POLYMER MIXTURES, FILM STRUCTURES UNDERSTANDING MIXTURE, BLOWED AND MOLDED FILMS UNDERSTANDING MIXTU

专利摘要:
compositions of mixtures of polyethylene and film there is a mixture of polymers comprising a first and a second copolymer of polyethylene, which has good processability, and which, when transformed into film, shows a good balance between resistance-hardness, tear in the md reasonable, as well as good optical properties.
公开号:BR112015015290B1
申请号:R112015015290-2
申请日:2013-12-12
公开日:2021-03-30
发明作者:Patrick Lam；Victoria Ker；Karen Grabow
申请人:Nova Chemicals (International) S.A.；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] A mixture of polymers is presented having good processability, good balance between resistance-hardness, and which shows good optical properties when transformed into films. A polymer blend comprises 5-95% by weight of a first polyethylene copolymer having a density of 0.916 to 0.936 g / cm3, a hot flow rate (I2) of 0.1 to 2.0 g / 10 min , a hot flow rate (I21 / I2) of 32 to 50, a molecular weight distribution (Mw / Mn) of 3.6 to 6.5, an inverted comonomer distribution profile, as determined by GPC-FTIR , a multimodal TREF profile, and a distribution range index of the CDBI50 composition of 45 to 75% by weight, as determined by TREF; and that satisfies at least one of the following relationships: (i) (Mw / Mn)> 72 [(I21 / I2) -1 + 10—6 (Mn)]; (ii) δXO from 55o to 70o; (iii) δXO <83.0 - 1.25 (CDBI50) / (Mw / Mn); and (iv) δXO <80.7 - (CDBI50) / (Mw / Mn) in a δXO from 55o to 70o.
[002] The balance of the polymer mixture comprises a second polyethylene copolymer which is different from the first polyethylene copolymer. BACKGROUND TECHNIQUE
[003] The search for polyethylene products having an improved balance of physical properties and processability has resulted in the development of products having improved production capacity and even an improvement in the properties of end use, such as the increased tear properties of the film or impact by pitch.
[004] The Pub. De Ped. of Pat. US No. 2011/0003099 discusses linear low flow rate hot polyethylene (MFR) and linear high flow rate hot polyethylene (MFR), which are distinguished by an I21 / I2 of less than 30 and a I21 / I2 of more than 30, respectively.
[005] Resins having both a narrow molecular weight distribution and a low hot flow rate are well known and include resins produced with metallocene catalysts and phosphinimine catalysts. Such resins include, for example, ExxedMobil Exceed 1018® and those described in Pat. No. 5,420,220 and in Ped. of Pat. Canadian No. 2,734,167. These resins can be made into films having a good balance of physical and optical properties, but they can be difficult to process in the absence of processing aids, as indicated, for example, by a relatively low production capacity over a blown film line.
[006] Resins having a higher hot flow rate are more attractive to film producers, because they are, in general, easier to process. Pats. U.S. Nos. 6,255,426 and 6,476,171 and Pub. De Ped. of Pat. U.S. No. 2011/0003099 each describes the production and use of resins having fluidity ratios that are in excess of 30 and that have moderately wide molecular weight distributions. Resins are believed to contain significant amounts of long chain branching. The polymers disclosed in Pats. U.S. Nos. 6,255,426 and 6,476,171 are prepared with a bridged bis-indenyl zirconocene catalyst and have a composition distribution width index of more than 75%. Resins have been referred to as Enable® polymers in the patent literature (see, for example, the Example Polymers disclosed in US Pat. Pub. No. 2011/0003099), and although the resins were relatively easy to process , they also maintained a good balance of strength and hardness properties when blown on films. For example, the films had physical properties that were comparable to Exceed 1018 materials, despite their better shear-thinning behavior. The polymers published in Pub. De Ped. of Pat. US No. 2011/0003099 includes a new "Enable" grade resin having a low hot flow rate (I2 = 0.3), a relatively high hot flow rate (I21 / I2 is 46-58) and a moderately wide molecular weight distribution (eg, Mw / Mn is 3.4). Polymers also have a single peak in the TREF profile, with a T (75) -T (25) of less than 4 ° C.
[007] The manipulation of the comonomer distribution profile has also provided new structures for ethylene copolymers, in an effort to improve the balance between the physical properties and the processability of the polymer.
[008] It is generally the case that metallocene catalysts and other so-called "single site catalysts" typically incorporate the comonomer more evenly than traditional Ziegler-Natta catalysts when used for catalytic copolymerization of ethylene with alpha olefins. This fact is often demonstrated by measuring the composition distribution width index (CDBI) for the corresponding ethylene copolymers. The definition of the composition distribution amplitude index (CDBI50) can be found in PCT publication WO 93/03093 and in Pat. No. 5,206,075. CDBI50 is conveniently determined using techniques that isolate the polymer fractions based on their solubility (and, consequently, their comonomer content). For example, fractionation by elution with elevation of temperature (TFEF), as described by Wild et al. J. Poly. Sci., Poly. Phys. Ed. Vol. 20, p441, 1982. From the weight fraction versus composition distribution curve, the CDBI50 is determined by establishing the weight percentage of a copolymer sample that has a comonomer content within 50% of the average comonomer content on each side of the median. In general, Zielger-Natta catalysts produce ethylene copolymers with a lower CDBI50 than that of a single-sided catalyst, in a similar density, consistent with a heterogeneously branched copolymer. Typically, a plurality of protruding peaks are observed for such polymers in an analysis by TREF (fractionation by elution with elevation of temperature). Such peaks are consistent with the presence of heterogeneously branched material, which generally includes a highly branched fraction, an average branched fraction and a higher density fraction having little or no short chain branching. In contrast, metallocenes and other catalysts from a single site will very often produce ethylene copolymers having a CDBI50 greater than that of a Ziegler-Natta catalyst, at a similar density, and which often contain a single protruding peak in an analysis by TREF, consistent with a homogeneously branched copolymer.
[009] Despite the foregoing, methods have been developed to obtain polyethylene copolymer compositions having an extended comonomer distribution (ie, more similar to Ziegler-Natta), while, on the other hand, maintaining the typical product characteristics of resin by metallocene catalyst and a single location, such as high impact resistance for the blown film. Such resins can be prepared, for example, using a mixture of metallocene catalysts in a single reactor, using a plurality of polymerization reactors under different polymerization conditions, or by mixing the ethylene copolymers produced with metallocene.
[010] U.S. Patent Nos. 5,382,603, 5,382,631 and WO 93/03093 describe compositions of polyethylene mixtures having broad or narrow molecular weight distributions, and broad or narrow distributions of comonomers. For example, a mixture can have a narrow molecular weight distribution, while simultaneously having a bimodal composition distribution. Alternatively, a mixture can have a wide molecular weight distribution, while simultaneously having a unimodal composition distribution. The mixtures are prepared by mixing two polyethylene resins with similar or different molecular weights and contents of similar or different comonomers, where each resin is formed using a metallocene catalyst in a gas phase reactor.
[011] Pat. No. 5,548,014 describes metallocene-catalyzed resin mixtures, where one component has a high molecular weight, while the other component has a low molecular weight. The mixtures are suitable for the manufacture of hot melt adhesives.
[012] Pat. 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 mixture of ethylene copolymers, 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 mud phase-gas phase reactor in cascade), shows two distinct maximums in a TREF fractogram. The polymers are applied as a sealing layer to a heat sealable film.
[013] A mixed catalyst system containing an "unsatisfactory comonomer incorporator" and a "good comonomer incorporator" is disclosed in Pats. U.S. Nos. 6,828,394 and 7,141,632. The unsatisfactory comonomer incorporating catalyst may be a metallocene having at least one fused ring cyclopentadienyl linker, such as an indenyl linker, with appropriate substitution (e.g., alkyl substitution in position 1). The good comonomer incorporating catalyst was selected from an array of well-known metallocenes that were, in general, less sterically hindered in relation to the front end of the molecule than the unsatisfactory comonomer incorporator. These mixed catalyst systems produced polyethylene copolymers having a bimodal distribution by TREF, in which two elution peaks are well separated from each other, consistent with the presence of components of higher and lower densities. The mixed catalysts also produced ethylene copolymer having an extended molecular weight distribution with respect to the ethylene copolymer prepared with any of the individual metallocene component catalysts.
[014] A mixed catalyst system comprising three distinct metallocene catalysts is disclosed in U.S. Pat. No. 6,384,158. Copolymers of ethylene having extended molecular weight distributions were obtained when using these catalyst systems to polymerize ethylene with an alpha olefin, such as 1-hexene.
