ethylene/butene-1/hexene-1, ethylene/propylene/butene-1, ethylene/propylene/hexene-1, ethylene/propylene/norbornadiene, ethylene/propylene/1,4-hexadiene and the like.
[0132] In one embodiment of the invention, a copolymer of ethylene and an alpha-olefin having from 3 to 8 carbon atoms is made in a single reactor in the presence of a polymerization catalyst system comprising a single metal catalyst. group organotransition 4.
[0133] In one embodiment of the invention, a copolymer of ethylene and an alpha-olefin having 3 to 8 carbon atoms is made in a single gas phase reactor in the presence of a polymerization catalyst system comprising a single catalyst of group 4 organotransition metal.
[0134] In one embodiment of the invention, a copolymer of ethylene and an alpha-olefin having from 3 to 8 carbon atoms is made in a single reactor in the presence of a polymerization catalyst system comprising a single metal catalyst. group 4 organotransition; a catalyst activator; and a support.
[0135] In one embodiment of the invention, a copolymer of ethylene and an alpha-olefin having from 3 to 8 carbon atoms is made in a single gas phase reactor in the presence of a polymerization catalyst system comprising a single catalyst of group 4 organotransition metal; a catalyst activator; and a support.
[0136] In one embodiment of the invention, a copolymer of ethylene and an alpha-olefin having 3 to 8 carbon atoms is made in a single gas phase reactor in the presence of a polymerization catalyst system comprising a single catalyst of transition metal, where the only transition metal catalyst is a group 4 phosphinimine catalyst.
[0137] In one embodiment of the invention, a copolymer of ethylene and an alpha-olefin having 3 to 8 carbon atoms is made in a single gas phase reactor in the presence of a polymerization catalyst system comprising a single catalyst of transition metal, where the only transition metal catalyst is a group 4 phosphinimine catalyst having the formula: (1-R2-Indenyl)Ti(N=P(t-Bu)3)X2; wherein R2 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group, wherein the substituents for the alkyl, aryl or benzyl group are selected from the group consisting of from alkyl, aryl, alkoxy, aryloxy, alkylaryl, arylalkyl and halide substituents; and, where X is an activatable ligand.
[0138] In one embodiment of the invention, a copolymer of ethylene and an alpha-olefin having 3 to 8 carbon atoms is made in a single gas phase reactor with a polymerization catalyst system comprising: a phosphinimine catalyst ; an alkylaluminoxane cocatalyst; and a support.
[0139] In one embodiment of the invention, a copolymer of ethylene and an alpha-olefin having 3 to 8 carbon atoms is made in a single gas phase reactor with a polymerization catalyst system comprising: a phosphinimine catalyst ; an alkylaluminoxane cocatalyst; a support; and a catalyst modifier (which is further described below).
[0140] In one embodiment of the invention, a copolymer of ethylene and an alpha-olefin having 3 to 8 carbon atoms is made in a single gas phase reactor with a polymerization catalyst system comprising: a phosphinimine catalyst having the formula (1-R2-Ind)Ti(N=P(t-Bu)3)X2 where R2 is an alkyl group, an aryl group or a benzyl group wherein each of the alkyl group, the aryl group, or the benzyl group may be unsubstituted or substituted by at least one halide atom, and where X is an activatable linker; and an activator.
[0141] In one embodiment of the invention, a copolymer of ethylene and an alpha-olefin having from 3 to 8 carbon atoms is made in a single gas phase reactor with a polymerization catalyst system comprising: a phosphinimine catalyst having the formula (1-R2-Ind)Ti(N=P(t-Bu)3)X2 where R2 is an alkyl group, an aryl group or a benzyl group wherein each of the alkyl group, the aryl group, or the benzyl group may be unsubstituted or substituted by at least one halide atom, where X is an activatable linker; an activator; and an inert support.
[0142] In one embodiment of the invention, a copolymer of ethylene and an alpha-olefin having 3 to 8 carbon atoms is made in a single gas phase reactor with a polymerization catalyst system comprising: a phosphinimine catalyst having the formula (1-R2-Ind)Ti(N=P(t-Bu)3)X2 where R2 is an alkyl group, an aryl group or a benzyl group wherein each of the alkyl group, the aryl group, or the benzyl group may be unsubstituted or substituted by at least one halide atom, where X is an activatable linker; an activator; an inert support; and a catalyst modifier.
[0143] In one embodiment of the invention, the copolymer is a copolymer of ethylene and an alpha-olefin having 3 to 8 carbon atoms, and is made in a single gas phase reactor with a polymerization catalyst system comprising : a phosphinimine catalyst having the formula (1-C6F5CH2-Ind)Ti(N=P(t-Bu)3)X2 where X is an activatable linker; an activator; and an inert support.
[0144] In one embodiment of the invention, the copolymer is a copolymer of ethylene and an alpha-olefin having 3 to 8 carbon atoms, and is made in a single gas phase reactor with a polymerization catalyst system comprising : a phosphinimine catalyst having the formula (1-C6F5CH2-Ind)Ti(N=P(t-Bu)3)X2 where X is an activatable linker; an activator; an inert support; and a catalyst modifier.
[0145]The polymerization catalyst system can be fed to a reactor system in several ways. If the transition metal catalyst is supported on a suitable support, the transition metal catalyst can be fed to a reactor in dry mode using a dry catalyst feeder, examples of which are well known in the art. Alternatively, a sustained transition metal catalyst can be fed to a reactor as a suspension in a suitable diluent. If the transition metal catalyst is unsupported, the catalyst can be fed to a reactor as a solution or as a suspension in a suitable solvent or diluents. The polymerization catalyst system components, which can include a transition metal catalyst, an activator, a decontaminant, an inert support, and a catalyst modifier, can be combined prior to their addition to a polymerization zone, or they can be combined in route to a polymerization zone. To combine the in-stream polymerization catalyst system components into a polymerization zone, they can be fed as solutions or suspensions (in suitable solvents or diluents) using various feed line configurations that may become coincident before reaching the reactor. Such configurations can be designed to provide areas where the flow of catalyst system components to a reactor can mix and react with each other over various "run" times that can be moderated by changing solution or suspension flow rates. of catalyst system components. Catalyst Modifier
[0146] A "catalyst modifier" is a compound that, when added to a polymerization catalyst system or used in the presence thereof in appropriate amounts, can reduce, prevent or mitigate at least one: of scale, lamination, excursions of temperature, and static level of a material in a polymerization reactor; can change catalyst kinetics; and/or can change the properties of copolymer product obtained in a polymerization process.
[0147] A long-chain amine-type catalyst modifier can be added to a reactor zone (or associated process equipment) separately from the polymerization catalyst system, as part of the polymerization catalyst system, or both as described in the Application of Pat. Co-pending CA No. 2,742,461. The long-chain amine can be a long-chain substituted monoalkanolamine, or a long-chain substituted dialkanolamine as described in Pat. Co-pending CA No. 2,742,461, which is incorporated herein in its entirety.
[0148] In an embodiment of the invention, the catalyst modifier used comprises at least one long-chain amine compound represented by the formula: R9R10xN((CH2)nOH)y where R9 is a hydrocarbyl group having from 5 to 30 atoms of carbon, R10 is hydrogen or a hydrocarbyl group having 1 to 30 carbon atoms, x is 1 or 0, y is 1 when x is 1, y is 2 when x is 0, each n is independently an integer from 1 to 30 when y is 2, and n is an integer from 1 to 30 when y is 1.
[0149] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted monoalkanolamine represented by the formula R9R10N((CH2)nOH) where R9 is a hydrocarbyl group having anywhere from 5 to 30 atoms of carbon, R10 is a hydrogen or a hydrocarbyl group having anywhere from 1 to 30 carbon atoms, and n is an integer from 1 to 20.
[0150] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialkanolamine represented by the formula: R9N((CH2)nOH)((CH2)mOH) where R9 is a hydrocarbyl group having any place from 5 to 30 carbon atoms, and n and n are integers from 1 to 20.
[0151] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialkanolamine represented by the formula: R9N((CH2)xOH)2 where R9 is a hydrocarbyl group having anywhere from 6 to 30 carbon atoms, and x is an integer from 1 to 20.
[0152] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialkanolamine represented by the formula: R9N((CH2)xOH)2 where R9 is a hydrocarbyl group having anywhere from 6 to 30 carbon atoms, ex is 2 or 3.
[0153] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialkanolamine represented by the formula: R9N((CH2)xOH)2 where R9 is a linear hydrocarbyl group having anywhere from 6 to 30 carbon atoms, ex is 2 or 3.
[0154] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialkanolamine represented by the formula: R9N(CH2CH-2OH)2 where R9 is a linear hydrocarbyl group having anywhere from 6 to 30 carbon atoms.
[0155] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialkanolamine represented by the formula: R9N(CH2CH-2OH)2 where R9 is a linear saturated alkyl group having anywhere from 6 to 30 carbon atoms.
[0156] In one embodiment of the invention, the catalyst modifier comprises at least one long-chain substituted dialkanolamine represented by the formula: R9N(CH2CH2OH)2 where R9 is a hydrocarbyl group having anywhere from 8 to 22 carbon atoms .
[0157] In an embodiment of the invention, the catalyst modifier comprises a long-chain substituted dialkanolamine represented by the formula: C18H37N(CH2CH2OH)2.
[0158] In an embodiment of the invention, the catalyst modifier comprises long-chain substituted dialkanolamines represented by the formulas: C13H27N(CH2CH2OH)2 and C15H31N(CH2CH2OH)2.
[0159] In one embodiment of the invention, the catalyst modifier comprises a mixture of long-chain substituted dialkanolamines represented by the formula: R9N(CH2CH2OH)2 where R9 is a hydrocarbyl group having anywhere from 8 to 18 carbon atoms .
[0160] Non-limiting examples of catalyst modifiers that can be used in the present invention are Kemamine AS-990TM, Kemamine AS-650TM, Armostat-1800TM, bis-hydroxy-cocoamine, 2,2'-octadecyl-amino-bisethanol, and Atmer-163TM.
[0161] The amount of catalyst modifier added to a reactor (or other associated process equipment) is conveniently represented here as the parts per million (ppm) of catalyst modifier based on the weight of copolymer produced.
[0162] The amount of catalyst modifier included in a polymerization catalyst system is conveniently represented herein as one percent by weight (% by weight) of the catalyst modifier based on the total weight of the polymerization catalyst system (e.g. , the combined weight of the transition metal catalyst, the inert support, the cocatalyst and the catalyst modifier).
[0163]Catalyst modifier can be added to a polymerization reactor in various ways. The catalyst modifier can be added to a reactor system separately from the polymerization catalyst system or it can be combined with the polymerization catalyst system before feeding the combination to a reactor system.
[0164]If the catalyst modifier is added to the polymerization catalyst system prior to its addition to a reactor, then the catalyst modifier can be added at any point during the preparation of the polymerization catalyst system. Thus, a transition metal catalyst, at least one activator, at least one inert support, and at least one catalyst modifier can be combined in any order to form a polymerization catalyst system suitable for use in the present invention. In specific embodiments of the invention: the catalyst modifier can be added to a support after both the transition metal catalyst and cocatalyst have been added; the catalyst modifier can be added to a support before the transition metal catalyst or cocatalyst is added; the catalyst modifier can be added to a support after the transition metal catalyst, but before the cocatalyst; the catalyst modifier can be added to a support after the cocatalyst, but before the transition metal catalyst. Also, the catalyst modifier can be added in portions during any stage of preparation of the polymerization catalyst system.
[0165] The catalyst modifier may be included in the polymerization catalyst system (or where appropriate, added to a polymerization catalyst system component or components which may comprise a transition metal catalyst, the inert support and the cocatalyst) in any suitable way. By way of non-limiting example, the catalyst modifier can be dry mixed (if it is a solid) with the polymerization catalyst system (or a polymerization catalyst system component) or it can be added neat (if the polymerization modifier). catalyst is a liquid) or can be added as a solution or suspension in a suitable hydrocarbon solvent or diluent respectively. The polymerization catalyst system (or polymerization catalyst system components) can likewise be placed in solution or made into a suspension using suitable solvents or diluents respectively, followed by addition of the catalyst modifier (as a solid or pure liquid or as a solution or a suspension in suitable solvents or diluents) or vice versa. Alternatively, the catalyst modifier can be deposited on a separate support and the resulting sustained catalyst modifier dry mixed or in a suspension with the polymerization catalyst system (or a polymerization catalyst system component).
[0166] In an embodiment of the present invention, the catalyst modifier is added to a polymerization catalyst system already comprising the single transition metal catalyst, inert support and cocatalyst. The catalyst modifier can be added to the polymerization catalyst system turned off and prior to the addition of the polymerization catalyst system to the polymerization zone, or the catalyst modifier can be added to the polymerization catalyst system, or in-stream components for a polymerization reactor.
[0167]The catalyst modifier can be fed to a reactor system using any suitable method known to persons skilled in the art. For example, the catalyst modifier can be fed to a reactor system as a solution or as a suspension in a suitable solvent or diluent respectively. Suitable solvents or diluents are inert hydrocarbons well known to persons skilled in the art and generally include aromatics, paraffinic, and cycloparaffinic such as, for example, benzene, toluene, xylene, cyclohexane, fuel oil, isobutane, mineral oil, kerosene and the like. Other specific examples include, but are not limited to, hexane, heptanes, isopentane and mixtures thereof. Alternatively, the catalyst modifier can be added to an inert support material and then fed to a polymerization reactor as a dry feed or a suspension feed. The catalyst modifier can be fed into multiple positions in a reactor system. When considering a fluidized bed process, for example, the catalyst modifier can be fed directly to any area of the reaction zone (eg when added as a solution), or any area of the entrainment zone, or it can be fed to any area within the closed recirculation loop, where such areas are found to be effective sites that feed a catalyst modifier.
[0168] When added as a solution or mixture with a solvent or diluent respectively, the catalyst modifier can become, for example, from 0.1 to 30% by weight of the solution or mixture, or from 0.1 to 20 % by weight, or from 0.1 to 10 % by weight, or from 0.1 to 5 % by weight or from 0.1 to 2.5 % by weight or from 0.2 to 2.0 % by weight, although a person skilled in the art will recognize that possibly wider ranges may also be used and so the invention should not be limited in this regard.
[0169]The catalyst modifier can be added to a reactor with all or a portion of one or more of the monomers or cycle gas.
[0170] The catalyst modifier can be added to a reactor through a dedicated feed line or added to any convenient feed stream including an ethylene feed stream, a comonomer feed stream, a catalyst feed line or a recycling line.
[0171]The catalyst modifier can be fed to a location in a fluid bed system in a continuous or intermittent manner.
[0172] In one embodiment of the invention, the rate of addition of a catalyst modifier to a reactor will be programmed using static measured reactor levels (or other lead indicators such as reactor temperature) as programming inputs, thus as to maintain a constant or predetermined level of static (or eg temperature) in a polymerization reactor.
[0173]The catalyst modifier can be added to a reactor at a time before, after or during the start of the polymerization reaction.
[0174] The catalyst modifier can be added to the polymerization catalyst system or to one or more polymerization catalyst system components (for example, a phosphinimine catalyst, inert support, or cocatalyst) en route to a reaction zone .
[0175] In one embodiment of the invention, the catalyst modifier is added directly to a reaction zone, separately from the polymerization catalyst system. More typically, it is thus added by spraying a catalyst modifier solution or mixture directly into a reaction zone.
[0176] In one embodiment of the invention, the catalyst modifier is included (combined) with the polymerization catalyst system before adding the combination directly to a reaction zone.
[0177] In an embodiment of the invention, the catalyst modifier is added to a polymer generation bed present in a reactor before starting the polymerization reaction by introducing a catalyst.