[015] The Pub. Of Ped. of Pat. U.S. No. 2011/0212315 describes a linear ethylene copolymer having a multimodal comonomer distribution profile, as measured using DSC, TREF or CRYSTAF techniques. Copolymers maintain a high resistance to pitch impact when blown on film and are relatively easy to process, as indicated by a reduced shear thinning index, compared to ethylene copolymers having a unimodal comonomer distribution profile. Exemplified ethylene copolymer compositions, which have a hot flow rate of less than 30, are prepared in an individual gas phase reactor, using a mixed catalyst system comprising a metallocene catalyst and a metal catalyst late transition period.
[016] Pat. US No. 7,534,847 demonstrates that the use of a chromium-based transition metal catalyst gives 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 CRYSTAF fractionation.
[017] Pat. No. 6,932,592 describes a very low density ethylene copolymer (i.e., <0.916 g / cm3), produced with a large non-bridged metallocene bis-Cp catalyst. A preferred metallocene is bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride. The examples show that in the gas phase, the supported versions of this catalyst produce copolymer from ethylene and 1-hexene which has a CDBI of between 60 and 70% and a bimodal comonomer distribution, as measured by elution fractionation with elevated temperature (TREF).
[018] Pat. 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 profile by TREF. Polymerization is carried out in the gas phase using a so-called "restricted geometry" catalyst having an indenyl binder.
[019] Pats. U.S. Nos. 6,248,845, 6,528,597, 7,381,783 and the Pub. of Pat. No. 2008/0108768 disclose that a large metallocene with a hafnium-based binder and a small amount of zirconium can be used to provide an ethylene / 1-hexene copolymer that has a bimodal TREF profile. It is taught that the precursor compounds of hafnium chloride used to synthesize large 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 vary from 0.1 mol% to 5 mol%. Consequently, the final hafnocene catalysts contain small amounts (i.e., 0.1 to 5 mol%) of their zirconocene analogs. Since zirconium-based catalysts may have higher activity than their hafnium analogues, it is possible that the prepared products have a significant contribution from zirconocene species. If this is the case, then it may not be surprising that a TREF bimodal profile results. The patent provides data for molded and blown film applications, which shows that, compared to Exceed type resins, polymers are more easily extruded, with less motor load, higher production and reduced top pressure. The resins give molded film with high tear values and blown film with high impact values by pitch.
[020] Pats. U.S. Nos. 6,956,088, 6,936,675, 7,179,876 and 7,172,816 disclose that the use of a large hafnium catalyst with "substantially individual" binder provides an ethylene copolymer composition having a CDBI of below 55%, especially below 45%, as determined by CRYSTAF. Remember that hafnocene catalysts derived from hafnium chloride are expected to have zirconocene contaminants present in low amounts. U.S. Patent Nos. 6,936,675 and 7,179,876 additionally teach that the CDBI could be modified under different temperature conditions when using hafnocene catalysts. Polymerization at lower temperatures gave an ethylene copolymer having a wider composition distribution index (CDBI) in relation to the polymers obtained at higher temperatures. For example, the use of bis (n-propylcyclopentadienyl) hafnium dichloride or bis (n-propylcyclopentadienyl) hafnium catalysts in a gas phase reactor, for the polymerization of ethylene and 1-hexene at <80 ° C, gave copolymers having a CDBI of between 20 and 35%, compared to the CDBI values of between 40 and 50% for copolymers obtained at 85 ° C. Disclosed polymers may, for certain reduction reasons, provide films having a machine-directed tear value of more than 500 g / 25.4 μm, a throw impact resistance of more than 500 g / 25.4 μm, as well as good hardness. Polymers also have good processability. Mixtures of polymers of the type just described, with several differentiated polyethylenes, such as, for example, high density polyethylene, linear low density polyethylene and very low density polyethylene, are disclosed in U.S. Pat. No. 8,247,065.
[021] Pat. No. 5,281,679 describes bis-cyclopentadienyl metallocene catalysts that have secondary or tertiary carbon substituents on a cyclopentadienyl ring. The catalysts provide polyethylene materials with extended molecular weight during gas phase polymerization.
[022] Large cyclic metallocene catalysts with bridging binders are described in Pats. U.S. Nos. 6,339,134 and 6,388,115, which give easier-to-process ethylene polymers.
[023] A hafnocene catalyst is used in Pat. No. 7,875,690 to give an ethylene copolymer in a gas phase fluidized bed reactor. The copolymer has a so-called "wide orthogonal composition distribution", which provides improved physical properties and extractable lows. A wide orthogonal composition distribution is one in which the comonomer is incorporated predominantly into the chains of high molecular weights. The copolymers had a density of at least 0.927 g / cm3. Polyethylene copolymers having a similarly wide distribution of the orthogonal composition, but a lower density, are disclosed in U.S. Pat. No. 8,084,560 and in Pub. De Ped. of Pat. No. 2011 / 0040041A1. Again, a hafnocene catalyst is used in a gas phase reactor to give the ethylene copolymer.
[024] Pat. No. 5,525,689 also discloses the use of a hafnium 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 / cm3, an Mw / Mn of up to 4.0, and were prepared in the gas phase.
[025] Pat. 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. The fluidity ratios of the disclosed polymers are generally below about 30. A cyclopentadienyl / fluorenyl metallocene catalyst, having an unsaturated pendant group, is used to prepare the ethylene copolymers. The patent application does not mention films or film properties.
[026] Pat. No. 6,469,103 discusses ethylene copolymer compositions comprising a first and a second ethylene copolymer component. The individual components are defined using ATREF-DV analytical methods, which show a bimodal or multimodal structure with respect to the arrangement of the comonomer. The compositions have an I10 / I2 value of more than 6.6 and a relatively narrow molecular weight distribution (ie, Mw / Mn is less than, or equal to, 3.3), consistent with the presence of branching long chain. Polymers are prepared using a double solution reaction system with mixed catalysts.
[027] A process for preparing ethylene polymer compositions, involving the use of at least two polymerization reactors, is described in Pat. No. 6,319,989. Ethylene copolymers have a molecular weight distribution of more than 4.0 and show two peaks when subjected to fractionation by crystallization analysis (CRYSTAF).
[028] Pat. US No. 6,462,161 describes the use of a restricted geometry type catalyst or a bridged metallocene bis-Cp catalyst to produce, in a single reactor, a polyolefin composition having long chain branching and a maximum molecular weight occurring in the part of the composition having the highest comonomer content (ie, an inverted comonomer distribution). Compositions prepared with a restricted geometry catalyst have multimodal TREF profiles, and relatively narrow molecular weight distributions (eg, the exemplified resins have an Mw / Mn of 2.19 to 3.4, see Table 1 in examples section of US Pat. No. 6,462,161). Compositions prepared with a bridged metallocene bis-Cp catalyst have complex TREF profiles and a somewhat broader molecular weight distribution (eg, the exemplified resins have an Mw / Mn of 3.43 or 6.0, see Table 1 in the examples section of US Pat. No. 6,462,161).
[029] Ethylene copolymers are taught in Pat. US No. 7,968,659, which have a hot flow index of 1.0 to 2.5, an Mw / Mn of 3.5 to 4.5, an elastic modulus in the G 'fusion (G "= 500 Pa ) of 40 to 150 Pa and a flow activation energy (Ea) in the range of 28 to 45 kJ / mol The restricted geometry catalysts are used to prepare the polymer compositions in the gas phase.
[030] Pat. US No. 7,521,518 describes the use of a restricted geometry catalyst to give an ethylene copolymer composition having an inverted comonomer distribution, as determined by various parameters of cross-fraction chromatography (CFC), and a molecular weight distribution from 2.5 to 10. Polymerization is carried out in the slurry phase. Mixtures of the copolymer composition are described in U.S. Pat. No. 7,166,676.
[031] Pat. No. 5,874,513 describes that the use of a mixture of components that give rise to a supported metallocene catalyst can, in a gas phase reactor, give an ethylene copolymer with reduced homogeneity of the comonomer distribution. The patent defines a parameter of the distribution of the composition Cb that is representative of the distribution of comonomers within the polymer composition. TREF analysis of the copolymer composition showed a bimodal distribution.
[032] Pat. No. 6,441,116 discloses a film comprising an ethylene copolymer with a distribution curve of the composition obtained by TREF having four distinct areas, including an area that defines a peak that is attributed to a highly branched component.
[033] is disclosed in Pat. US No. 5,487,938 an ethylene / alpha olefin copolymer produced with a Ziegler-Natta catalyst and having more than about 17 weight percent of a high density fraction, as determined by analytical TREF methods, and a molecular weight distribution (Mw / Mn) of less than about 3.6. The high density fraction has little short chain branching, although the balance of the copolymer composition is referred to as the fraction containing short chain branching. Consequently, the data is consistent with a bimodal distribution of incorporation of the comonomer in the ethylene copolymer.
[034] Pat. No. 6,642,340 describes an ethylene copolymer having a specific relationship between a melt flow rate and a melt stress. The polymers additionally comprise between 0.5 and 8% by weight of a component eluting at not less than 100 ° C in a TREF analysis.
[035] Pat. US No. 6,359,072 describes a polymer blend comprising from 10 to 90% by weight of a first polyethylene having a molecular weight distribution of 1.5 to 3 and a composition distribution width index (CDBI) of 50 to 80 percent, and 90 to 10% by weight of a second polyethylene having a molecular weight distribution of 3.5 to 15 and a CDBI of 75 to 95 percent. When blown on films, the polymer blend has improved optical properties over the film obtained from the first or second polyethylene alone.
[036] Pat. US No. 5,530,065 describes a mixture of polymers of a polymer per metallocene catalyst, having a narrow molecular weight distribution and a narrow comonomer distribution, and a polymer catalyzed by Ziegler-Natta, having a wide molecular weight distribution and a wide comonomer distribution. Mixtures of polymers give rise to films having good thermal sealing properties. Similarly, Pats. U.S. Nos. 5,844,045, 5,869,575 and 5,677,383 disclose that mixtures of heterogeneously branched resin, prepared with conventional Ziegler-Natta catalysts, with homogeneously branched resin, prepared with a restricted geometry catalyst are also suitable for preparing films.
[037] It is well known to mix high pressure low density polyethylene (HPLDPE) with linear low density polyethylene (LLDPE), to improve the processability of the LLDPE polymer (for an example of a mixture of this type, see WO 95/25141). However, such mixtures typically have unsatisfactory toughness and impact resistance compared to unmatched LLDPE.
[038] For a description of the mixtures comprising a linear low density polyethylene (LLDPE) having a high MFR and a high CDBI, including mixtures with HPLDPE, and of films comprising such mixtures, see: WO 2011/129956, Pats. U.S. Nos. 7,951,873, 7,601,409, 7,235,607, 8,080,294 and Pubs. of Peds. of Pats. U.S. Nos. 2006/0188678, US 2011/0165395, US 2012/0100356, 2011/0003099, 2007/0260016.
[039] There is still a potential for new mix compositions exhibiting a good balance of physical properties and good processability.
[040] We recently developed a new polymer composition with good processability and good physical properties. The polymer composition, which can be prepared with a phosphinimine catalyst, has a density of 0.916 g / cm3 to 0.930 g / cm3, a hot flow index (I2) of 0.1 to 1.0 g / 10 min , a hot flow rate (I21 / I2) of 32 to 50, a molecular weight distribution (Mw / Mn) of 3.6 to 6.0, an inverted comonomer distribution profile, as determined by GPC-FTIR , a multimodal TREF profile, and a distribution width index of the CDBI50 composition of 35 to 70% by weight, as determined by TREF. We now describe polymer blends that comprise a similar polymer composition and find that the copolymer composition improves melt strength, shear thinning behavior and pitch impact properties when combined with other linear low density polyethylene. , and causes a good balance between resistance-hardness, and good optical properties when mixtures comprising the copolymer composition are transformed into films.
[041] The use of phosphinfinine catalysts for the polymerization of gas phase olefins is the subject of U.S. Patent No. 5,965,677. The phosphinimine catalyst is an organometallic compound having a phosphinimine ligand, a cyclopentadienyl type ligand and two activable ligands, 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).
[042] In Ped. of Pat. Copending CA No. 2,734,167, we have shown that adequately substituted phosphinimine catalysts give narrow molecular weight distribution copolymers, which, when turned into films, have shown a good balance of optical and physical properties.
[043] Polymers and films prepared in the gas phase using several catalysts from a single location, including so-called "phosphinimine" catalysts, were disclosed in Advances in Polyolefins II, Napa, California -24 - 27 October 1999 ( "Development of NOVA's Single Site Catalyst Technology for use in the Gas Phase Process" - I. Coulter; D. Jeremic; A. Kazakov; I. McKay).
[044] 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), phosphinimine catalysts containing variously substituted cyclopentadienyl and indenyl ligands were shown to be active in relation to the gas polymerization of ethylene when in supported way.
[045] The Pub. De Ped. of Pat. No. 2008/0045406 discloses a supported phosphinimine catalyst comprising a C6F5-substituted indenyl linker. The catalyst was activated with an ionic activator having an active proton for use in the polymerization of ethylene with 1-hexene.
[046] The Pub. Of Ped. of Pat. No. 2006/0122054 discloses the use of a dual catalyst formulation, one component being a phosphinimine catalyst having an indenyl linker substituted by n-butyl. The patent is directed to the formation of bimodal resins, suitable for application in piping. DISCLOSURE OF THE INVENTION
[047] Polymer blends are provided with good processability, good balance between resistance-hardness, and which shows good optical properties when transformed into films.
[048] A polymer mixture comprising a polyethylene copolymer having a density of 0.916 to 0.936 g / cm3, a hot flow index (I2) of 0.1 to 2.0 g / 10 min is provided, a ratio hot flow (I21 / I2) from 32 to 50, a molecular weight distribution (Mw / Mn) from 3.6 to 6.5, an inverted comonomer distribution profile, as determined by GPC-FTIR, a profile multimodal TREF, a distribution range index of the CDBI50 composition of 45% by weight to 75% by weight, as determined by TREF; and that satisfies at least one of the following relationships: (i) (Mw / Mn)> 72 [(I21 / I2) -1 + 10—6 (Mn)]; (ii) δXO from 55o to 70o; (iii) δXO <83.0 - 1.25 (CDBI50) / (Mw / Mn); and (iv) δXO <80.7 - (CDBI50) / (Mw / Mn) in a δXO from 55o to 70o.
[049] A polymer blend comprising 5-99% by weight, based on the total weight of the polymer blend, of a polyethylene copolymer having a density of 0.916 to 0.936 g / cm3, a flow index at hot (I2) from 0.1 to 2.0 g / 10 min, a hot flow rate (I21 / I2) from 32 to 50, a molecular weight distribution (Mw / Mn) from 3.6 to 6, 5, an inverted comonomer distribution profile, as determined by GPC-FTIR, a multimodal TREF profile, a distribution amplitude index of the CDBI50 composition from 45% by weight to 75% by weight, as determined by TREF; and that satisfies at least one of the following relationships: (i) (Mw / Mn)> 72 [(I21 / I2) -1 + 10—6 (Mn)]; (ii) δXO from 55o to 70o; (iii) δXO <83.0 - 1.25 (CDBI50) / (Mw / Mn); and (iv) δXO <80.7 - (CDBI50) / (Mw / Mn) in a δXO from 55o to 70o.
[050] A polymer mixture is provided comprising: a) 5-95% by weight of a first polyethylene copolymer having a density of 0.916 to 0.936 g / cm3, a hot melt index (I2) of 0.1 at 2.0 g / 10 min, a hot flow rate (I21 / I2) of 32 to 50, a molecular weight distribution (Mw / Mn) of 3.6 to 6.5, a comonomer distribution profile inverted, as determined by GPC-FTIR, a multimodal TREF profile, a distribution amplitude index of the CDBI50 composition from 45% by weight to 75% by weight as determined by TREF and which additionally satisfies the ratio: (Mw / Mn) > 72 [(I21 / I2) -1 + 10-6 (Mn)]; and b) 95-5% by weight of a second polyethylene copolymer which is a linear low density polyethylene (LLDPE) different from the first polyethylene copolymer and having a density of 0.910 to 0.940 g / cm3, a hot flow index ( I2) from 0.2 to 5.0 g / 10 min, and a hot flow rate (I21 / I2) of less than 35.