[0178] In one embodiment of the invention, the catalyst modifier is added directly to a reaction zone, separately from a polymerization catalyst system, and the catalyst modifier is added as a mixture with an inert hydrocarbon.
[0179] In one embodiment of the invention, the catalyst modifier is added directly to a reaction zone, separately from a polymerization catalyst system, and the catalyst modifier is added as a mixture with an inert hydrocarbon, and is added during a polymerization reaction.
[0180] The total amount of catalyst modifier that can be fed to a reactor and/or included in the polymerization catalyst system is not specifically limited, but should not exceed an amount that makes the activity of the polymerization catalyst system to organotransition metal base falls below that which would be commercially acceptable.
[0181] In this regard, the amount of catalyst modifier fed to a reactor will generally not exceed about 150 ppm, or 100 ppm, or 75 ppm, or 50 ppm, or 25 ppm (parts per million based on the weight of the (co)polymer being produced), while the amount of catalyst modifier included in the polymerization catalyst system will generally not exceed about 10 percent by weight (based on the total weight of the polymerization catalyst system, including the catalyst modifier).
[0182] In embodiments of the invention, the catalyst modifier fed to a reactor will be from 150 to 0 ppm, and including narrower ranges within this range, such as but not limited to, from 150 to 1 ppm, or 150 at 5 ppm, or from 100 to 0 ppm, or from 100 to 1 ppm, or from 100 to 5 ppm, or from 75 to 0 ppm, or from 75 to 1 ppm, or from 75 to 5 ppm, or from 50 to 0 ppm, or 50 to 1 ppm, or 50 to 5 ppm, or 25 to 0 ppm, or 25 to 1 ppm, or 25 to 5 ppm (parts per million by weight of polymer being produced).
[0183] In embodiments of the invention, the amount of catalyst modifier included in the polymerization catalyst system will be from 0 to 10 percent by weight, and including narrower ranges within this range, such as but not limited to, 0 to 6.0 percent by weight, or from 0.25 to 6.0 percent by weight, or from 0 to 5.0 percent by weight, or from 0.25 to 5.0 percent by weight, or from 0 to 4.5 percent by weight, or from 0.5 to 4.5 percent by weight, or from 1.0 to 4.5 percent by weight, or from 0.75 to 4.0 per percent by weight, or from 0 to 4.0 percent by weight, or from 0.5 to 4.0 percent by weight, or from 1.0 to 4.0 percent by weight, or from 0 to 3, 75 percent by weight, or from 0.25 to 3.75 percent by weight, or from 0.5 to 3.5 percent by weight, or from 1.25 to 3.75 percent by weight, or from 1.0 to 3.5 percent by weight, or from 1.5 to 3.5 percent by weight, or from 0.75 to 3.75 percent by weight, or from 1.0 to 3.75 per cent. weight percent (wt% is the weight percent of catalyst modifier based on weight t total polymerization catalyst system; for example, the combined weight of an organotransition metal catalyst, an inert support, a catalyst activator and a catalyst modifier).
[0184] Other catalyst modifiers can be used in the present invention and include compounds such as metal carboxylate salts (see, US Patent Nos. 7,354,88O; 6,300,436; 6,306,984; 6,391,819; 6,472,342 and 6,608. 153, for examples), polysulfones, polymeric polyamines, and sulfonic acids (see, US Patent Nos. 6,562,924; 6,022,935 and 5,283,278, for examples). Polyoxyethylenealkylamines, which are described in, for example, Pat. European No 107,127 can also be used. Other catalyst modifiers include aluminum stearate and aluminum oleate. Catalyst modifiers are supplied commercially under the trade names OCTASTATTM and STADISTM Catalyst modifier STADIS is described in U.S. Patent Nos. 7,476,715; 6,562,924 and 5,026,795 and is available from Octel Starreon. STADIS generally comprises a copolymer of polysulfone, a polymeric amine and an oil-soluble sulfonic acid.
[0185]Commercially available catalyst modifiers sometimes contain unacceptable amounts of water for use with polymerization catalysts. Consequently, the catalyst modifier can be treated with a substance that removes water (for example, by reaction to form inert products, or adsorption or absorption methods), such as a metal alkyl decontaminant or molecular sieves. See, for example, U.S. Patent Application No. 2011/0184124 for the use of a decontaminant compound to remove water from a metal carboxylate antistatic agent. Alternatively, and preferably, a catalyst modifier can be dried under reduced pressure and elevated temperatures to reduce the amount of water present (see, Examples section below). For example, a catalyst modifier can be treated with elevated temperatures (eg at least 10 °C above room temperature or ambient temperature) under reduced pressure (eg below atmospheric pressure) to distill water, as can be obtained using a dynamic vacuum pump. Decontaminant
[0186]Optionally, cleaners are added to the polymerization process. The present invention can be carried out in the presence of any suitable decontaminant or cleaners. Cleaners are well known in the art.
[0187] In one embodiment of the invention, scavengers are organoaluminium compounds having the formula: Al3(X3)n(X4)3-n, where (X3) is a hydrocarbyl having from 1 to about 20 carbon atoms; (X4) is selected from alkoxide or aryloxide, any of which have from 1 to about 20 carbon atoms; halide; or hydride; and n is a number from 1 to 3, inclusive; or alkylaluminoxanes having the formula: R32Al1O(R3Al1O)mAl1R32 wherein each R3 is independently selected from the group consisting of C1-20 hydrocarbyl radicals and is from 3 to 50. Some preferred non-limiting scavengers useful in the present invention include aluminum triisobutyl , triethylaluminum, trimethylaluminum or other trialkylaluminum compounds.
[0188] The decontaminant can be used in any suitable amount, but by way of non-limiting examples only, it may be present in an amount to provide an Al:M molar ratio (where M is the metal of the organometallic compound) of about 20 to about 2000, or from about 50 to about 1000, or from about 100 to about 500. Generally, the decontaminant is added to the reactor before the catalyst and in the absence of additional poisons and decreases over time. to 0, or is added continuously.
[0189]Optionally, wipers can be independently supported. For example, an inorganic oxide that has been treated with an organoaluminum compound or alkylaluminoxane can be added to the polymerization reactor. The method of adding the organoaluminum or alkylaluminoxane compounds to the support is not specifically defined and is carried out by procedures well known in the art. The ethylene copolymer composition
[0190] In the present invention, the term "ethylene copolymer" is used interchangeably with the term "copolymer", or "polyethylene copolymer" and all connote a polymer consisting of polymerized ethylene units and at least one type of alpha olefin polymerized.
[0191] In the present invention, the ethylene copolymer compositions are preferably not polymer blends, but optionally they can be used as a component in a polymer blend. The term polymer "blend" is intended to connote a dry blend of two similar or different polymers, blends resulting in the reactor from the use of multiple or blended catalyst systems in a single reactor zone, and blends resulting from the use of one catalyst in at least two reactors operating under different polymerization conditions, or mixtures that involve the use of at least two different catalysts in one or more reactors under the same or different conditions (for example, a resulting mixture of reactors in series each run under different conditions or with different catalysts).
[0192] Preferably, the ethylene copolymer compositions are copolymers of ethylene and an alpha olefin selected from 1-butene, 1-hexene and 1-octene.
[0193] In embodiments of the invention, the ethylene copolymer composition will comprise at least 75% by weight of ethylene units, or at least 80% by weight of ethylene units, or at least 85% by weight of units of ethylene with the balance being an alpha-olefin unit, based on the weight of the ethylene copolymer composition.
[0194] In embodiments of the invention, the ethylene copolymer will have a melt index (I2) of 0.01 to 3.0 g/10 min, or 0.1 to 2.0 g/10 min, or from 0.25 to 2.0 g/10 min, or from 0.01 to 1.0 g/10 min, or from 0.1 to 1.0 g/10 min, or less than 1.0 g/ 10 min, or from 0.1 to less than 1.0 g/10 min, or from 0.25 to 1.0 g/10 min, or from 0.25 to 0.9 g/10 min, or from 0.25 to 0.80 g/10 min, or from 0.2 to 0.9 g/10 min, or from 0.20 to 0.85 g/10 min, or from 0.25 to 0.85 g /10 min.
[0195] In embodiments of the invention, the ethylene copolymer will have a density of 0.916 g/cc to 0.932 g/cc including narrower bands within this range, such as, for example, from 0.917 g/cc to 0.932 g/ cc, or from 0.916 g/cc to 0.930 g/cc, or 0.917 g/cc to 0.930 g/cc, or from 0.916 g/cc to 0.925 g/cc, or from 0.917 g/cc to 0.927 g/cc, or from 0.917 g/cc to 0.926 g/cc, or from 0.917 g/cc to 0.925 g/cc, or from 0.917 g/cc to 0.923 g/cc, or from 0.918 g/cc to 0.932 g/cc, or 0.918 g/cc to 0.930 g/cc, or 0.918 to 0.930 g/cc, or 0.918 to 0.928 g/cc (note: "g" means gram; "cc" means cubic centimeter, cm3)
[0196] In an embodiment of the invention, the ethylene copolymer will have a density of 0.916 g/cc to 0.930 g/cc. In one embodiment of the invention, the ethylene copolymer will have a density greater than 0.916 g/cc to less than 0.930 g/cc. In one embodiment of the invention, the ethylene copolymer will have a density of 0.917 g/cc to 0.927 g/cc. In one embodiment of the invention, the ethylene copolymer composition will have a density of 0.918 g/cc to 0.927 g/cc.
[0197] The ethylene copolymer of the present invention can have a unimodal, broad unimodal, bimodal, or multimodal profile on a gel permeation chromatography (GPC) curve generated according to the method of ASTM D6474-99. The term "unimodal" is defined here to mean that there will be only one significant peak or maximum evident in the GPC curve. A unimodal profile includes a broad unimodal profile. By the term "bimodal" it is meant that in addition to a first peak, there will be a secondary or sustaining peak that represents a higher or lower molecular weight component (ie, the molecular weight distribution can be said to have two maxima in a molecular weight distribution curve). Alternatively, the term “bimodal” connotes the presence of two maxima in a molecular weight distribution curve generated according to the method of ASTM D6474-99. The term "multimodal" denotes the presence of two or more, typically more than two, maxima in a molecular weight distribution curve generated according to the method of ASTM D6474-99.
[0198] In an embodiment of the invention, the ethylene copolymer will have a unimodal profile on a gel permeation chromatography (GPC) curve generated according to the method of ASTM D6474-99. The term "unimodal" is defined here to mean that there will be only one significant peak or maximum evident in the GPC curve. A unimodal profile includes a broad unimodal distribution curve or profile.
[0199] In embodiments of the invention, the ethylene copolymer will exhibit a weight average molecular weight (MW) as determined by gel permeation chromatography (GPC) of 30,000 to 250,000, including narrower ranges within this range, such as , for example, from 50,000 to 200,000, or from 50,000 to 175,000, or from 75,000 to 150,000, or from 80,000 to 125,000.
[0200] In embodiments of the invention, the ethylene copolymer will exhibit a number average molecular weight (Mn) as determined by gel permeation chromatography (GPC) of 5,000 to 100,000 including narrower ranges within this range, such as by for example, from 7,500 to 100,000, or from 7,500 to 75,000, or from 7,500 to 50,000, or from 10,000 to 100,000, or from 10,000 to 75,000, or from 10,000 to 50,000.
[0201] In embodiments of the invention, the ethylene copolymer will exhibit a Z-average molecular weight (MZ) as determined by gel permeation chromatography (GPC) of 50,000 to 1,000,000 including narrower ranges within this range such as, for example, from 75,000 to 750,000, or from 100,000 to 500,000, or from 100,000 to 400,000, or from 125,000 to 375,000, or from 150,000 to 350,000, or from 175,000 to 325,000.
[0202] In embodiments of the invention, the ethylene copolymer will have a molecular weight distribution (Mw/Mn) as determined by gel permeation chromatography (GPC) of 3.5 to 7.0, including narrower bands within of this range, such as, for example, from 3.5 to 6.5, or from 3.6 to 6.5, or from 3.6 to 6.0, or from 3.5 to 5.5, or from 3.6 to 5.5, or 3.5 to 5.0, or 4.0 to 6.0, or 4.0 to 5.5.
[0203] In embodiments of the invention, the ethylene copolymer will have a Z-average molecular weight distribution (Mz/Mw) as determined by gel permeation chromatography (GPC) of 2.0 to 5.5, including ranges narrower within this range, such as, for example, from 2.0 to 5.0, or from 2.0 to 4.5, or from 2.0 to 4.0, or from 2.0 to 2.5 , or from 2.0 to 3.0.
[0204] In one embodiment of the invention, the ethylene copolymer will have a flat comonomer incorporation profile as measured using Gel Permeation Chromatography with Infrared Fourier Transform detection (GPC-FTIR). In one embodiment of the invention, the ethylene copolymer will have a negative (i.e., "normal") comonomer incorporation profile as measured using GPC-FTIR. In one embodiment of the invention, the ethylene copolymer will have an inverse (i.e., "reverse") or partially inverse comonomer incorporation profile as measured using GPC-FTIR. If comonomer incorporation decreases with molecular weight, as measured using GPC-FTIR, the distribution is described as “normal” or “negative”. If comonomer incorporation is approximately constant with molecular weight, as measured using GPC-FTIR, the comonomer distribution is described as “flat” or “uniform”. The terms "reverse comonomer distribution" and "partially reverse comonomer distribution" mean that in the GPC-FTIR data obtained for the copolymer, there are one or more higher molecular weight components having a higher comonomer incorporation than in a or more low molecular weight segments. The term "reverse comonomer distribution(d)" is used herein to mean that over the entire molecular weight range of the ethylene copolymer, comonomer contents for the various polymer fractions are not substantially uniform and the molecular weight fractions more high of these have proportionately higher comonomer contents (ie, if comonomer incorporation goes up with molecular weight, the distribution is described as “reverse” or “reversed”). Where comonomer incorporation rises with increasing molecular weight and then decreases, comonomer distribution is still considered “reverse” but can also be described as “partially reversed”.
[0205] In one embodiment of the invention, the ethylene copolymer will have an inverted comonomer incorporation profile as measured using GPC-FTIR.
[0206] In one embodiment of the invention, the ethylene copolymer will have a comonomer incorporation profile as determined by GPC-FTIR that satisfies the following condition: SCB/1000C at MW of 200,000 - SCB/1000C at MW of 50,000 is a positive number or greater than 1.0; where SCB/1000C is the comonomer content determined as the number of short chain branches per thousand carbons and MW is the corresponding molecular weight (ie, the absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0207] In one embodiment of the invention, the ethylene copolymer will have a comonomer incorporation profile as determined by GPC-FTIR that satisfies the following condition: SCB/1000C to MW of 200,000 - SCB/1000C to MW of 50,000 > 2.0; where SCB/1000C is the comonomer content determined as the number of short chain branches per thousand carbons and MW is the corresponding molecular weight (ie, absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0208] In one embodiment of the invention, the ethylene copolymer will have a comonomer incorporation profile as determined by GPC-FTIR that satisfies the following condition: SCB/1000C to MW of 200,000 - SCB/1000C to MW of 50,000 > 5.0; where SCB/1000C is the comonomer content determined as the number of short chain branches per thousand carbons and MW is the corresponding molecular weight (ie, absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0209] In one embodiment of the invention, the ethylene copolymer will have a comonomer incorporation profile as determined by GPC-FTIR that satisfies the following condition: SCB/1000C to MW of 200,000 - SCB/1000C to MW of 50,000 > 6.0; where SCB/1000C is the comonomer content determined as the number of short chain branches per thousand carbons and MW is the corresponding molecular weight (ie, absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0210] In one embodiment of the invention, the ethylene copolymer will have a comonomer incorporation profile as determined by GPC-FTIR that satisfies the following condition: SCB/1000C to MW of 200,000 - SCB/1000C to MW of 50,000 > 7.0; where SCB/1000C is the comonomer content determined as the number of short chain branches per thousand carbons and MW is the corresponding molecular weight (ie, absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0211] In one embodiment of the invention, the ethylene copolymer will have a melt flow ratio (MFR = I21/I2) of 30 to 60. In other embodiments of the invention, the ethylene copolymer will have an I21/ I2 from 30 to 55, or from 30 to 50, or from 30 to 45, or from 32 to 50 or from 35 to 55, or from 36 to 50, or from 36 to 48, or from 36 to 46, or from 35 to 50, or greater than 35 to less than 50, or greater than 35 to 50.
[0212] In an embodiment of the invention, the ethylene copolymer has a melt flow rate (I21/I2) of 30 to 50. In an embodiment of the invention, the ethylene copolymer has a flow rate of melt (I21/I2) of greater than 30 to 50. In one embodiment of the invention, the ethylene copolymer has a melt flow ratio (I21/I2) of 32 to 50. In one embodiment of the invention , the ethylene copolymer has a melt flow ratio (I21/I2) of 35 to 50. In one embodiment of the invention, the polyethylene copolymer has a melt flow ratio (I21/I2) of 36 to 50 In one embodiment of the invention, the polyethylene copolymer has a melt flow ratio (I21/I2) of 32 to 55. In one embodiment of the invention, the polyethylene copolymer has a melt flow ratio ( I21/I2) from 36 to 55.
[0213] In embodiments of the invention, the ethylene copolymer will have a width distribution index of the composition CDBI50, as determined by temperature elution fractionation (TREF), from 35% to 75% by weight, or from 35 to 70% by weight, or 40% to 75% by weight. In embodiments of the invention, the copolymer will have a CDBI50 from 40% to 70%, or 45% to 70%, or from 45% to 65%, or from 45 to 60%, or from 45% to 69%, or from 50% to 69%, or from 50% to 70%, or from 50% to 66%, or from 50% to 65%, or from 50% to 60%, or from 55% to 70%, or from 55 from 65%, or from 60% to 70%, or from 60% to 65% (by weight).
[0214] In an embodiment of the invention, the polyethylene copolymer has a CDBI50 of 35% by weight to 70% by weight. In one embodiment of the invention, the polyethylene copolymer has a CDBI50 of 45% by weight to 69% by weight.
[0215] The composition distribution of an ethylene copolymer can also be characterized by the value T(75)-T(25), where the T(25) is the temperatures at which 25% by weight of the eluted copolymer is obtained, and the T(75) is the temperature at which 75% by weight of the eluted copolymer is obtained in a TREF experiment.
[0216] In an embodiment of the present invention, the ethylene copolymer will have a T(75)-T(25) of 10 to 30 °C as determined by TREF. In one embodiment of the present invention, the ethylene copolymer will have a T(75)-T(25) of 10 to 25 °C as determined by TREF. In one embodiment of the present invention, the ethylene copolymer will have a T(75)-T(25) of 10 to 22.5°C as determined by TREF. In one embodiment of the present invention, the ethylene copolymer will have a T(75)-T(25) of 12.5 to 25 °C as determined by TREF. In one embodiment of the present invention, the ethylene copolymer will have a T(75)-T(25) of 12.5 to 22.5 °C as determined by TREF. In one embodiment of the present invention, the ethylene copolymer will have a T(75)-T(25) of 12.5 to 20.0 °C as determined by TREF. In one embodiment of the present invention, the ethylene copolymer will have a T(75)-T(25) of 10.0 to 20 °C as determined by TREF.
[0217] In embodiments of the invention, the ethylene copolymer will have a CY a-parameter (also called Carreau-Yasuda shear exponent) from 0.01 to 0.4, or from 0.05 to 0, 4, or from 0.05 to 0.3, or from 0.01 to 0.3, or from 0.01 to 0.25, or from 0.05 to 0.25.
[0218] In embodiments of the invention, the ethylene copolymer will have a normalized pseudoplastic index, SHI <0.1 rad/s (i.e., ^*o,i/no) of from 0.001 to 0.90, or from 0.001 to 0.8, or from 0.001 to 0.5, or less than 0.9, or less than 0.8, or less than 0.5, or less than 0.35.
[0219] In one embodiment of the invention, the ethylene copolymer will have a TREF profile, as measured by elution fractionation with increasing temperature, which is multimodal, comprising at least two elution intensity maxima or peaks.
[0220] In one embodiment of the invention, the ethylene copolymer will have an amount of copolymer eluting at a temperature at or below 40 °C, less than 5% by weight as determined by fractionation by elution with increasing temperature ( TREF).
[0221] In one embodiment of the invention, the ethylene copolymer will have an amount of copolymer eluting at a temperature of 90 °C to 105 °C, from 5 to 45 % by weight as determined by elution fractionation with increasing temperature (TREF). In one embodiment of the invention, the ethylene copolymer will have an amount of copolymer eluting at a temperature of 90°C to 105°C, from 5 to 40% by weight as determined by fractionation by elution with increasing temperature (TREF) . In one embodiment of the invention, the ethylene copolymer will have an amount of copolymer eluting at a temperature of 90°C to 105°C, from 5 to 35% by weight as determined by fractionation by elution with increasing temperature (TREF) . In one embodiment of the invention, 5 to 30% by weight of the ethylene copolymer will be represented within a temperature range of 90°C to 105°C in a TREF profile. In one embodiment of the invention, 10 to 30% by weight of the ethylene copolymer will be represented within a temperature range of 90°C to 105°C in a TREF profile. In one embodiment of the invention, from 5 to 25% by weight of the ethylene copolymer will be represented within a temperature range of 90°C to 105°C in a TREF profile. In one embodiment of the invention, from 10 to 25% by weight of the ethylene copolymer will be represented within a temperature range of 90°C to 105°C in a TREF profile. In another embodiment of the invention, from 12 to 25% by weight of the ethylene copolymer will be represented in a temperature range of 90 °C to 105 °C in a TREF profile. In another embodiment of the invention, from 10 to 22.5% by weight of the ethylene copolymer will be represented in a temperature range of 90 °C to 105 °C in a TREF profile.
[0222] In embodiments of the invention, less than 1% by weight, or less than 0.5% by weight, or less than 0.05% by weight, or 0% by weight of the ethylene copolymer will elute at a temperature above 100 °C in a TREF analysis.
[0223] In one embodiment of the invention, the ethylene copolymer will have a TREF profile, as measured by elution fractionation with increasing temperature, comprising: i) a multimodal TREF profile comprising at least the elution intensity maxima (or peaks); ii) less than 5% by weight of the copolymer represented at a temperature at or below 40°C; and iii) from 5 to 40% by weight of the copolymer represented at a temperature of 90 °C to 105 °C.
[0224] In an embodiment of the invention, the ethylene copolymer has a trimodal TREF profile comprising three maxima (or peaks) of elution intensity.
[0225] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maxima (or peaks) that occur at elution temperatures T(low), T(medium) or " abbreviated med) and T(high), where T(low) is 60°C to 82°C, T(average) is 75°C to 90°C, but greater than T(low), and T(high) is 90°C to 100°C, but higher than T(low). In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maxima (or peaks) that occur at elution temperatures T(low), T(medium) or abbreviated "med" ) and T(high), where T(low) is 62 °C to 82 °C, T(medium) is 76 °C to 89 °C, but higher than T(low), and T(high) ) is from 90°C to 100°C. In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high); where T(low) occurs at 64°C at 82°C, T(medium) occurs at 78°C at 89°C, but is higher than T(low), and T(high) occurs at 90°C to 100°C. In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high); where T(low) occurs at 64°C at 82°C, T(medium) occurs at 78°C at 87°C, but is higher than T(low), and T(high) occurs at 90 °C to 96 °C, but higher than T(average).
[0226] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maxima (or peaks) that occur at elution temperatures T(low), T(medium) or " abbreviated med) and T(high), where T(low) is 64°C to 82°C, T(mean) is 75°C to 90°C, but is higher than T(low) , and T(high) is 90 °C to 100 °C, but is higher than T(mean). In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maxima (or peaks) that occur at elution temperatures T(low), T(medium) or abbreviated "med" ) and T(high), where T(low) is 65 °C to 75 °C, T(average) is 76 °C to 89 °C, and T(high) is 90 °C to 100 °C.
[0227] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maxima (or peaks) that occur at elution temperatures T(low), T(medium) or " abbreviated med) and T(high), where T(low) is 65°C to 75°C, T(average) is 76°C to 87°C, and T(high) is 90°C C to 100°C.
[0228] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maxima (or peaks) that occur at elution temperatures T(low), T(medium) or " abbreviated med) and T(high), where T(low) is 65°C to 75°C, T(average) is 75°C to 85°C, but is higher than T(mean) , and the T(high) is 90°C to 100°C.
[0229] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maxima (or peaks) that occur at elution temperatures T(low), T(medium) or " abbreviated med) and T(high), where the peak intensity at T(low) and T(high) are greater than the peak intensity at T(medium).
[0230] In embodiments of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maxima (or peaks) that occur at elution temperatures T(low), T(medium) or "med ” abbreviated) and T(high), where the T(medium)-T(low) is 3 °C to 25 °C, or 5 °C to 20 °C; or from 5 °C to 15 °C, or from 7 °C to 15 °C.
[0231] In embodiments of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maxima (or peaks) that occur at elution temperatures T(low), T(medium) or "med ” abbreviated) and T(high), where the T(high)-T(average) is 3 °C to 20 °C, or 3 °C to 17 °C, or 3 °C to 15 °C, or from 5°C to 20°C, or from 5°C to 17°C, or from 5°C to 15°C, or from 7°C to 17°C, or from 7°C to 15°C or from 10 °C to 17 °C, or from 10 °C to 15 °C.
[0232] In embodiments of the invention, the copolymer has a multimodal TREF profile defined by three maxima (or peaks) of elution intensity that occur at elution temperatures T(low), T(medium) or abbreviated "med" ) and T(high), where the T(high)-T(low) is from 15 °C to 35 °C, or from 15 °C to 30 °C, or from 17 °C to 30 °C, or from 15 °C to 27 °C, or 17 °C to 27 °C, or 20 °C to 30 °C or 20 °C to 27 °C.
[0233] In an embodiment of the invention, the copolymer has a multimodal TREF profile defined by three elution intensity maxima (or peaks) that occur at elution temperatures T(low), T(medium) or "med" abbreviated) and T(high), where the peak intensity at T(low) and T(high) are greater than the peak intensity at T(medium); and where the T(medium)-T(low) is 3°C to 25°C; where the T(high)-T(mean) is 5°C to 15°C; and where the T(high)-T(low) is 15 °C to 35 °C.
[0234] In one embodiment of the invention, the ethylene copolymer has a multimodal TREF profile defined by three elution intensity maxima (or peaks) that occur at elution temperatures T(low), T(medium) or " abbreviated med) and T(high), where the peak intensity at T(low) and T(high) are greater than the peak intensity at T(medium); and where the T(medium)-T(low) is 3 °C to 15 °C; where the T(high)-T(mean) is 5°C to 15°C; and where the T(high)-T(low) is 15°C to 30°C.
[0235] In embodiments of the invention, the ethylene copolymer has a multimodal TREF profile defined by three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high), where the T (low) is 64°C at 82°C, T(average) is 76°C at 89°C, but is higher than T(low), and T(high) is 90°C at 100 °C and where the peak intensity at T(low) and T(high) is greater than the peak intensity at T(medium); and where the T(medium)-T(low) is 3 °C to 25 °C, or 5°C to 20 °C; or from 5 °C to 15 °C, or from 7 °C to 15 °C.
[0236] In embodiments of the invention, the ethylene copolymer has a multimodal TREF profile defined by three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high), where the T (low) is 64°C to 75°C, T(mean) is 76°C to 86°C, and T(high) is 90°C to 100°C and where the peak intensity in T (low) and T(high) is greater than the peak intensity at T(medium); and where the T(medium)-T(low) is 3 °C to 25 °C, or 5°C to 20 °C; or from 5 °C to 15 °C, or from 7 °C to 15 °C.
[0237] In embodiments of the invention, the ethylene copolymer has a multimodal TREF profile defined by three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high), where the T (low) is 64°C at 82°C, T(average) is 76°C at 89°C, but is higher than T(low), and T(high) is 90°C at 100 °C and where the peak intensity at T(low) and T(high) is greater than the peak intensity at T(medium); and where the T(high)-T(average) is from 3 °C to 20 °C, or from 3 °C to 17 °C, or from 3 °C to 15 °C, or from 5 °C to 20 °C, or from 5°C to 17 °C, or from 5 °C to 15 °C, or from 7 °C to 17 °C, or from 7 °C to 15 °C or from 10 °C to 17 °C, or from 10 °C to 15 °C.
[0238] In embodiments of the invention, the ethylene copolymer has a multimodal TREF profile defined by three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high), where the T (low) is 64°C to 75°C, T(mean) is 76°C to 86°C, and T(high) is 90°C to 100°C and where the peak intensity in T (low) and T(high) is greater than the peak intensity at T(medium); and where the T(high)-T(average) is 3 °C to 20 °C, or 3 °C to 17 °C, or 3 °C to 15 °C, or 5 °C to 20 ° C, or from 5 °C to 17 °C, or from 5 °C to 15 °C, or from 7 °C to 17 °C, or from 7 °C to 15 °C or from 10 °C to 17 °C , or from 10°C to 15°C.
[0239] In embodiments of the invention, the ethylene copolymer has a multimodal TREF profile defined by three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high), where the T (low) is 64°C at 82°C, T(average) is 76°C at 89°C, but is higher than T(low), and T(high) is 90°C at 100 °C and where the peak intensity at T(low) and T(high) is greater than the peak intensity at T(medium); and where the T(high)-T(low) is from 15 °C to 35 °C, or from 15 °C to 30 °C, or from 17 °C to 30 °C, or from 15 °C to 27 ° C, or from 17 °C to 27 °C, or from 20 °C to 30 °C or from 20 °C to 27 °C.
[0240] In embodiments of the invention, the ethylene copolymer has a multimodal TREF profile defined by three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high), where the T (low) is 65 °C to 75 °C, T(average) is 76 °C to 86 °C, and T(high) is 90 °C to 100 °C and where the peak intensity in T (low) and T(high) is greater than the peak intensity at T(medium); and where the T(high)-T(low) is from 15 °C to 35 °C, or from 15 °C to 30 °C, or from 17 °C to 30 °C, or from 15 °C to 27 ° C, or from 17 °C to 27 °C, or from 20 °C to 30 °C or from 20 °C to 27 °C.
[0241] In an embodiment of the invention, the ethylene copolymer has two melting peaks as measured by differential scanning calorimetry (DSC).
[0242] In one embodiment of the invention, the ethylene copolymer will satisfy the condition: (CDBI50 - 3) < [15/(a + 0.12)]; where the CDBI50 is the distribution width index of the composition in % by weight, determined by TREF analysis and “a” is the Carreau-Yasuda shear exponent determined by dynamic mechanical analysis (DMA).
[0243] In embodiments of the invention, the ethylene copolymer will have an extractable hexane level of <3.0% by weight, or <2.0% by weight, or <1.5% by weight or <1. 0% by weight. In one embodiment of the invention, the copolymer has an extractable hexane level of from 0.2 to 3.0% by weight, or from 0.2 to 2.5% by weight, or from 0.2 to 2.0 % by weight.
[0244] In one embodiment of the invention, the ethylene copolymer will have a processability increase index (X) of at least 1.0, where the processability increase index (X) is defined by: X = 96 - 2.14 [(MFR0'5) + 1 x 10 - 4 (Mw - Mn)]/δXO where δXO is the crossover phase angle of a van Gurp-Palmen (VGP) representation as determined by dynamic mechanical analysis ( DMA), MFR is the melt flow ratio I21/I2, Mw is the weight average molecular weight and Mn is the number average molecular weight determined by gel permeation chromatography (GPC).
[0245] In an embodiment of the invention, the ethylene copolymer will have a processability increase index (/) greater than 1.0 and less than 1.50.
[0246] In an embodiment of the invention, the ethylene copolymer will have a processability increase index (/) greater than 1.0 and less than 1.30.
[0247] In an embodiment of the invention, the ethylene copolymer will have a processability increase index (/) greater than 1.0 and less than 1.20.
[0248] In one embodiment of the invention, the ethylene copolymer will satisfy the condition: δXO< 96 - 2.14 [(MFR0'5) + 1 x 10 - 4 (Mw - Mn)] where δXO is the angle of crossover phase at a frequency of 1.0 rad/s in a VGP representation as determined by dynamic mechanical analysis (DMA), MFR is the melt flux ratio I21/I2, Mw is the weight average molecular mass and Mn is the number average molecular weight determined by gel permeation chromatography (GPC).
[0249] In an embodiment of the invention, the ethylene copolymer satisfies the following ratio: (Mw/Mn) > 68 [(I21/I2)-1 + 10 - 6 (Mn)].
[0250] In an embodiment of the invention, the ethylene copolymer satisfies the following relationship: δXO < [80 - 1.22 (CDBl50)/(Mw/Mn)], where δXO is the crossover phase angle of a van Gurp-Palmen (VGP) representation as determined by dynamic mechanical analysis (DMA) and CDBI50 is the comonomer width index distribution as determined by TREF analysis.
[0251] In an embodiment of the invention, the ethylene copolymer satisfies both of the following ratios: (Mw/Mn) > 68 [(I21/I2)-1 + 10 - 6 (Mn)] and δ XO < [80 - 1.22 (CDBI50)/(Mw/Mn)]. Film Production
[0252]The extrusion blow-molded film process is a well-known process for preparing plastic film. The process employs an extruder that heats, melts and transports the molten plastic and force through an annular mold. Typical extrusion temperatures are 330 to 500 oF (165 to 260 °C), especially 350 to 460 oF (176 to 237 °C).
[0253] Polyethylene copolymer film is drawn from the mold and formed into a tube shape and eventually passed through a pair of suction or nip rollers. Internal compressed air is then introduced from a mandrel causing the tube to increase in diameter to form a “bubble” of the desired size. Thus, the blow molded film is stretched in two directions, that is, in the axial direction (by the use of forced air that "blows" the diameter of the bubble) and in the longitudinal direction of the bubble (by the action of a winding element that pulls the bubble through the machinery). External air is also introduced around the circumference of the bubble to cool the melt as it exits the mold. The film width is varied by introducing more or less internal air into the bubble, thus increasing or decreasing the bubble size. Film thickness is mainly controlled by increasing or decreasing the speed of the traction roll or nip roll to control the suction rate.