[051] A polymer mixture is provided comprising: a) 5-95% by weight of a first polyethylene copolymer having a density of 0.916 to 0.936 g / cm3, a hot melt index (I2) of 0.1 at 1.0 g / 10 min, a hot flow rate (I21 / I2) of 32 to 50, a molecular weight distribution (Mw / Mn) of 3.6 to 6.5, a comonomer distribution profile inverted, as determined by GPC-FTIR, a multimodal TREF profile, a distribution amplitude index of the CDBI50 composition from 45% by weight to 75% by weight, as determined by TREF and which additionally satisfies the ratio: (Mw / Mn )> 72 [(I21 / I2) -1 + 10—6 (Mn)]; and b) 95-5% by weight of a second polyethylene copolymer which is a linear low density polyethylene (LLDPE) having a density of 0.910 to 0.940 g / cm3, a hot melt index (I2) of 0.2 to 5.0 g / 10 min, and a hot flow rate (I21 / I2) of less than 32.
[052] A mixture of polymers is provided comprising: a) 5-95% by weight of a first polyethylene copolymer having a density of 0.916 to 0.936 g / cm3, a hot melt index (I2) of 0.1 at 1.0 g / 10 min, a hot flow rate (I21 / I2) of at least 30, a molecular weight distribution (Mw / Mn) of 3.6 to 6.5, a comonomer distribution profile inverted, as determined by GPC-FTIR, a multimodal TREF profile, a distribution amplitude index of the CDBI50 composition from 45% by weight to 75% by weight, as determined by TREF and which additionally satisfies the ratio: (Mw / Mn )> 72 [(I21 / I2) -1 + 10—6 (Mn)]; and b) 95-5% by weight of a second polyethylene copolymer which is a linear low density polyethylene (LLDPE) having a density of 0.910 to 0.940 g / cm3, a hot melt index (I2) of 0.2 to 5.0 g / 10 min, and a hot flow rate (I21 / I2) of less than 35. BRIEF DESCRIPTION OF THE DRAWINGS
[053] Figure 1A shows an analysis by fractionation by elution with elevation of temperature (TREF) and the profile of a first polyethylene copolymer used according to the present invention.
[054] Figure 1B shows an analysis by fractionation by elution with elevation of temperature (TREF) and the profile of a first polyethylene copolymer used according to the present invention.
[055] Figure 2 shows a gel permeation chromatography (GPC) with detection of the refractive index of a first polyethylene copolymer used in accordance with the present invention.
[056] Figure 3 shows a gel permeation chromatography with infrared detection of the Fourier transform (GPC-FTIR) obtained for a first polyethylene copolymer prepared according to the present invention. The comonomer content, shown as the number of short chain branches per 1000 carbons (y-axis), is given in relation to the molecular weight of the copolymer (x-axis). The upward sloping line (from 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 the highest molecular weights and, consequently, the comonomer incorporation is said to be "inverted".
[057] Figure 4A shows graphs of the phase angle vs. the complex modulus and the phase angle vs. the complex viscosity for resins 2A and 2B as determined by dynamic mechanical analysis (DMA).
[058] Figure 4B shows graphs of the phase angle vs. the complex modulus and the phase angle vs. the complex viscosity for resin 1A, as determined by DMA.
[059] Figure 5 shows a graph of the equation: Mw / Mn = 72 [(I21 / I2) -1 + 10-6 (Mn)]. The values of equation 72 [(I21 / I2) -1 + 10-6 (Mn)] (the y axis) are plotted against the corresponding Mw / Mn values (the x axis) for resins 1A-1F, as well as for several commercially available resins that have an I2 hot melt index of 1.5 g / 10 min or less and a density of between 0.916 and 0.930 g / cm3.
[060] Figure 6 shows a graph of the equation: δXO = 83 - 1.25 (CDBI50) / (Mw / Mn). The values of equation 80 - 1.25 (CDBI50 / (Mw / Mn) (the x-axis) are plotted against the corresponding cross-phase angle (δXO) values (the y-axis) for resins 1A-1F, as well as for several commercially available resins that have an I2 hot melt index of 1.5 g / 10 min or less and a density of between 0.916 and 0.930 g / cm3.
[061] Figure 7 shows a graph of the equation: δXO = 80.7 - (CDBI50) / (Mw / Mn). The values of the equation 80.7 - (CDBI50) / (Mw / Mn) (the x-axis) are plotted against the corresponding phase angle (δXO) values (the y-axis) for resins 1A-1F, as well as for several commercially available resins that have a hot melt index I2 of 1.5 g / 10 min or less and a density of between 0.916 and 0.930 g / cm3. The dotted lines show which resins have a δXOde value between 55 ° and 70 °.
[062] Figure 8 shows a graph of the shear thinning ratio (q * 0.1 / q * 1ü) against the weight fraction of the first polyethylene copolymer for the mixtures prepared according to the present invention.
[063] Figure 9 shows a graph of the melt strength (cN) for mixtures and components of mixtures according to various embodiments of the present invention. The Figure also shows a graph of the improvement in melt strength (in percentage) for three different mixtures, prepared according to the invention. BEST MODE FOR CARRYING OUT THE INVENTION
[064] The present invention provides mixtures of polymers that have good processability and melt strength and, when processed into film, have a relatively high impact impact resistance as well as good optical properties.
[065] In one embodiment of the invention, the polymer blend comprises a polyethylene copolymer having a density of 0.916 to 0.936 g / cm3, a hot flow rate (I2) of 0.1 to 2.0 g / 10 min , a hot flow rate (I21 / I2) of 32 to 50, a molecular weight distribution (Mw / Mn) of 3.6 to 6.5, an inverted comonomer distribution profile, as determined by GPC-FTIR , a multimodal TREF profile, and a distribution range index of the CDBI50 composition of 45 to 75% by weight, as determined by TREF; and which satisfies at least one of the following relationships: i) (Mw / Mn)> 72 [(I21 / I2) -1 + 10—6 (Mn)]; ii) δXO from 55o to 70o; iii) δXO <83.0 - 1.25 (CDBI50) / (Mw / Mn); and iv) δXO <80.7 - (CDBI50) / (Mw / Mn) in a δXO from 55o to 70o.
[066] As used herein, the terms "linear low density polyethylene" and "LLDPE" refer to a polyethylene homopolymer or, more preferably, a copolymer having a density of about 0.910 g / cm3 to about 0.945 g / cm3. Unlike high pressure low density polyethylene (HPLDPE), LLDPE is a linear polymer that contains a minimal amount or a relatively small amount, or zero, of long chain branching compared to HPLDPE. HPLDPE, in contrast, is often referred to as "branched", because it has a relatively large number of long-chain branches that extend from the polymeric backbone.
[067] In the present invention, the term "polyethylene copolymer" is used interchangeably with the term "ethylene copolymer", or "copolymer" and both mean a polymer consisting of polymerized ethylene units and at least one type of alpha polymerized olefin, with ethylene being the monomer most present.
[068] Comonomers that are generally useful for preparing polyethylene copolymers include α-olefins, such as C3-C20 alpha-olefins, preferably C3-C10 alpha-olefins, and more preferably alpha-olefins of C3-C8. The α-olefin comomer can be linear or branched, and two or more comonomers can be used, if desired. Examples of suitable comonomers include propylene; 1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl, or propyl substituents; 1-hexene; 1-hexene with one or more methyl, ethyl, or propyl substituents; 1-heptene; 1-heptene with one or more methyl, ethyl, or propyl substituents; 1-octene; 1-octene with one or more methyl, ethyl, or propyl substituents; 1-nonene; 1-nonene with one or more methyl, ethyl, or propyl substituents; 1-decene substituted with ethyl, methyl, or dimethyl; 1-dodecene; and styrene. Specifically, but without limitation, combinations of ethylene with a comonomer can include: ethylene propylene, ethylene butene, ethylene 1-pentene; ethylene 4-methyl-1-pentene; ethylene 1-hexene; ethylene 1-octene; ethylene decene; ethylene dodecene; ethylene 1-hexene 1-pentene; ethylene 1-hexene 4-methyl-1-pentene; ethylene 1-hexene 1-octene; ethylene 1-hexene decene; ethylene 1-hexene dodecene; ethylene 1-octene 1-pentene; ethylene 1-octene 4-methyl-1-pentene; ethylene 1-octene 1-hexene; ethylene 1-octene decene; ethylene 1-octene dodecene; their combinations and similar permutations.
[069] Polyethylene copolymers having more than two types of monomers, such as terpolymers, are also included within the term "copolymer" as used herein.
[070] In the embodiments of the invention, the first and second components of the polyethylene copolymer blend 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. weight of ethylene units, with the balance being an alpha-olefin unit, based on the weight of each component of the mixture.