[0254]The bubble is then collected immediately after passing through the suction or nip rollers. The cooled film can then be processed by cutting or sealing to produce a variety of consumer products. While not wishing to be bound by theory, it is generally believed by one skilled in the art of blow molded film fabrication that the physical properties of the finished films are influenced both by the molecular structure of the ethylene copolymer and by the processing conditions. For example, processing conditions are thought to influence the degree of molecular orientation (in both the machine direction and the axial or transverse direction).
[0255] A balance of molecular orientation "machine direction" ("MD") and "transverse direction" ("TD" - which is perpendicular to MD) is generally considered desirable for films associated with the invention (eg strength dart impact, machine steering tear properties and transverse steering may be affected).
[0256]Thus, it is recognized that these elongation forces in the “bubble” can affect the physical properties of the finished film. In particular, it is known that the "explosion ratio" (ie, the ratio of the blow molded bubble diameter to the annular mold diameter) can have a significant effect on the dart impact strength and tear strength of the film. finished.
[0257] The above description refers to the preparation of monolayer films. Multilayer films can be prepared by 1) a “co-extrusion” process that allows more than one stream of molten polymer to be introduced to an annular mold that results in a multilayer film membrane, or 2) a process of lamination in which the film layers are laminated together.
[0258] In one embodiment of the invention, the films of this invention are prepared using the blow molded film process described above.
[0259] An alternative process is the so-called melt-film process, in which polyethylene is melted in an extruder, then forced through a linear slit mold, thereby “molding” a flat, thin film. The extrusion temperature for molding the film is typically slightly hotter than that used in the blow molded film process (typically with operating temperatures of 450 to 550oF). In general, the cast film is cooled (quickly cooled) faster than the blow molded film.
[0260] In one embodiment of the invention, the films of this invention are prepared using a cast film process. Additions
[0261] The ethylene copolymer composition used in the present invention to make films, may also contain additives such as, for example, primary antioxidants (such as hindered phenols, including vitamin E); secondary antioxidants (especially phosphites and phosphonites); nucleating agents, plasticizers or PPA processing auxiliary polymers (eg, process aid linked to fluoroelastomer and/or polyethylene glycol), acid cleaners, stabilizers, anti-corrosive agents, blowing agents, other ultraviolet light absorbers such as anti-aging antioxidants chain, etc., suppressors, anti-static agents, slip agents, anti-blocking agent, pigments, dyes and fillers, and curing agents such as peroxide.
[0262] These and other additives common in the polyolefin industry may be present in copolymer compositions from 0.01 to 50% by weight in one embodiment, and from 0.1 to 20% by weight in another embodiment , and from 1 to 5% by weight in yet another embodiment, wherein a desirable range may comprise any combination of any upper limit of % by weight with any lower limit of % by weight.
[0263] In one embodiment of the invention, antioxidants and stabilizers such as organic phosphites and phenolic antioxidants may be present in the copolymer compositions from 0.001 to 5% by weight in one embodiment, and from 0.01 to 0.8 % by weight in another embodiment, and from 0.02 to 0.5% by weight in yet another embodiment. Non-limiting examples of suitable organic phosphites are tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168) and tris (nonyl phenyl) phosphite (WESTON 399). Non-limiting examples of phenolic antioxidants include octadecyl-3,5-di-t-butyl-4-hydroxyhydrocinnamate (IRGANOX 1076) and pentaerythryl-tetracis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ( IRGANOX 1010); and 1,3,5-Tri(3,5-di-tert-butyl-4-hydroxybenzylisocyanurate (IRGANOX 3114).
[0264] Fillers may be present in the ethylene copolymer composition from 0.1 to 50% by weight in one embodiment, and from 0.1 to 25% by weight of the composition in another embodiment, and from 0.2 to 10% by weight in yet another embodiment. Fillers include but are not limited to titanium dioxide, silicon carbide, silica (and other silica oxides, precipitated or not), antimony oxide, lead carbonate, zinc white, lithopone, zircon, corundum, spinel, apatite , powdered barite, barium sulfate, magnesite, carbon black, dolomite, calcium carbonate, talc and hydrotalcite composed of Mg, Ca, or Zn ions with Al, Cr or Fe and CO3 and/or HPO4, hydrated or not ; quartz powder, hydrochloric magnesium carbonate, glass fibers, clays, alumina, and other metal oxides and carbonates, metal hydroxides, chromium, phosphorus and brominated flame retardants, antimony trioxide, silica, silicone, and mixtures thereof. These fillers can include any other fillers and porous fillers and supports that are known in the art.
[0265] Fatty acid salts may also be present in copolymer compositions. Such salts may be present from 0.001 to 2% by weight of the copolymer composition in one embodiment, and from 0.01 to 1% by weight in another embodiment. Examples of fatty acid metal salts include lauric acid, stearic acid, succinic acid, lactic acid stearyl, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, and erucic acid, suitable metals including Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb and so on. Desirable fatty acid salts are selected from magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate, and magnesium oleate.
[0266] With respect to the physical process of producing the mixture of ethylene copolymer and one or more additives, sufficient mixing should occur to ensure that a uniform mixture will be produced prior to conversion to a finished product. The copolymer can be in any physical form when used to blend with one or more additives. In one embodiment, reactor beads, defined as polymer beads that are isolated from the polymerization reactor, are used for mixing with the additives. The reactor beads have an average diameter of 10 µm to 5 mm, and 50 µm to 10 mm in another embodiment. Alternately, the ethylene copolymer is in the form of pellets, such as, for example, having an average diameter of 1 mm to 6 mm which is formed from melt extrusion of the reactor granules.
[0267] One method of mixing the additives with the ethylene copolymer is to contact the components in a glass beaker or other physical mixing means, the copolymer being in the form of reactor granules. This can then be followed, if desired, by melt blending in an extruder. Another method of mixing the components is to melt the mixture of copolymer pellets with additives directly in an extruder, or any other means of melt mixing. Film Properties.
[0268] The film, or film layer of the present invention is made from the ethylene copolymers defined above. Generally, an additive described above is blended with the ethylene copolymer prior to film production. Ethylene copolymers and films have a balance of processing and mechanical properties. Consequently, the films of the present invention will have an impact strength per dart of >500 g/mil, a 1% MD drying modulus greater than 150 MPa, and a 1% TD drying modulus greater than 170 MPa in combination with good film processing output rates.
[0269] In embodiments of the invention, the film will have an impact per dart of > 500 g/mil, or > 550 g/mil, or > 600 g/mil. In another embodiment of the invention, the film will have an impact per dart of 500 g/mil to 750 g/mil. In another embodiment of the invention, the film will have an impact per dart from 500 g/mil to 700 g/mil. In yet another embodiment of the invention, the film will have an impact per dart from 550 g/mil to 750 g/mil. In yet another embodiment of the invention, the film will have an impact per dart from 600 g/mil to 750 g/mil. In another embodiment of the invention, the film will have an impact per dart from 600 g/mil to 700 g/mil. In another embodiment of the invention, the film will have an impact per dart from 550 g/mil to 700 g/mil.
[0270] In embodiments of the invention, the film will have an MD tear to TD tear ratio (MD tear/TD tear) less than 0.75, or < 0.70, or < 0.60 , or < 0.50, or < 0.40, or < 0.45; or < 0.35. In another embodiment of the invention, the film will have an MD tear to TD tear ratio of 0.10 to 0.75. In yet another embodiment of the invention, the film will have an MD tear to TD tear ratio of 0.1 to 0.6. In yet another embodiment of the invention, the film will have an MD tear to TD tear ratio of 0.2 to 0.55. In yet another embodiment of the invention, the film will have an MD tear to TD tear ratio of 0.2 to 0.50.
[0271] In embodiments of the invention, a 1 mil film will have a machine direction secant modulus (MD) at 1% tension of > 150 MPa, or > 160 MPa, or > 175 MPa, or > 180 MPa > 190 MPa. In one embodiment of the invention, a 1 mil film will have a machine direction secant modulus (MD) at 1% tension of 150 MPa to 250 MPa. In one embodiment of the invention, a 1 mil film will have a machine direction secant modulus (MD) at 1% tension of 160 MPa to 240 MPa. In another embodiment of the invention, a 1 mil film will have a machine direction secant modulus (MD) at 1% tension of 170 MPa to 230 MPa. In yet another embodiment of the invention, a 1 mil film will have a machine direction secant modulus (MD) at 1% tension of 180 MPa to 220 MPa.
[0272] In one embodiment of the invention, a 1 mil film will have a transverse direction (TD) secant modulus at 1% tension of > 170 MPa, or > 175 MPa, or > 180 MPa, or > 190 MPa, or > 200 MPa. In one embodiment of the invention, a 1 mil film will have a transverse direction (TD) secant modulus at 1% tension of 170 MPa to 270 MPa. In another embodiment of the invention, a 1 mil film will have a transverse direction (TD) secant modulus at 1% tension of 180 MPa to 260 MPa. In yet another embodiment of the invention, a 1 mil film will have a transverse direction (TD) secant modulus at 1% tension of 190 MPa to 250 MPa. In another embodiment of the invention, a 1 mil film will have a transverse direction (TD) secant modulus at 1% tension of 200 MPa to 240 MPa.
[0273] The film or film layer may, for example, have a total thickness ranging from 0.5 mils to 4 mils (note: 1 mil = 0.0254 mm), which will depend, for example, on the aperture of the mold used during film molding or film blowing.
[0274]The above description applies to monolayer films. However, the film of the present invention can be used in a multilayer film. Multilayer films can be manufactured using a co-extrusion process or a lamination process. In co-extrusion, a plurality of molten polymer streams are fed into an annular mold (or flat cast) resulting in a multi-layer film on cooling. In lamination, a plurality of films are joined using, for example, adhesives, heat and pressure joining, and the like. A multilayer film structure, for example, can control bonding layers and/or sealing layers.
[0275]The film of the present invention can be a skin layer or a core layer and can be used in at least one or a plurality of layers in a multilayer film. The term “core” or the phrase “core layer” refers to any inner film layer in a multilayer film. The phrase “skin layer” refers to an outer layer of a multi-layer film (for example, as used in the production of packaging products). The phrase "sealing layer" refers to a film that is involved in sealing the film to itself or to another layer in a multilayer film. A "bonding layer" refers to any inner layer that adheres two layers together.
[0276]By way of example only, the thickness of multilayer films can be from about 0.5 mil to about 10 mil in total thickness. EXAMPLES General
[0277] All reactions involving air and/or moisture sensitive compounds were conducted under nitrogen using Schlenk techniques and standard cannula, or in a glove box. Reaction solvents were purified using the system described by Pangborn et. al. in Organometallics 1996, v15, page 1518 or used directly after being stored in activated 4A molecular sieves. The methylaluminoxane used was a 10% MAO solution in toluene supplied by Albemarle which was used as received. The support used was Sylopol 2408 silica obtained by W.R. Grace. & Co. The support was calcined by fluidization with air at 200 °C for 2 hours followed by nitrogen at 600 °C for 6 hours and stored under nitrogen.
[0278] Melt Index, I2, in g/10 min was determined on a Tinius Olsen Plastomer (Model MP993) according to ASTM D1238 Procedure A (Operating Manual) at 190°C with a weight of 2.16 kg . Melt Index, 110, was determined in accordance with ASTM D1238 Procedure A at 190°C with a weight of 10 kilograms. High charge melt index, I21, in g/10 min was determined according to Procedure A of ASTM D1238 at 190°C with a weight of 21.6 kilograms. The melt flux ratio (also sometimes called the melt index ratio) is I21/I2.
[0279] Polymer density was determined in grams per cubic centimeter (g/cc) according to ASTM D1928.
[0280] Molecular weight information (Mw, Mn and Mz in g/mol) and molecular weight distribution (Mw/Mn), and z-average molecular weight distribution (MZ/MW) were analyzed by permeation chromatography in gel (GPC), using an instrument sold under the trade name “Waters 150c”, with 1,2,4-trichlorobenzene as the mobile phase at 140 °C. Samples were prepared by dissolving the polymer in this solvent and were conducted without filtration. Molecular weights are expressed as equivalent polyethylenes with a relative standard deviation of 2.9% for the number average molecular weight ("Mn") and 5.0% for the weight average molecular weight ("Mw"). Polymer sample solutions (1 to 2 mg/mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel for 4 hours at 150 oC in an oven. The antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in order to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. Sample solutions were chromatographed at 140 oC in a PL 220 high temperature chromatography unit equipped with four Shodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate of 1.0 mL/ minute, with a differential refractive index (DRI) as the concentration detector. BHT was added to the mobile phase at a concentration of 250 ppm to protect the columns from oxidative degradation. The sample injection volume was 200 mL. Raw data were processed with GPC Cirrus software. Columns were calibrated with narrowly distributed polystyrene standards. Polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink Equation as described in ASTM standard test method D6474.
[0281] The branching frequency of copolymer samples (i.e., short chain branching, SCB per 1000 carbons) and the C6 comonomer content (in % by weight) was determined by Fourier Transform Infrared Spectroscopy ( FTIR) as per ASTM method D6645-01. A Thermo-Nicolet 750 Magna-IR Spectrophotometer equipped with OMNIC software version 7.2a was used for the measurements.
[0282]The determination of branching frequency as a function of molecular weight (and hence comonomer distribution) was performed using high temperature gel permeation chromatography (GPC) and FT-IR of the eluent. Standards of polyethylene with a known branching content, polystyrene and hydrocarbons with a known molecular weight were used for calibration.
[0283] Extractable hexane using compression molded plates was determined according to ASTM D5227.
[0284]To determine the width distribution index of the composition CDBI50 (which is also called CDBI(50) in the present invention so that CDBI50 and CDBI(50) are used interchangeably), a solubility distribution curve is first generated for the copolymer. This is accomplished using data acquired from the TREF technique (see below). This solubility distribution curve is a representation of the weight fraction of the copolymer that is solubilized as a function of temperature. This is converted to a cumulative distribution curve of weight fraction versus comonomer content, from which the CDBI50 is determined by establishing the percentage by weight of a copolymer sample that has a comonomer content within 50% of the average comonomer content in each side of the mean (see, WO 93/03093 for the definition of CDBI50). The weight percentage of copolymer eluting at 90 to 105 °C is determined by calculating the area under the TREF curve at an elution temperature of 90 to 105 °C. The weight percent of copolymer eluting below or 40°C and above 100°C was determined similarly. For the purpose of simplifying the correlation of composition with elution temperature, all fractions are considered to have a Mn^15,000, where Mn is the number average molecular weight of the fraction. Any low weight fractions present generally represent an insignificant portion of the polymer. The remainder of this description and the appended claims maintain this convention of assuming that all fractions have Mn^15,000 in the CDBI50 measurement.