[071] The term "polymer mixture" is intended in this document to mean a dry mixture of two different polymers, mixtures within the reactor, including mixtures that arise from the use of multiple or mixed catalyst systems in an individual reactor zone, and mixtures that result from the use of one or more catalysts in one or more reactors, under the same or different conditions (eg, a mixture that results from reactors in series, each running under different conditions and / or with different catalysts ).
[072] In one embodiment of the invention, the polymer blend will comprise a first polyethylene copolymer and a second polyethylene copolymer, each of which is further described below. THE FIRST POLYETHYLENE COPOLYMER
[073] The polymer blend of the present invention comprises 1-99% by weight of a first polyethylene copolymer, which, in an embodiment of the invention, has a density of 0.916 g / cm3 to 0.936 g / cm3, an index of hot flow (I2) from 0.1 to 2.0 g / 10 min, a hot flow rate (I21 / I2) of at least 28, a molecular weight distribution (Mw / Mn) of 3.0 to 7.0, an inverted comonomer distribution profile, as determined by GPC-FTIR, a multimodal TREF profile, and a distribution amplitude index of the CDBI50 composition of 35 to 75% by weight, as determined by TREF.
[074] In one embodiment of the invention, the first polyethylene copolymer satisfies the following relationship: (Mw / Mn)> 72 [(I21 / I2) -1 + 10—6 (Mn)], where Mw / Mn is the distribution molecular weight, Mw is the weight average molecular weight, Mn is the numerical average molecular weight, I2 is the hot flow rate in g / 10 min, and I21 is the hot flow rate at high load in g / 10 min.
[075] In the embodiments of the invention, the first polyethylene copolymer has an δXO of less than 70 ° or from 55 ° to 70 °, where δXO is the transverse phase angle of a Van Gurp-Palmen graph (VGP), as determined by dynamic mechanical analysis (DMA).
[076] In one embodiment of the invention, the first polyethylene copolymer satisfies the following ratio: δXO <83.0 - 1.25 (CDBI50) / (Mw / Mn), where δXO is the transverse phase angle of a graph of Van Gurp-Palmen (VGP), as determined by dynamic mechanical analysis (DMA), and CDBI50 is the comonomer distribution quantity index, as determined through TREF analysis.
[077] In one embodiment of the invention, the first polyethylene copolymer satisfies the following relationship: δXO <80.7 - (CDBI50) / (Mw / Mn) at an δXO from 55 ° to 70 °, where δXO is the phase angle cross-section of a Van Gurp-Palmen (VGP) graph, as determined by dynamic mechanical analysis (DMA), and CDBI50 is the comonomer distribution quantity index, as determined through TREF analysis.
[078] In one embodiment of the invention, the first polyethylene copolymer satisfies one or more of the following ratios: i) (Mw / Mn) ^ 72 [(I21 / I2) -1 + 10—6 (Mn)], where Mw / Mn is the molecular weight distribution, Mw is the weight average molecular weight, Mn is the numerical average molecular weight, I2 is the hot flow rate in g / 10 min, and I21 is the hot flow rate under load high in g / 10 min; ii) δXO from 55 ° to 70 °, where δXO is the transverse phase angle of a Van Gurp-Palmen graph (VGP), as determined by dynamic mechanical analysis (DMA); iii) δXO <83.0 - 1.25 (CDBI50) / (Mw / Mn), where δXO is the transverse phase angle of a Van Gurp-Palmen graph (VGP), as determined by dynamic mechanical analysis (DMA) , and CDBI50 is the comonomer distribution quantity index, as determined through TREF analysis; and iv) δXO <80.7 - (CDBI50) / (Mw / Mn) in a δXO from 55o to 70o, where δXO is the transverse phase angle of a Van Gurp-Palmen graph (VGP), as determined by analysis dynamic mechanics (DMA), and CDBI50 is the comonomer distribution quantity index, as determined through TREF analysis.
[079] In the embodiments of the invention, the first polyethylene copolymer is an ethylene copolymer and an alpha olefin selected from 1-butene, 1-hexene and 1-octene.
[080] In one embodiment of the invention, the first polyethylene copolymer is a copolymer of ethylene and 1-hexene.
[081] In the embodiments of the invention, the composition of the first polyethylene copolymer 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 ethylene units , with the balance being an alpha-olefin unit, based on the weight of the ethylene copolymer composition.
[082] In the embodiments of the invention, the first polyethylene copolymer will have a hot melt index (I2) of 0.01 to 3.0 g / 10 min, or 0.1 to 2.5 g / 10 min, or from 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 0.1 to less than 1.0 g / 10 min, or 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. In the embodiments of the invention, the first polyethylene copolymer will have a hot melt index (I2) of more than 1.0 to 2.0 g / 10 min, or of more than 1.0 to 1.75 g / 10 min, or more than 1.0 to 1.5 g / 10 min.
[083] In one embodiment of the invention, the first polyethylene copolymer has a hot melt index (I2) of less than 1.0 g / 10 min.
[084] In one embodiment of the invention, the first polyethylene copolymer has a hot melt index (I2) of 0.25 to 0.80 g / 10 min.
[085] In the embodiments of the invention, the first polyethylene copolymer will have a density of 0.916 g / cm3 to 0.936 g / cm3, including the narrowest bands within this range, such as, for example, from 0.916 g / cm3 to 0.935 g / cm3, or from 0.916 g / cm3 to 0.932 g / cm3, or from 0.916 g / cm3 to 0.930 g / cm3, or from 0.917 g / cm3 to 0.932 g / cm3, or from 0.917 g / cm3 to 0.930 g / cm3 , or from 0.916 g / cm3 to 0.925 g / cm3, or from 0.917 g / cm3 to 0.927 g / cm3, or from 0.917 g / cm3 to 0.926 g / cm3, or from 0.917 g / cm3 to 0.925 g / cm3, or from 0.917 g / cm3 to 0.923 g / cm3, or from 0.918 g / cm3 to 0.932 g / cm3, or from 0.918 g / cm3 to 0.930 g / cm3, or from 0.918 to 0.930 g / cm3, or from 0.918 to 0.928 g / cm3, or from 0.920 to 0.935 (note: "g" means gram; "cm3" means cubic centimeter, cm3).
[086] In one embodiment of the invention, the first polyethylene copolymer will have a density of 0.916 g / cm3 to 0.936 g / cm3. In one embodiment of the invention, the first polyethylene copolymer will have a density from more than 0.916 g / cm3 to less than 0.930 g / cm3. In one embodiment of the invention, the first polyethylene copolymer will have a density of 0.917 g / cm3 to 0.927 g / cm3. In one embodiment of the invention, the composition of the first polyethylene copolymer will have a density of 0.918 g / cm3 to 0.927 g / cm3.
[087] The first polyethylene copolymer of the present invention can have a unimodal, wide unimodal, bimodal, or multimodal profile, in a gel permeation chromatography (GPC) curve generated according to the ASTM D6474-99 method. The term "unimodal" is defined here to mean that there will only be a significant peak or maximum evident on the GPC curve. A unimodal profile includes a wide unimodal profile. By the term "bimodal" it is intended that there will be a secondary peak or shoulder that represents a component of greater or lesser molecular weight (i.e., the molecular weight distribution can be said to have two maxima in a molecular weight distribution curve). Alternatively, the term "bimodal" means the presence of two maxima in a molecular weight distribution curve generated according to the ASTM D6474-99 method. The term "multimodal" means the presence of two or more maximums in a molecular weight distribution curve generated according to the ASTM D6474-99 method.
[088] In one embodiment of the invention, the first polyethylene copolymer will have a unimodal profile on a gel permeation chromatography (GPC) curve generated according to the ASTM D6474-99 method. The term "unimodal" is defined here to mean that there will only be a significant peak or maximum evident on the GPC curve. A unimodal profile includes a wide unimodal distribution profile or curve.
[089] In the embodiments of the invention, the first polyethylene copolymer will exhibit a weight average molecular weight (MW) as determined by gel permeation chromatography (GPC) from 30,000 to 250,000, including the narrowest 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 130,000.
[090] In the embodiments of the invention, the first polyethylene copolymer will exhibit a numerical average molecular weight (Mn) as determined by gel permeation chromatography (GPC) from 5,000 to 100,000, including the narrowest ranges within this range, such as, 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.
[091] In the embodiments of the invention, the first polyethylene copolymer will exhibit an average molecular weight Z (MZ) as determined by gel permeation chromatography (GPC) from 50,000 to 1,000,000, including the narrowest ranges within this range, such as such as 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 375,000, or from 175,000 to 400,000, or from 200,000 to 400,000, or 225,000 to 375,000.