[0285]The specific temperature rise elution fractionation (TREF) method used here was as follows. Homogeneous polymer samples (pelletized, 50 to 150 mg) were introduced into the reactor vessel of a crystallization-TREF unit (Polymer ChARTM). The reactor vessel was filled with 20 to 40 ml of 1,2,4-trichlorobenzene (TCB), and heated to the desired dissolution temperature (eg 150 °C) for 1 to 3 hours. The solution (0.5 to 1.5 ml) was then loaded onto the TREF column filled with stainless steel beads. After equilibrating at a certain stabilization temperature (eg 110°C) for 30 to 45 minutes, the polymer solution was allowed to crystallize with a temperature drop from the stabilization temperature at 30°C (0.1 or 0 .2°C/minute). After equilibrating at 30 °C for 30 minutes, the crystallized sample was eluted with TCB (0.5 or 0.75 mL/minute) with a temperature rise of 30 °C to the stabilization temperature (0.25 or 1, 0°C/minute). The TREF column was cleaned at the end of the conduction for 30 minutes at the dissolution temperature. Data were processed using Polymer ChAR software, Excel spreadsheet and internally developed TREF software.
[0286] The TREF procedures described above are well known to persons skilled in the art and can be used to determine the modality of a TREF profile, a CDBI50, a % by weight copolymer eluting at or below 40 °C, a % by weight of copolymer eluting above 100 °C, a % by weight of copolymer eluting at 90 °C to 105 °C, a value of T(75)-T(25), as well as temperatures or temperature ranges where the maximum elution intensity (elution peaks) occurs.
[0287] Melting points including a peak melting point (Tm) and percent crystallinity of the copolymers are determined using a TA Instrument Q1000 Thermal Analyzer at 10°C/min. In a DSC measurement, a heat-cool-heat cycle from room temperature to 200 °C or vice versa is applied to the polymers to minimize the thermo-mechanical history associated with them. The melting point and percent crystallinity are determined by the primary peak temperature and the total area under the DSC curve respectively from the second heating data. The peak melting temperature Tm is the highest temperature peak when two peaks are present in a bimodal DSC profile (typically also having the highest peak height).
[0288]The melt strength of a polymer is measured in a RH-7 Rosand capillary rheometer (barrel diameter = 15 mm) with a 2 mm Diameter flat mold, L/D ratio 10:1 at 190 °C. Pressure Transducer: 10,000 psi (68.95 MPa). Piston Speed: 5.33 mm/min. Haul-off angle: 52°. Haul-off increment speed: 50 to 80 m/min2 or 65 ± 15 m/min2. A molten polymer is extruded through a capillary matrix at a constant rate and then the polymer filament is drawn at an increasing haul-off speed until it breaks. The maximum stress constant value in the plateau region of a stress versus time curve is defined as the melt strength for the polymer.
[0289]Dynamic mechanical analysis (DMA). Dynamic Mechanical Analysis (DMA). Rheological measurements (eg, low-stress (10%) oscillatory shear measurements) were performed on a 25 mm diameter rotational Rheometrics SR5 Dynamic Stress rheometer of parallel plates in a frequency sweep mode under a full nitrogen blanket . Polymer samples are appropriately stabilized with the antioxidant additives and then inserted into the test facility for at least one minute pre-heating to measure normal stress decreasing back to zero. All DMA experiments are conducted at 10% voltage, 0.05 at 100 rad/s and 190 °C. Orchestrator software is used to determine viscoelastic parameters including storage modulus (G’), loss modulus (G”), phase angle (δ), complex modulus (G*) and complex viscosity (q*).
[0290]The complex viscosity data |n*(w)| versus frequency (w) were then curve fitted using the three-parameter empirical Carreau-Yasuda (CY) models modified to obtain the zero shear viscosity at the characteristic viscous relaxation time TΠ, and the amplitude of the a-parameter of rheology. The simplified empirical Carreau-Yasuda (CY) model used is as follows:|n*(w) | = no/[1 + (tn w)um] (1 - n)/um where: |n*(w) | = magnitude of complex shear viscosity; no = zero shear viscosity; tn = characteristic relaxation time; a = rheology parameter “amplitude” (which is also called the “Carreau-Yasuda shear exponent” or the “CY a-parameter” or simply the “a-parameter” in the present invention); n = corrects the slope of the final power law, set at 2/11; and w = angular frequency of oscillatory shear strain. Details of the significance and interpretation of the CY model and derived parameters can be found in: C.A. Hieber and H.H. Chiang, Rheol. Acta, 28, 321 (1989); C.A. Hieber and H.H. Chiang, Polim. Eng. Sci., 32, 931 (1992); and R.B. Bird, R.C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987); each of which is incorporated herein by reference in their entirety.
[0291] The Pseudoplastic Index (SHI) was determined according to the method in US Patent Application No. 2011/0212315: the SHI is defined as SHI(w)=n*(w)/n0 for any given frequency (w) for the measurement of dynamic viscosity, where n0 is the zero shear viscosity >190°C determined by means of an empirical Cox-Merz-rule. n* is the complex viscosity @190 °C determinable at shear or dynamic (sinusoidal) deformation of a copolymer as determined on a Rheometrics SR5 Stress rotational rheometer using parallel plate geometry. According to Cox-Merz-Rule, when frequency (w) is expressed in radiant units, at low shear rates, the numerical value of n* is equal to that of conventional intrinsic viscosity based on low-shear capillary measurements. The person skilled in the field of rheology is well versed with determination n0 in this manner.
[0292] The films in the present examples were made on a blow molded film production line manufactured by Battenfeld Gloucester Engineering Company of Gloucester, Mass using a mold diameter of 4 inches, and a mold opening of 35 or 100 mil ( note: a PPA-type fluoroelastomer was added to inv. 1 resin for film production purposes; competitive resin 2 analysis shows ca 250 to 300 ppm of a PPA fluoroelastomer is present; competitive resin 3 analysis suggests ca. 600 ppm of polyethylene glycol and PPA fluoroelastomer in total is present). This blow molded film production line has a standard output greater than 100 pounds per hour and is equipped with a 50 horsepower engine. Helical speed was 35 to 50 RPM. The helical expander has a diameter of 2.5 mil and a length/diameter (L/D) ratio of 24/1. Melting Temperature and Freezing Line Height (FLH) are 420 to 430°F (215 to 221°C) and 16 inches respectively. The blow molded film bubble is air cooled. Typical burst ratio (BUR) for blow molded films prepared in this line are 1.5/1 to 4/1. An annular mold having an opening of 85 mils was used for these experiments. The films in this example were prepared using a 2.5:1 BUR sights and a 1.0 mils film thickness sights.
[0293]Haze (%) was measured according to the procedures specified in ASTM D 1003-07, using a BYK-Gardner Haze Meter (Haze-gard plus Model).
[0294] The dart impact strength was measured on a dart impact tester (Model D2085AB/P) made by Kayeness Inc. in accordance with ASTM D-1709-04 (method A).
[0295]Elmendorf tear strengths in machine direction (MD) and transverse (TD) were measured on a ProTearTM Tear Tester made by Thwing-Albert Instrument Co. according to ASTM D-1922.
[0296] Puncture resistance was measured on an MTS Universal Systems Tester (Model SMT(ALTA)-500N-192) in accordance with ASTM D-5748
[0297] MD or TD secant modulus was measured on a 5-Head Universal Tester Instrument (Model TTC-102) at a crosshead speed of 0.2 in/min up to 10% voltage in accordance with ASTM D- 882-10. The secant modulus of MD or TD was determined by an initial slope of the stress-stress curve from a source at 1% stress.
[0298]The film tension test was conducted on a 5-Head Universal Tester Instrument (Model TTC-102) in accordance with ASTM D-882-10.
[0299]Gloss was measured on a BYK-Gardner 45° Micro-Gloss unit in accordance with ASTM D2457-03.
[0300] A seal was prepared by clamping two 2.0 mil strips of film between heated upper and lower sealing bars in an SL-5 Sealer made by Lako Tool for 0.5 seconds, 40 psi clamping pressure of the seal bar for each temperature in the range between the beginning of the seal to completely melt. The resistance or sealability parameter was measured as a function of seal temperature on a 5-Head Universal Tester Instrument (Model TTC-102) in accordance with ASTM F88-09. Inventive Example 1 Catalyst System Preparation Synthesis of (1-C6F5CH2-Indenyl)((t-Bu)3P=N)TiCl2.
[0301] To distilled indene (15.0 g, 129 mmols) in heptane (200 ml) was added BuLi (82 ml, 131 mmols, 1.6 M in hexanes) at room temperature. The resulting reaction mixture was stirred overnight. The mixture was filtered and the filter cake washed with heptane (3 x 30 mL) to provide indenyllithium (15.62 g, 99% yield). Indenyllithium (6.387 g, 52.4 mmols) was added as a solid over 5 minutes to a stirred solution of C6F5CH2-Br (13.65 g, 52.3 mmols) in toluene (100 mL) at room temperature. The reaction mixture was heated to 50 °C and stirred for 4 h. The product mixture was filtered and washed with toluene (3 x 20 ml). The combined filtrates were evaporated to dryness to give 1-C6F5CH2-indene (13.58 g, 88%). To a stirred suspension of TiCl4,2THF (1.72 g, 5.15 mmols) in toluene (15 mL) was added (t-Bu)3P=N-Li solid (1.12 g, 5 mmols) at room temperature . The resulting reaction mixture was heated at 100 °C for 30 min and then allowed to cool to room temperature. This mixture containing ((t-Bu)3P=N)TiCl3 (1.85 g, 5 mmols) was used in the next reaction. To a THF (10 mL) solution of 1-C6F5CH2-indene (1.48 g, 5 mmols) cooled to -78 °C was added n-butyllithium (3.28 mL, 5 mmols, 1.6 M in hexanes ) for 10 minutes. The resulting dark orange solution was stirred for 20 minutes and then transferred via a double-ended needle to a toluene suspension of ((t-Bu)3P=N)TiCl3 (1.85 g, 5 mmols) . Cooling was removed from the reaction mixture which was stirred for an additional 30 minutes. Solvents were evaporated to obtain a yellow pasty residue. The solid was re-dissolved in toluene (70 ml) at 80 °C and filtered hot. The toluene was evaporated to obtain pure (1-C6F5CH2-Indenyl)((t-Bu)3P=N)TiCl2 (2.35 g, 74%). Catalyst modifier drying.
[0302]950 g of commercially available Armostat® 1800 (mp 50 oC, bp > 300 oC), which was used as a catalyst modifier, was loaded into a 2 L round bottom flask and melted in an oil bath at 80°C The oil bath temperature was then raised to 110°C and a high vacuum was applied while maintaining agitation. First, a batch of bubbles was observed due to the release of gas vapor and moisture. Approximately two hours later, gas release ceased and heating/evacuation was continued for another hour. The Armostat 1800 material was then cooled to room temperature and stored under a nitrogen atmosphere until use.
[0303]To determine the moisture level in Armostat 1800, 15% by weight of a solution of Armostat in pre-dried toluene was prepared and the moisture of the solution was determined by Karl-Fischer titration method. Moisture levels in Armostat 1800 as received from the commercial supplier, as well as those dried by traditional methods (ie drying the solution over molecular sieves) and through the use of low pressure water distillation were determined. Unpurified catalyst modifier was found to make a 15% by weight toluene solution having 138 ppm H2O. The catalyst modifier which was dried on molecular sieves was found to make a 15% by weight toluene solution having 15 to 20 ppm H2O. The catalyst modifier which was dried by vacuum water distillation was found to make a 15% by weight toluene solution having 14 to 16 ppm H2O. It has thus been shown that simple vacuum distillation to remove water is as effective as drying methods using molecular sieves. In fact, vacuum distillation has an advantage over using molecular sieves as a drying agent in that it is much less time consuming (molecular sieves needed in 2 days to dry the catalyst modifier sufficiently and several batches of sieves were required), and more cost effective (the use of sieves led to a decrease in the concentration of catalyst modifier in toluene solution due to catalyst modifier absorption in the sieves, and large amounts of solvent required to sufficiently solubilize the catalyst modifier so as to render efficient contact with the sieves). Sustained Catalyst Preparation
[0304] Sylopol 2408 silica purchased from Grace Davison was calcined by fluidization with air at 200 °C for 2 hours and subsequently with nitrogen at 600 °C for 6 hours. 114.273 grams of the calcined silica was added to 620 ml of toluene. 312.993 g of a MAO solution containing 4.5% by weight of Al purchased from Albemarle was added to the silica suspension quantitatively. The mixture was stirred for 2 hours at room temperature. The agitation rate must be such as not to break the silica particles. 2.742 grams of (1-C6F5CH2-Indenyl)((t-Bu)3P=N)TiCl2 (prepared as above in Example 1) was weighed into a 500 ml Pyrex flask and 300 ml of toluene added. The complex metal solution was added to the silica suspension quantitatively. The resulting suspension was stirred for 2 hours at room temperature. 21.958 g of 18.55% by weight toluene solution of Armostat® 1800 were weighed into a small container and quantitatively transferred to the silica slurry. The resulting mixture was stirred for an additional 30 minutes after the suspension was filtered, providing a clear filtrate. The solid component was washed with toluene (2 x 150 ml) and then with pentane (2 x 150 ml). The final product was vacuum dried between 450 and 200 mtorr and stored under nitrogen until use. The finished catalyst had a light yellow to light orange color. The catalyst had 2.7 wt% Armostat present. Polymerization
[0305]Continuous ethylene/1-hexene gas phase copolymerization experiments were conducted in a 56.4L Technical Scale Reactor (TSR) in continuous gas phase operation (for an example of a TSR reactor setup see Application of Eur. Pat. No. 659,773A1). Ethylene polymerizations were conducted at 75°C to 90°C with a 300 pounds per square inch (psig) total operating pressure gauge. The gas phase compositions for ethylene and 1-hexene were controlled through closed loop process control for values of 65.0 and 0.5 to 2.0 mol%, respectively. Hydrogen was calibrated in the reactor at a molar feed ratio of 0.0008 to 0.0015 relative to the ethylene feed during polymerization. Nitrogen constituted the remainder of the gas phase mixture (approximately 38 mol%). A typical production rate for these conditions is 2.0 to 3.0 kg of polyethylene per hour. A generation bed was used and before starting the polymerization, it was washed with a small amount of triethylaluminum, TEAL to clean the impurities. Prior to the introduction of the catalyst, TEAL was fluxed from the reactor. The catalyst was fed to the reactor along with a small amount of diluted TEAL solution (0.25 wt%) during the initial phase. The addition of TEAL was discontinued once the desired polymer production rate was achieved. Alternatively, the reactor can be started with the catalyst feed line alone during the initial phase of polymerization (i.e., without initially feeding the TEAL solution). The polymerization reaction was started under conditions of low comonomer concentration, followed by stepwise adjustment of the comonomer to ethylene ratio to provide the target polymer density. Steady state polymerization conditions are given in Table 1. Polymer data for the resulting inventive resin 1 is given in Table 2 (C2 = ethylene; C6 = 1-hexene; C6/C2 is the molar feed ratio of each component to the reactor). Film data for inventive film 1 made of inventive resin 1 is given in Table 3. Comparative Example 1 Catalyst System Preparation
[0306]The phosphinimine catalyst compound (1,2-(n-propyl)(C6F5)Cp)Ti(N=P(t-Bu)3)Cl2 was made in a similar manner to the procedure given in U.S. Pat. No. 7,531,602 (see, Example 2). Sustained Catalyst Preparation
[0307] To a suspension of dehydrated silica (122.42 g) in toluene (490 ml) was added a 10% by weight MAO solution (233.84 g of 4.5% by weight Al in toluene) during 10 minutes. The vessel containing MAO was rinsed with toluene (2 x 10 mL) and added to the reaction mixture. The resulting suspension was stirred with an overhead stirrer assembly (200 rpm) for 1 hour at room temperature. To this suspension a toluene solution (46 ml) of (1,2-(n-propyl)(C6F5)Cp)Ti(N=P(t-Bu)3)Cl2 (2.28 g) was added for 10 minutes. This solution may need to be gently heated to 45°C for a brief period (5 minutes) to completely dissolve the molecule. The container containing the molecule was rinsed with toluene (2 x 10 mL) and added to the reaction mixture. After stirring for 2 hours (200 rpm) at room temperature a toluene solution (22 mL) of Armostat-1800 (which was previously dried according to the above method for “Drying a Catalyst Modifier”) at 8.55 % by weight was added to the suspension which was further stirred for 30 minutes. The suspension was filtered and rinsed with toluene (2 x 100 ml) and then with pentane (2 x 100 ml). The catalyst was vacuum dried to less than 1.5 wt% residual volatiles. The solid catalyst was isolated and stored under nitrogen until further use. The catalyst had 2.7 wt% Armostat present. Polymerization
[0308]Continuous ethylene/1-hexene gas phase copolymerization experiments were conducted in a 56.4L Technical Scale Reactor (TSR) in continuous gas phase operation. Ethylene polymerizations were conducted at 75°C to 90°C with a 300 pounds per square inch (psig) total operating pressure gauge. The gas phase compositions for ethylene and 1-hexene were controlled by means of closed-loop process control for values of 65.0 and 0.5 to 2.0 mol%, respectively. Hydrogen was calibrated in the reactor at a molar feed ratio of 0.0008 to 0.0015 relative to the ethylene feed during polymerization. Nitrogen constituted the remainder of the gas phase mixture (approximately 38 mol%). A typical production rate for these conditions is 2.0 to 3.0 kg of polyethylene per hour. Relevant polymerization data is given in Table 1. Polymer data for the resulting comparative resin 1 is given in Table 2. Film data for comparative film 1 made of comparative resin 1 is given in Table 3.Table 1


[0309] Also included in Table 2 are comparative resins 2 to 7. Corresponding film properties for comparative resins 2 to 4 are given in Table 3. Comparative resin 2 is a copolymer of ethylene Exceed 1018TM of 1-hexene, which is commercially available from ExxonMobil. Comparative resin 3 is believed to be a representative resin of Enable 20-05TM that is commercially available from ExxonMobil. Comparative resin 4 is a cast blend of FP-019C and LF-Y819-A. LF-Y819 represents 5% by weight of the molten mixture. Y819-A, is a high pressure low density material having a melt index of 0.75 g/10 min and a density of 0.919 g/cc, available from NOVA Chemicals. FPs-019-C is a linear low density material having a melt index of 0.8 g/10 min and a density of 0.918 g/cc, manufactured using a Ziegler-Natta catalyst, also available from NOVA Chemicals. Comparative resins 5 and 6 are ELITE 5100GTM and ELITE 5400GTM respectively which are manufactured using a double reactor solution process with a mixed catalyst system and are commercially available from the Dow Chemical Company. Comparative resin 7 is DOWLEX 2045GTM, which is made with a Ziegler-Natta catalyst in a solution reactor, and is also commercially available from the Dow Chemical Company.







[0310] As shown in Table 2, the ethylene copolymer composition of the present invention (inv. 1) has a melt flow rate that is distinct from a resin prepared with (1,2-(n-propyl)(C6F5 )Cp)Ti(N=P(t-Bu)3)Cl2 (comp. 1) and commercially available EXCEED 1018CATM (comp. 2). The inventive resins (see, inv. 1 but also inv. 2 to 8 discussed below) have an MFR greater than 30, while comparative resins 1 and 2 each have a melt flow rate less than 30. In addition Furthermore, the copolymer composition of the invention is distinct from an Enable 20-05 resin (comp. 3) which has a similar melt flow rate (MFR of 41.2) but a very different TREF profile. The TREF profile of the inventive resins is multimodal (or trimodal with three prominent peaks separated by 5 °C or more), whereas the resin comp. 3 has a single peak evident in the TREF analysis. Inventive resin 1 as well as inv. 2 to 8, have a distribution width index of the composition CDBI50 less than 70% by weight, while the resin comp. 3 has a CDBI50 greater than 85%. Comparison of inventive resin 1 with ELITE resins (Comparative Examples 5 and 6) shows that although each can have a multimodal TREF profile (note: that Elite resin is a copolymer of ethylene and 1-octene, and the inventive resin is a copolymer of ethylene and 1-hexene), inventive resin 1 has a broader molecular weight distribution (Mw/Mn greater than 3.5) and a higher MFR (I21/I2 is greater than 32). Comparative resin 7, which is DOWLEX 2045G, and is manufactured using a Ziegler-Natta catalyst, has a bimodal TREF profile and an MFR of less than 30.
[0311] When blow molded on film, resin inv. 1 has good dart impact values, good stiffness, and is easy to process as indicated by the low pseudoplastic index (SHI) and high specific output rates.
[0312]As shown in Table 3, the dart impact of resin inv. 1 is quite high at over 600 g/mil and is almost as good as a comp resin. 2, which has a much lower melt flow rate (I21/I2). Resin inv. 1 also has a higher javelin impact value than comparative resins of similar melt index and/or melt flow rate: compare eg resin comp. 3 (an Enable type resin) and comp. 4 (a molten blend of LLDPE and HPLDPE) which have impact values per dart of 473 g/mil and 317 g/mil respectively with inventive resin 1, which has an impact value per dart of 638 g/mil.
[0313]The stiffness of resin inv. 1, as indicated by 1% TD and MD drying modulus is higher compared to comparative resins 2, 3 or 4. As shown in Table 3, inventive resin 1 has a MD drying modulus 1% greater than 190 MPa when blow molded into a 1 mil film. Comparative resins 2, 3, and 4 have a 1% MD drying modulus of 137, 187, and 167 MPa respectively when blow molded into a 1 mil film. Resin inv. 1 has a 1% TD drying modulus greater than 210 MPa when blow molded into 1 mil film. Comparative resins 2, 3 and 4 have a 1% TD drying modulus of 166, 208 and 208 MPa respectively when blow molded into a 1 mil film.
[0314] In terms of processability, inventive resin 1 is extruded with a higher specific output rate at lower head pressure than unmixed comparative resin 2 which has a lower melt flow rate (see, Table 3). The inventive resin 1 has a similar specific output rate compared to the comp resin. 3, but at lower extruder head pressure. The resin comp. 4 is a melt blend comprising a linear low density resin LLDPE and 5% by weight high pressure low density polyethylene resin (HPLDPE) which is known to impart improved processability to an LLDPE due to the presence of long chain branching. Nevertheless, inventive resin 1 shows higher specific output even at lower extruder head pressure than comparative resin 4 (see, Table 3). Inventive Examples 2 to 8
[0315] In a series of additional experiments: i) the amount of Armostat-1800 present in the catalyst system (in % by weight based on the total weight of the polymerization catalyst system); ii) the organotransition metal catalyst bearing on a silica support (in Ti mmol/gram of polymerization catalyst system); and iii) the amount of catalyst activator, methylaluminoxane MAO (in wt% Al based on the total weight of the polymerization catalyst system) was changed to see how the catalyst system responded to changes in its formulation. The catalyst systems used in Inventive Examples 2 to 8 were prepared in substantially the same way and using the same phosphinimine catalyst as the catalyst system described in Inventive Example 1, except that the levels of Armostat-1800, metal organotransition (carrying Ti) or catalyst activator (carrying Al) were changed (see, Table 4A). A total of seven other catalyst system formulations (Table 4A) were prepared and an ethylene copolymer of 1-hexene was prepared in a manner similar to that described above for Inventive Example 1 (see, Table 4B for process conditions of polymerization).
[0316] The catalyst system formulation data and polymerization data are provided in Table 4A and Table 4B respectively and correspond to Inventive Examples 2 to 8 (C2 = ethylene; C6 = 1-hexene; N2 = nitrogen; H2 = hydrogen; C6/C2 is the molar feed ratio of these components to the reactor). Selected product parameters for the resulting ethylene copolymers (inventive ethylene copolymers 2 to 8) are given in Table 5.