[092] In the embodiments of the invention, the first polyethylene copolymer will have a molecular weight distribution (Mw / Mn) as determined by gel permeation chromatography (GPC) from 3.0 to 7.0, including the narrowest ranges within this range, such as, for example, from 3.5 to 7.0, or from 3.5 to 6.5, or from 3.0 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 from 3.5 to 5.0, or from 4.0 to 6.0, or from 4.0 to 5.5.
[093] In one embodiment of the invention, the first polyethylene copolymer has a molecular weight distribution (Mw / Mn) of 4.0 to 5.5.
[094] In the embodiments of the invention, the first polyethylene copolymer will have an average molecular weight distribution Z (Mz / Mw) as determined by gel permeation chromatography (GPC) from 2.0 to 5.5, including the most narrow within this range, such as, for example, 2.0 to 5.0, or 2.0 to 4.5, or 2.0 to 4.0, or 2.0 to 2.5, or from 2.0 to 3.0, or from 2.0 to 3.5.
[095] In one embodiment of the invention, the first polyethylene copolymer has an average molecular weight distribution Z (Mz / Mw) of 2.0 to 4.0.
[096] In one embodiment of the invention, the first ethylene copolymer will have a fixed comonomer incorporation profile, as measured using Gel Permeation Chromatography with Fourier Transform Infrared detection (GPC-FTIR). In one embodiment of the invention, the first ethylene copolymer will have a negative (i.e. "normal") comonomer incorporation profile, as measured using GPC-FTIR. In one embodiment of the invention, the first ethylene copolymer will have an inverted (i.e., "inverse") or partially inverted comonomer embedding profile, as measured using GPC-FTIR. If the comonomer incorporation decreases with molecular weight, as measured using GPC-FTIR, the distribution is described as "normal" or "negative". If the comonomer incorporation is approximately constant with the molecular weight, as measured using GPC-FTIR, the comonomer distribution is described as "fixed" or "uniform". The terms "inverted comonomer distribution" and "partially inverted 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 one or more segments of smaller molecular weights. The term "inverted comonomer distribution" is used in this document to mean that, across the molecular weight range of the ethylene copolymer, the comonomer contents for the various polymer fractions are not substantially uniform and their larger molecular weight fractions have proportionally higher comonomer contents (ie, if the comonomer incorporation increases with molecular weight, the distribution is described as "inverted" or "inverse"). Where incorporation of the comonomer increases with increasing molecular weight and then decreases slightly, or where incorporation of the comonomer initially decreases with molecular weight and then increases in even greater molecular weight, the distribution of the comonomer is still considered "inverted", but also be described as "partially inverted".
[097] In one embodiment of the invention, the first polyethylene copolymer will have an inverted comonomer incorporation profile, as measured using GPC-FTIR.
[098] In one embodiment of the invention, the first polyethylene copolymer will have a comonomer incorporation profile, as determined by GPC-FTIR, which satisfies the following condition: SCB / 1000 in PM of 200,000 - SCB / 1000 in PM of 50,000 is a positive number or greater than 1.0; where "-" is a minus sign, SCB / 1000 is the comonomer content determined as the number of short chain branches per thousand carbons and PM is the corresponding molecular weight (ie, the absolute molecular weight) in a GPC or GPC chromatography -FTIR.
[099] In one embodiment of the invention, the first polyethylene copolymer will have a comonomer incorporation profile as determined by GPC-FTIR that satisfies the following condition: SCB / 1000 in PM of 200,000 - SCB / 1000 in PM of 50,000> 2 , 0; where SCB / 1000 is the comonomer content determined as the number of short chain branches per thousand carbons and PM is the corresponding molecular weight (i.e., the absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0100] In one embodiment of the invention, the first polyethylene copolymer will have a comonomer incorporation profile as determined by GPC-FTIR that satisfies the following condition: SCB / 1000C in PM of 200,000 - SCB / 1000C in PM of 50,000> 3 , 0; where SCB / 1000C is the comonomer content determined as the number of short chain branches per thousand carbons and PM is the corresponding molecular weight (i.e., the absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0101] In one embodiment of the invention, the first polyethylene copolymer will have a comonomer incorporation profile as determined by GPC-FTIR that satisfies the following condition: SCB / 1000C in PM of 200,000 - SCB / 1000C in PM of 50,000> 4 , 0; where SCB / 1000C is the comonomer content determined as the number of short chain branches per thousand carbons and PM is the corresponding molecular weight (i.e., the absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0102] In one embodiment of the invention, the first polyethylene copolymer will have a comonomer incorporation profile as determined by GPC-FTIR that satisfies the following condition: SCB / 1000 in PM of 200,000 - SCB / 1000 in PM of 50,000> 5 , 0; where SCB / 1000 is the comonomer content determined as the number of short chain branches per thousand carbons and PM is the corresponding molecular weight (i.e., the absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0103] In one embodiment of the invention, the first polyethylene copolymer will have a comonomer incorporation profile as determined by GPC-FTIR that satisfies the following condition: SCB / 1000 in PM of 200,000 - SCB / 1000 in PM of 50,000> 6 , 0; where SCB / 1000 is the comonomer content determined as the number of short chain branches per thousand carbons and PM is the corresponding molecular weight (i.e., the absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0104] In one embodiment of the invention, the first polyethylene copolymer will have a comonomer incorporation profile as determined by GPC-FTIR that satisfies the following condition: SCB / 1000C in PM of 200,000 - SCB / 1000C in PM of 50,000 of 2 , 0 to 8.0, including the narrowest ranges within this range; where SCB / 1000C is the comonomer content determined as the number of short chain branches per thousand carbons and PM is the corresponding molecular weight (i.e., the absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0105] In one embodiment of the invention, the first polyethylene copolymer will have a comonomer incorporation profile as determined by GPC-FTIR that satisfies the following condition: SCB / 1000C in PM of 200,000 - SCB / 1000C in PM of 50,000 of 3 , 0 to 7.0, including the narrowest ranges within this range; where SCB / 1000C is the comonomer content determined as the number of short chain branches per thousand carbons and PM is the corresponding molecular weight (i.e., the absolute molecular weight) in a GPC or GPC-FTIR chromatography.
[0106] In the embodiments of the invention, the first polyethylene copolymer will have a hot flow rate (the MFR = I21 / I2) of 28 to 60, or 30 to 60 or 32 to 60. In the additional embodiments of the invention, the copolymer will have an I21 / I2 of at least 28, or at least 30, or 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 36 to 48, or 36 to 46, or 35 to 50, or more than 35 to less than 50, or more than 35 to 50.
[0107] In one embodiment of the invention, the first polyethylene copolymer has a hot flow rate (I21 / I2) of 32 to 50. In one embodiment of the invention, the first polyethylene copolymer has a hot flow rate ( I21 / I2) from 35 to 50. In one embodiment of the invention, the first polyethylene copolymer has a hot flow rate (I21 / I2) of 36 to 50.
[0108] In the embodiments of the invention, the first polyethylene copolymer will have a distribution amplitude index of the composition CDBI50, as determined by fractionation by temperature elution (TREF), from 40% to 75% by weight, or from 45% to 75% by weight, or from 50% to 75% by weight, or from 55% to 75% by weight, or from 60% to 75% by weight. In the embodiments of the invention, the first polyethylene copolymer will have a CDBI50 of 50% to 70%, or 55% to 70%, or 50% to 69%, or 55% to 69%, or 55% to 65% , or from 60% to 75%, or from 60% to 70%, or from 60% to 69%, or from 55% to 67%, or from 60% to 66% (by weight).
[0109] In one embodiment of the invention, the first polyethylene copolymer has a CDBI50 of 50% by weight to 77% by weight. In one embodiment of the invention, the first polyethylene copolymer has a CDBI50 of 55% by weight to 75% by weight. In one embodiment of the invention, the first polyethylene copolymer has a CDBI50 of 60% by weight to 73% by weight.
[0110] The distribution of the composition of a polyethylene copolymer can also be characterized by the value of T (75) -T (25), where T (25) is the temperature at which 25% by weight of the eluted copolymer is obtained, and T (75) is the temperature at which 75% by weight of the eluted copolymer is obtained, in a TREF experiment, as described in the Examples section.