[0317] As can be seen in Tables 2 and 5, all inventive resins 1 to 8 have a reverse comonomer distribution, a multimodal TREF profile (eg trimodal), a CDBI50 within the range of 40 to 70% in weight, an MFR within the range of 32 to 50, a Mw/Mn within the range of 3.5 to 6.0, and a partial melt index (I2 less than 1.0). Each of the inventive resins 1 through 8 shown in Tables 2 and 5 also have a unimodal broad molecular weight distribution (see, Figure 2 as representative of the inventive ethylene copolymers).
[0318]A representative TREF curve is shown in Figure 1 for inventive resin 1. A representative GPC curve is shown for inventive resin 1 in Figure 2. A representative GPC-FTIR curve is shown for inventive resin 1 in Figure 3.
[0319] The good processability of the inventive copolymers is also manifested in a polymer architecture model that is based on van Gurp-Palmen (VGP) fusion rheology behavior as determined by dynamic mechanical analysis (DMA), refractive index data (RI) of gel permeation chromatography (GPC) and the melt flow rate information (I21/I2). The model is a polymer processability model, and provides a polymer “processability increase index” (/) that can be usefully applied to distinguish resins having relatively low and relatively high processability.
[0320] A van Gurp-Palmen analysis is a means by which to study a polymer architecture (eg molecular weight distribution, linearity, etc.) as reflected by polymer melt morphology. A VGP curve is simply a representation of the phase angle (δ) versus complex modulus (G*), where the two rheology parameters are obtained using the frequency sweep test in dynamic mechanical analysis (DMA). The processability model represents the effects of resin architecture on VGP parameters such as complex modulus (G*) and phase angle (δ). A change in a VGP curve from a reference value curve or a decrease in phase angles in the middle range of the complex modulus may indicate changes in polymer melt morphology.
[0321] The present processability model still needs to determine a VGP crossover rheology parameter that is defined as the intersection point obtained between the representation of the phase angle (δ) vs. complex modulus (G*) and a representation of the phase angle (δ) vs. complex viscosity (q*). Based on a linear viscoelastic theory, the VGP crossover rheology parameter (δXO) occurs at a frequency (w) that equals unity. It is the phase angle where G* and q* are equivalent. Consequently, the VGP crossover rheology parameter can be determined in a single DMA test.
[0322]The VGP crossover graphical representation for resins sold under the trade names Exceed 1018 (Comp. 2) and Enable (Comp. 3) is included in Figures 4A and 4B respectively. The graphical representation of VGP crossover for inventive resin 1 is shown in Figure 4B. The graphical representation of VGP crossover for comparative resin 1, made according to Comparative Example 1, is included in Figure 4A. Finally, the resin sold under the trade name Elite 5400G (Comp. 6) is included in Figure 4B. VGP crossover points are dependent on the copolymer architecture. Generally, for resins that are easier to process, such as inventive copolymer 1 and comparative resin 3, the VGP phase angle at which crossover occurs defined as δXO is lower than for resins that are more difficult to process , such as comparative copolymers 1 and 2 (compare Figures 4A and 4B). For resins that are easier to process, the shape of the phase angle-complex viscosity curves and the shape of the complex modulus-phase angle curves are skewed a little and more closely resemble mirror images of each other. , in relation to the curves obtained for the resins that are more difficult to process (compare the curves in Figure 4A with the curves in Figure 4B).
[0323] The complex crossover modulus (G*XO) (or alternatively the complex crossover viscosity, n*XO) was found to relate to the melt index, I2 in the following way: (1) G*XO = 6798.3 (I2)-0.9250
[0324] Consequently, a polymer with a higher molecular weight would have a higher complex crossover modulus. The relationship in equation 1 was found to hold regardless of polymer density or molecular weight distribution.
[0325]VGP crossover phase angle δXO will be a function of various resin parameters. Polymer density was found to have a limited effect on the crossover phase angle, independent of other polymer architecture (or microstructural) effects. Molecular weight distribution (Mw/Mn) was found to have an effect on the crossover phase angle of VGP.
[0326]The representation of the crossover phase angle and complex crossover modulus shows that resins having good processability and poor processability can be relatively well differentiated by imposing a restriction on the two crossover parameters of VGP. Consequently, resins that are relatively easy to process will satisfy the inequality (2): (2) δXO < 76.6 - 9 x104 (G*XO).
[0327] In order to remove the effects of molecular weight distribution (MW/Mn) and weight average molecular weight (Mw) on the δXO and consequently to determine effects of polymer architecture (or microstructural) on processability, these effects must be dissociated from the δXO determination to allow the position of different Mw/Mn and Mw resins on the same semi-qualitative scale. For a semi-qualitative measurement of polymer architecture (or microstructural) effects, one has to design experiments to dissociate molecular weight and molecular weight distribution effects on melting rheology parameters.
[0328]A composite structural constraint of δXO--- is derived in order to separate the resin into two groups, according to its melting rheology behavior. Expressing δXO--- as a function of melt flow ratio (I21/I2), and number average molecular weights (Mn) and weight average (Mw) according to inequality (3), the inventive and comparative resins are separated again into two groups having different relative processability: (3) δXO < 96 - 2.14 [(MFR0'5) + 1 x 10 - 4 (Mw - Mn)].
[0329] Figure 5 shows a representation of the line for the equation: δXO = 96 - 2.14 [(MFR0.5) + 1 x 10 - 4 (Mw - Mn)] as well as the plotted data corresponding to the angle values of VGP crossover phase (δXO) and 96 - 2.14 [(MFR0.5) + 1 x 10 - 4 (Mw - Mn)] for inventive resins 1 to 5 and comparative resins 1 to 3 and 5 to 7 .
[0330]The inequality (3) allows molecular weight dissociation and molecular weight distribution effects on δXO including melt flow data and GPC data. As a result, resins of differing molecular weight and molecular weight distribution can be ranked against one another using melt flow, DMA and GPC data only.
[0331]The crossover phase angle δXO- generally follows a relationship with a composite function of the melt flow rate and molecular weights for linear ethylene-α-olefin copolymers. Thus, without wishing to be bound by theory, any changes in the VGP crossover phase angle measured by DMA are here attributed to other aspects of polymer architecture affecting melt rheology. The relative effect of such architectural aspects (or microstructure) on the value of δXO- manifests itself in a greater negative deviation from the reference value defined by inequality (3). Consequently, inequality (3) allows classifying ethylene copolymers according to undefined architectural or microstructure effects in the crossover phase angle, where those architectural/microstructure effects do not include molecular weight or molecular weight distribution.
[0332]The degree to which the phase angle of VGP δXO is different for resins that are easier to process can be evaluated using a processability increase index (%). According to the present model, the processability increase index is defined in a semi-quantitative way in the following equation 4: (4) % = 96 - 2.14 [(MFR0'5) + 1 x 10 - 4 (Mw - Mn)]/δXO.
[0333] % values are close to or greater than unity for polymers that show a significant improvement in the processability of architecture/microstructure polymers and affect less than unity for polymers that show little or no improvement in polymer processability of architecture/microstructure and affect (eg less than about 0.97). As the data in Tables 2 and 5 show, inventive resins 1 to 8 as well as comparative resins 3 and 6 each have a processability increase index % greater than 1.0, while comparative resins 1, 2, 5 and 7 have a processability increase index % less than 1.0. This is fully compatible with the higher output rates and lower currents and pressures associated with blown film of inventive resin 1 and comparative resin 3 versus comparative resins 1 and 2 (see, Table 3). Consequently, in terms of processability, inventive resin 1 as well as comparative resin 3 are similar and better than comparative resins 1 and 2.
[0334] In addition to the above, and as shown in Tables 2 and 5, is the fact that the inventive ethylene copolymers 1 to 8 satisfy the following ratios: (i) (Mw/Mn) > 68 [(I21/I2) -1 + 10 - 6 (Mn)]; and (ii) δXO < [80 - 1.22 (CDB150)/(Mw/Mn)]; where δXO is the crossover phase angle, Mw, M-n, I21, I2 and CDBI50 are all as defined above. The data provided in Table 2 further show that none of the comparative resins 1 to 7 satisfy any of the conditions: (i) (Mw/Mn) > 68 [(121/l2)-1 + 10 - 6 (Mn)] or (ii) δXO < [80 - 1.22 (CDB150)/(Mw/Mn)].
[0335]For other purposes of comparison, the inventive ethylene copolymers 1 to 8 were plotted against several commercially known resins in Figure 6. Figure 6 shows a graphical representation of the equation: (Mw/Mn) = 68 [(l21/l2 )-1 + 10 - 6 (Mn)], as well as a representation of Mw/Mn vs. values 68 [(121/12)-1 + 10 - 6 (Mn)] for resins inv. 1 to 8 and various commercially known resins. The commercial resins included in Figure 6 for comparison purposes are all resins having an Ml of 1.5 or less and a density between 0.916 and 0.930 g/cm3 and which are sold under trade names such as, EliteTM, ExceedTM, MarflexTM, StarflexTM, DowlexTM, SURPASSTM, SCLAlRTM, NOVAPOLTM and EnableTM. As can be seen from Figure 6, none of these commercial grades satisfies the condition: (Mw/Mn) > 68 [(l21/l2)-1 + 10 - 6 (Mn)]. In contrast, all inv. 1 to 8 satisfy the condition: (Mw/Mn) > 68 [(l21/l2)-1 + 10 - 6 (Mn)]. This work demonstrates the distinct architecture of the inventive ethylene copolymers.
[0336]For other purposes of comparison, inventive ethylene copolymers 1 to 8 were plotted against several commercially known resins in Figure 7. Figure 7 shows a graphical representation of the equation: δXO = [80 - 1.22 (CDBl50)/ (Mw/Mn)], as well as a representation of δXO vs. values of [80 - 1.22 (CDBI50)/(Mw/Mn)] for resins inv. 1 to 8 and various commercially known resins. The commercial resins included in Figure 7 for comparison purposes are all resins having an Ml of 1.5 or less and a density between 0.916 and 0.930 g/cm3 and which are sold under trade names such as, EliteTM, ExceedTM, MarflexTM , StarflexTM, DowlexTM, SURPASSTM, SCLAlRTM, NOVAPOLTM and EnableTM. As can be seen from the figure, none of these commercial grades satisfies the condition: <XO < [80 - 1.22 (CDBl5o)/(Mw/Mn)]. In contrast, all inv. 1 to 8 satisfy the condition: δXO < [80 - 1.22 (CDBl50)/(Mw/Mn)]. This work further demonstrates the distinct architecture of the inventive ethylene copolymers. INDUSTRIAL APPLICABILITY
[0337] Copolymerization of ethylene with transition metal catalysts is an important industrial process that provides polymers that are used in numerous commercial applications, such as, for example, film extrusion for use in food packaging. The present invention provides ethylene copolymers which are relatively easy to process and which can be made into film having a good balance of physical properties such as javelin impact and stiffness.