[0111] In one embodiment of the present invention, the first polyethylene copolymer will have a T (75) -T (25) of 5 to 25 ° C, as determined by TREF. In one embodiment of the present invention, the first polyethylene copolymer will have a T (75) -T (25) of 7 to 25 ° C, as determined by TREF. In one embodiment of the present invention, the first polyethylene 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 first polyethylene copolymer will have a T (75) -T (25) of 7 to 22.5 ° C, as determined by TREF. In one embodiment of the present invention, the first polyethylene copolymer will have a T (75) -T (25) of 7.0 at 20 ° C, as determined by TREF. In one embodiment of the present invention, the first polyethylene copolymer will have a T (75) -T (25) of 5 to 17.5 ° C, as determined by TREF. In one embodiment of the present invention, the first polyethylene copolymer will have a T (75) -T (25) of 7 to 17.5 ° C, as determined by TREF.
[0112] In the embodiments of the invention, the first polyethylene copolymer will have a parameter a of CY (also called the 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 0.30, or from 0.05 to 0.25.
[0113] In the embodiments of the invention, the first polyethylene copolymer will have a normalized shear thinning index, SHI at 0.1 rad / s (ie  * 0.1 / 0) 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.
[0114] In one embodiment of the invention, the first polyethylene copolymer will have a TREF profile, as measured by fractionation by elution with elevation of the temperature, which is multimodal, comprising at least two maximums or peaks of elution intensity.
[0115] In one embodiment of the invention, the first polyethylene copolymer will have an amount of copolymer, eluting at a temperature at or below 40 ° C, of less than 5% by weight, as determined by fractionation by elevation elution temperature (TREF).
[0116] In one embodiment of the invention, the first polyethylene copolymer will have an amount of copolymer, eluting at a temperature of 90 ° C to 105 ° C, from 5 to 30% by weight, as determined by elution fractionation with elevation of temperature (TREF). In an embodiment of the invention, 5 to 25% by weight of the first polyethylene copolymer will be represented within a temperature range of 90 ° C to 105 ° C in a TREF profile. In an embodiment of the invention, 7.5 to 25% by weight of the first polyethylene copolymer will be represented within a temperature range of 90 ° C to 105 ° C in a TREF profile. In an embodiment of the invention, 10 to 25% by weight of the first polyethylene 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 5 to 22.5% by weight of the first polyethylene 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 5 to 20.0% by weight of the first polyethylene copolymer will be represented in a temperature range of 90 ° C to 105 ° C in a TREF profile.
[0117] In the 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 first polyethylene copolymer will elute in a temperature of over 100 ° C in an analysis by TREF.
[0118] In one embodiment of the invention, the first polyethylene copolymer will have a TREF profile, as measured by elution fractionation with temperature rise, comprising: i) a multimodal TREF profile comprising at least two highs (or peaks) of elution intensity; ii) less than 5% by weight of the copolymer represented at a temperature at or below 40 ° C; and iii) from 5 to 25% by weight of the copolymer represented at a temperature of 90 ° C to 105 ° C.
[0119] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile comprising at least two maximums (or peaks) of elution intensity.
[0120] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by at least two maxima (or peaks) of intensity occurring at the eluting temperatures T (low), and T (high), where T (low) is 60 ° C to 87 ° C, and T (high) is 88 ° C to 100 ° C.
[0121] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by at least two maxima (or peaks) of intensity occurring at the eluting temperatures T (low), and T (high), where T (low) is 62 ° C to 87 ° C, and T (high) is 89 ° C to 100 ° C.
[0122] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by at least two maxima (or peaks) of intensity occurring at the eluting temperatures T (low), and T (high), where T (low) is 65 ° C to 85 ° C, and T (high) is 90 ° C to 100 ° C.
[0123] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by at least two maxima (or peaks) of intensity occurring at the eluting temperatures T (low), and T (high), where T (low) is 65 ° C to 85 ° C, and T (high) is 90 ° C to 98 ° C.
[0124] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by at least two maxima (or peaks) of intensity occurring at the eluting temperatures T (low), and T (high), where T (low) is 70 ° C to 85 ° C, and T (high) is 90 ° C to 98 ° C.
[0125] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by at least two maxima (or peaks) of intensity occurring at the eluting temperatures T (low), and T (high), where T (low) is 70 ° C to 80 ° C, and T (high) is 90 ° C to 98 ° C.
[0126] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by at least two maxima (or peaks) of intensity occurring at the eluting temperatures T (low), and T (high), where T (low) is 70 ° C to 80 ° C, and T (high) is 90 ° C to 95 ° C.
[0127] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by at least two maximums (or peaks) of elution intensity occurring at the elution temperatures T (low), and T (high), where (high) -T (low) is 7.5 ° C to 35 ° C, or 10.0 ° C to 30 ° C, or 12.5 ° C to 30 ° C, or 7.0 ° C to 27 ° C, or 7 ° C to 25 ° C, or 10 ° C to 27 ° C, or 10 ° C to 25 ° C, or 10 ° C to 22.5 ° C, or from 12.5 ° C to 22.5 ° C.
[0128] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by at least two maxima (or peaks) of intensity occurring at the eluting temperatures T (low), and T (high), where T (low) is 65 ° C to 85 ° C, and T (high) is 90 ° C to 98 ° C, where (high) -T (low) is 7.5 ° C to 35 ° C, or from 10.0 ° C to 30 ° C, or from 12.5 ° C to 30 ° C, or from 7.0 ° C to 27 ° C, or from 7 ° C to 25 ° C, or from 10 ° C at 27 ° C, or from 10 ° C to 25 ° C, or from 10 ° C to 22.5 ° C, or from 12.5 ° C to 22.5 ° C.
[0129] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile comprising at least three maximums (or peaks) of elution intensity.
[0130] In one embodiment of the invention, the first polyethylene copolymer has a trimodal TREF profile comprising three maximums (or peaks) of elution intensity.
[0131] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at the elution temperatures T (low), T (average or "average" for abbreviate) and T (high), where the intensity of the T (low) and T (high) peaks is greater than the intensity of the peak in T (average).
[0132] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at the elution temperatures T (low), T (average or "average" for abbreviate) and T (high), where T (low) is 60 ° C to 87 ° C, T (high) is 88 ° C to 100 ° C, and T (average) is greater than T (low) , but less than T (high).
[0133] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at the elution temperatures T (low), T (average or "average" for abbreviate) and T (high), where T (low) is 62 ° C to 87 ° C, T (high) is 89 ° C to 100 ° C, and T (average) is greater than T (low) , but less than T (high).
[0134] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at the elution temperatures T (low), T (average or "average" for abbreviate) and T (high), where T (low) is 65 ° C to 85 ° C, T (high) is 90 ° C to 100 ° C, and T (average) is greater than T (low) , but less than T (high).
[0135] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at the elution temperatures T (low), T (average or "average" for abbreviate) and T (high), where T (low) is 65 ° C to 85 ° C, T (high) is 90 ° C to 98 ° C, and T (average) is greater than T (low) , but less than T (high).
[0136] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at the elution temperatures T (low), T (average or "average" for abbreviate) and T (high), where T (low) is 65 ° C to 80 ° C, T (high) is 90 ° C to 98 ° C, and T (average) is greater than T (low) , but less than T (high).
[0137] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at the elution temperatures T (low), T (average or "average" for abbreviate) and T (high), where T (low) is 65 ° C to 87 ° C, T (high) is 88 ° C to 100 ° C, and T (average) is greater than T (low) , but less than T (high), where (high) -T (low) is 7.5 ° C to 35 ° C, or 10.0 ° C to 30 ° C, or 12.5 ° C at 30 ° C, or from 7.0 ° C to 27 ° C, or from 7 ° C to 25 ° C, or from 10 ° C to 27 ° C, or from 10 ° C to 25 ° C.
[0138] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at the elution temperatures T (low), T (average or "average" for abbreviate) and T (high), where T (low) is 62 ° C to 82 ° C, T (average) is 76 ° C to 89 ° C, but is greater than T (low), and T ( high) is 90 ° C to 100 ° C. In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at elution temperatures T (low), T (mean or "mean" for short) and T (high), where T (low) is 65 ° C to 80 ° C, T (average) is 75 ° C to 90 ° C, but is greater than T (low), and T (high) is from 90 ° C to 100 ° C, but it is greater than T (mean). In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at elution temperatures T (low), T (mean or "mean" for short) and T (high), where T (low) is 67 ° C to 78 ° C, T (average) is 79 ° C to 89 ° C, and T (high) is 90 ° C to 100 ° C. In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at elution temperatures T (low), T (mean or "mean" for short) and T (high), where T (low) is 67 ° C to 78 ° C, T (average) is 80 ° C to 87 ° C, and T (high) is 88 ° C to 98 ° C.