权利要求:
Claims (21)
[0001]
1. Olefin polymerization process to produce an ethylene copolymer, the process CHARACTERIZED in that it comprises placing ethylene and at least one alpha olefin having 3 to 8 carbon atoms into contact with a polymerization catalyst system in a single gas phase reactor; ethylene copolymer having a density of 0.916 g/cm3 to 0.930 g/cm3, a melt index (I2) of 0.1 g/10 min to 1.0 g/10 min, a melt flow rate (I21 /I2) from 32 to 50, a molecular weight distribution (Mw/Mn) from 3.6 to 6.5, a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile, and an index of distribution width of composition CDBI50 from 35% by weight to 70% by weight as determined by TREF; wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, a catalyst activator, and a catalyst modifier; and wherein the only transition metal catalyst is a group 4 phosphinimine catalyst having the formula: (1-R2-Indenyl)Ti(N=P(t-Bu)3)X2; wherein R2 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group, wherein the substituents for the alkyl, aryl or benzyl group are selected from the group consisting of in alkyl, aryl, alkoxy, aryloxy, alkylaryl, arylalkyl and halide substituents; and where X is an activatable ligand.
[0002]
2. Process according to claim 1, CHARACTERIZED by the fact that the ethylene copolymer has a CDBI50 of 45% by weight to 69% by weight.
[0003]
3. Process according to claim 1, CHARACTERIZED by the fact that the ethylene copolymer has a melt index (I2) lower than 1.0 g/10 min.
[0004]
4. Process according to claim 1, CHARACTERIZED by the fact that the multimodal TREF profile comprises three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high); where the T(low) is 62°C to 82°C, the T(average) is 76°C to 89°C, but higher than the T(low), and the T(high) is 90° C to 100°C.
[0005]
5. Process according to claim 1, CHARACTERIZED by the fact that the ethylene copolymer has a Z-average molecular weight distribution (Mz/Mw) from 2.0 to 4.0.
[0006]
6. Process according to claim 1, CHARACTERIZED by the fact that the catalyst activator is an alkylaluminoxane.
[0007]
7. Process according to claim 1, CHARACTERIZED by the fact that the catalyst modifier comprises at least one long-chain amine compound.
[0008]
8. Ethylene Copolymer CHARACTERIZED by the fact that it has a density of 0.916 g/cm3 to 0.930 g/cm3, a melt index (I2) of 0.1 g/10 min to 1.0 g/10 min, a ratio melt flux (I21/I2) from 32 to 50, a molecular weight distribution (Mw/Mn) from 3.6 to 6.5, a reverse comonomer distribution profile as determined by GPC-FTIR, a profile of multimodal TREF, and a CDBI50 composition width distribution index of 45% by weight to 69% by weight as determined by TREF; wherein the ethylene copolymer is made by a process to polymerize ethylene and an alpha olefin having 3 to 8 carbon atoms in a single gas phase reactor in the presence of a polymerization catalyst system comprising a single transition metal catalyst, a support and a catalyst activator; and wherein the only transition metal catalyst is a group 4 phosphinimine catalyst.
[0009]
9. Ethylene copolymer according to claim 8, CHARACTERIZED by the fact that the melt index (I2) is less than 1.0 g/10 min.
[0010]
10. Ethylene copolymer according to claim 8, CHARACTERIZED by the fact that the ethylene copolymer has a T(75)-T(25) of 10°C to 25°C as determined by TREF.
[0011]
11. Ethylene copolymer according to claim 8, CHARACTERIZED by the fact that the ethylene copolymer has a Z-average molecular weight distribution (Mz/Mw) of 2.0 to 4.0.
[0012]
12. Ethylene copolymer according to claim 8, CHARACTERIZED by the fact that the multimodal TREF profile comprises three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high); where the T(low) is 62°C to 82°C, the T(average) is 76°C to 89°C, but higher than the T(low), and the T(high) is 90° C to 100°C.
[0013]
13. Ethylene copolymer according to claim 12, CHARACTERIZED by the fact that the peak intensity at T(low) and T(high) is greater than the peak intensity at T(medium).
[0014]
14. Ethylene copolymer according to claim 12, CHARACTERIZED by the fact that the T(medium)-T(low) is 3°C to 25°C.
[0015]
15. Ethylene copolymer according to claim 12, CHARACTERIZED by the fact that the T(high)-T(medium) is from 5°C to 15°C.
[0016]
16. Ethylene copolymer according to claim 12, CHARACTERIZED by the fact that the T(high)-T(low) is from 15°C to 35°C.
[0017]
17. Ethylene copolymer according to claim 8, CHARACTERIZED by the fact that the amount of ethylene copolymer eluting at a temperature of 90°C to 105°C is 5 to 30% by weight as determined by TREF.
[0018]
18. Ethylene Copolymer CHARACTERIZED by the fact that it has a density of 0.916 g/cm3 to 0.930 g/cm3, a melt index (I2) of 0.2 g/10 min to 0.85 g/10 min, one ratio melt flow (I21/I2) of 36 to 50, a molecular weight distribution (Mw/Mn) of 4.0 to 6.0, a Z-average molecular weight distribution (Mz/Mw) of 2.0 at 4.0, a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile comprising three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high), where the T(low) is 62°C to 82°C, the T(average) is 76°C to 89°C, but higher than the T(low), and the T(high) is 90°C at 100°C, and a CDBI50 composition distribution width index of 45% by weight to 69% by weight as determined by TREF; wherein the ethylene copolymer is made by a process to polymerize ethylene and an alpha olefin having 3 to 8 carbon atoms in a single gas phase reactor in the presence of a polymerization catalyst system comprising a single transition metal catalyst, a support, and a catalyst activator; and wherein the only transition metal catalyst is a Group 4 organotransition metal catalyst.
[0019]
19. Ethylene copolymer that is not a blend CHARACTERIZED by the fact that it has a density of 0.916 g/cm3 to 0.930 g/cm3, a melt index (I2) of 0.2 g/10 min to 0.85 g/ 10 min, a melt flow rate (I21/I2) of 36 to 50, a molecular weight distribution (Mw/Mn) of 4.0 to 6.0, a Z-average molecular weight distribution (Mz/Mw ) from 2.0 to 4.0, a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile comprising three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high), where T(low) is 62°C to 82°C, T(medium) is 76°C to 89°C, but higher than T(low), and T(high) is from 90°C to 100°C, and a distribution width index of the composition CDBI50 from 45% by weight to 69% by weight as determined by TREF.
[0020]
20. Olefin polymerization process to produce an ethylene copolymer, the process CHARACTERIZED in that it comprises placing ethylene and at least one alpha olefin having 3 to 8 carbon atoms in contact with a polymerization catalyst system in a single gas phase reactor to provide an ethylene copolymer having a density of 0.916 g/cm3 to 0.930 g/cm3, a melt index (I2) of 0.2 g/10 min to 0.85 g/10 min, one ratio melt flow (I21/I2) of 36 to 50, a molecular weight distribution (Mw/Mn) of 4.0 to 6.0, a Z-average molecular weight distribution (Mz/Mw) of 2.0 at 4.0, a reverse comonomer distribution profile as determined by GPC-FTIR, a multimodal TREF profile comprising three intensity peaks that occur at elution temperatures T(low), T(medium) and T(high), where the T(low) is 62°C to 82°C, the T(average) is 76°C to 89°C, but higher than the T(low), and the T(high) is 90°C at 100°C, and a distribution width index the composition CDBI50 from 35% by weight to 70% by weight as determined by TREF; wherein the polymerization catalyst system comprises a single transition metal catalyst, a support, and a catalyst activator; and wherein the only transition metal catalyst is a group 4 organotransition metal catalyst having the formula: (1-R2-Indenyl)Ti(N=P(t-Bu)3)X2; wherein R2 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group, wherein the substituents for the alkyl, aryl or benzyl group are selected from the group consisting of from alkyl, aryl, alkoxy, aryloxy, alkylaryl, arylalkyl and halide substituents; and where X is an activatable ligand.
[0021]
21. Ethylene Copolymer CHARACTERIZED by the fact that it has a density of 0.916 g/cm3 to 0.930 g/cm3, a melt index (I2) of 0.1 g/10 min to 1.0 g/10 min, a ratio melt flux (I21/I2) from 32 to 50, a molecular weight distribution (Mw/Mn) from 3.6 to 6.5, a reverse comonomer distribution profile as determined by GPC-FTIR, a profile of Multimodal TREF, and a CDBI50 composition width distribution index of 45% by weight to 69% by weight as determined by TREF, and which satisfies the following relationships: (i) δXO < [80 - 1.22 (CDBl50)/ (Mw/Mn); and (ii) (Mw/Mn) > 68 [(I21/I2)-1 + 10-6 (Mn)]; and δXO < 96 - 2.14 [(MFR0-5) + 1 x 10-4 (Mw - Mn)]; where δXO is the phase angle at which the complex modulus (G*) and complex viscosity (q*) are equivalent in a graph of phase angle versus complex modulus versus complex viscosity as determined by dynamic mechanical analysis; and wherein the ethylene copolymer is made by a process to polymerize ethylene and an alpha olefin having 3 to 8 carbon atoms in a single gas phase reactor in the presence of a polymerization catalyst system comprising a single transition metal catalyst , a support, and a catalyst activator, and wherein the only transition metal catalyst is a group 4 organotransition metal catalyst.

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同族专利:

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公开号 | 公开日

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MX2014014715A|2015-03-04|

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KR20150027235A|2015-03-11|

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BR112014031920A2|2017-06-27|

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CA2798855A1|2013-12-21|

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US9079991B2|2015-07-14|

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JP6211073B2|2017-10-11|

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2020-02-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-12-08| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-03-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-04-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/05/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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CA2780508|2012-06-21|

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CA 2780508|CA2780508A1|2012-06-21|2012-06-21|Polyethylene composition, film and polymerization process|

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CA2798855|2012-12-14|

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CA2798855A|CA2798855C|2012-06-21|2012-12-14|Ethylene copolymers having reverse comonomer incorporation|

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PCT/CA2013/000498|WO2013188950A1|2012-06-21|2013-05-24|Ethylene copolymers, film and polymerization process|

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