[0139] In the embodiments of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at the elution temperatures T (low), T (mean or "mean" for short) ) and T (high), where T (average) -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.
[0140] In the embodiments of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at the elution temperatures T (low), T (mean or "mean" for short) ) and T (high), where 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 5 ° C to 17 ° C, or 5 ° C to 15 ° C, or 7 ° C to 17 ° C, or 7 ° C to 15 ° C or 10 ° C to 17 ° C, or 10 ° C to 15 ° C.
[0141] In the embodiments of the invention, the first polyethylene copolymer has a multimodal TREF profile defined by three maximums (or peaks) of elution intensity occurring at the elution temperatures T (low), T (mean or "mean" for short) ) and T (high), where T (high) -T (low) is 15 ° C to 35 ° C, or 15 ° C to 30 ° C, or 17 ° C to 30 ° C, or 15 ° C to 27 ° C, or 17 ° C to 27 ° C, or 20 ° C to 30 ° C or 20 ° C to 27 ° C, or 15 ° C to 25 ° C or 15 ° C at 22.5 ° C.
[0142] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile comprising three maximums (or peaks) of elution intensity occurring at elution temperatures T (low), T (mean or "mean" for short) ) and T (high), where the intensity of the T (low) and T (high) peaks is greater than the intensity of the peak in T (average); and where T (mean) -T (low) is from 3 ° C to 25 ° C; where T (high) -T (average) is 5 ° C to 15 ° C; and where T (high) -T (low) is 15 ° C to 35 ° C.
[0143] In one embodiment of the invention, the first polyethylene copolymer has a multimodal TREF profile comprising three maximums (or peaks) of elution intensity occurring at elution temperatures T (low), T (mean or "mean" for short) ) and T (high), where the intensity of the T (low) and T (high) peaks is greater than the intensity of the peak in T (average); and where T (mean) -T (low) is 3 ° C to 15 ° C; where T (high) -T (average) is 5 ° C to 15 ° C; and where T (high) -T (low) is 15 ° C to 30 ° C.
[0144] In one embodiment of the invention, the first polyethylene copolymer has two melting peaks, as measured by differential scanning calorimetry (DSC).
[0145] In the embodiments of the invention, the first polyethylene copolymer will have a hexane extractable 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 first polyethylene copolymer has a hexane extractable level of 0.2 to 3.0% by weight, or 0.2 to 2.5% by weight, or 0.2 to 2 , 0% by weight, or from 0.2 to 1.0% by weight. THE SECOND POLYETHYLENE COPOLYMER
[0146] The polymer blend of the present invention can comprise from 99 to 1% by weight of the second polyethylene copolymer. Preferably, the second polyethylene copolymer is a linear low density polyethylene (LLDPE). The second polyethylene copolymer is preferably a different polymer than the first polyethylene copolymer. The second polyethylene copolymer can be distinguished from the first polyethylene copolymer differing in at least one property or characteristic. As a non-limiting example, the second polyethylene copolymer can be distinguished from the first polyethylene copolymer not satisfying the following relationship: (Mw / Mn)> 72 [(I21 / I2) -1 + 10—6 (Mn)]. Alternatively, and also by way of non-limiting example, the second polyethylene copolymer can be distinguished from the first polyethylene copolymer having a hot flow rate (I21 / I2) less than the first polyethylene copolymer.
[0147] In one embodiment of the invention, the second polyethylene copolymer has a density of about 0.910 g / cm3 to about 0.940 g / cm3. In one embodiment of the invention, p second polyethylene copolymer will have a density ranging from a minimum of about 0.910 g / cm3, or about 0.912 g / cm3, or about 0.915 g / cm3, or about 0.916 g / cm3, or about 0.917 g / cm3 to a maximum of about 0.927 g / cm3, or about 0.930 g / cm3, or about 0.935 g / cm3, or about 0.940 g / cm3. In one embodiment of the invention, the second polyethylene copolymer will have a density of 0.912 g / cm3 to 0.940 g / cm3, or 0.915 g / cm3 to 0.935 g / cm3, or 0.915 to 0.930 g / cm3, or 0.916 to 0.930 g / cm3, or from 0.915 to 0.925 g / cm3, or from 0.916 to 0.924 g / cm3, or from 0.917 to 0.923 g / cm3, or from 0.918 to about 0.922 g / cm3.
[0148] In one embodiment of the invention, the second polyethylene copolymer will have a molecular weight distribution (Mw / Mn) of about 1.5 to about 6.0. In the embodiments of the invention, the second polyethylene copolymer will have a molecular weight distribution (Mw / Mn) ranging from a minimum of about 1.5, or about 1.7, or about 2.0, or about 2 , 5, or about 3.0, or about 3.5, or about 3.7, or about 4.0 to a maximum of about 5, or about 5.25, or about 5, 5, or about 6.0. In the embodiments of the invention, the second polyethylene copolymer will have a molecular weight distribution (Mw / Mn) of 1.7 to 5.0, or 1.5 to 4.0, or 1.8 to 3.5, or 2.0 to 3.0. Alternatively, in the embodiments of the invention, the second polyethylene copolymer will have a molecular weight distribution (Mw / Mn) of 3.6 to 5.4, or 3.8 to 5.1, or 3.9 to 4, 9.
[0149] In one embodiment of the invention, the second polyethylene copolymer will have a hot melt index (I2) of 0.1 g / 10 min to 20 g / 10 min. In the embodiments of the invention, the second polyethylene copolymer will have a hot melt index (I2) ranging from 0.75 g / 10 min to 15 g / 10 min, or from 0.85 g / 10 min to 10 g / 10 min, or from 0.9 g / 10 min to 8 g / 10 min. In the embodiments of the invention, the second polyethylene copolymer will have a hot melt index (I2) ranging from a minimum of about 0.20 g / 10 min, or 0.25 g / 10 min, or about 0.5 g / 10 min, or about 0.75 g / 10 min, or about 1 g / 10 min, or about 2 g / 10 min up to a maximum of about 3 g / 10 min, or about 4 g / 10 min, or about 5 g / 10 min.
[0150] In the embodiments of the invention, the second polyethylene copolymer will have a hot melt index (I2) of about 0.75 g / 10 min to about 6 g / 10 min, or about 1 g / 10 min at about 8 g / 10 min, or from about 0.8 g / 10 min to about 6 g / 10 min, or from about 1 g / 10 min to about 4.5 g / 10 min, or from 0.20 g / 10 min to 5.0 g / 10 min, or from 0.30 g / 10 min to 5.0 g / 10 min, or from 0.40 g / 10 min to 5.0 g / 10 min, or from 0.50 g / 10 min to 5.0 g / 10 min.
[0151] In the embodiments of the invention, the second polyethylene copolymer will have a hot flow rate (I21 / I2) of less than about 36, or less than 35, or less than 32, or less than 30 In the embodiments of the invention, the second polyethylene copolymer will have a hot flow rate (I21 / I2) of 10 to 36, or 10 to 35, or 10 to 32, or 10 to 30, or 12 to 35 or from 12 to 32, or from 12 to 30, or from 14 to 27, or from 14 to 25, or from 14 to 22, or from 15 to 20.
[0152] In an embodiment of the invention, the second polyethylene copolymer will have a CBDI50 of> 50 weight percent or a CBDI50 of <50 weight percent, as determined by TREF analysis.
[0153] In the embodiments of the invention, the second polyethylene copolymer will have a distribution amplitude index of the composition CDBI50, as determined by fractionation by temperature elution (TREF), from 25% to 95% by weight, or from 35 to 90 % by weight, or from 40% to 85% by weight, or from 40% to 80% by weight. CATALYSTS AND PROCESS
[0154] The first and second polyethylene copolymers can be prepared using any suitable catalyst, including, for example, so-called single-site catalysts, or Ziegler-Natta catalysts or traditional chrome-based catalysts. Processes such as solution-phase polymerization, gas-phase polymerization or slurry-phase polymerization can be employed to prepare the first and second polyethylene copolymers.
[0155] Illustrative Ziegler-Natta catalyst compounds are disclosed in Ziegler Catalysts 363-386 (G. Fink, R. Mulhaupt and H.H. Brintzinger, eds., Springer-Verlag 1995); in European Patents Nos. EP 103120; EP 102503; EP 231102; EP 703246; in U.S. Patent Nos. 4,115,639; 4,077,904; 4,302,565; 4,302,566; 4,482,687; 4,564,605; 4,721,763; 4,879,359; 4,960,741; 5,518,973; 5,525,678; 5,288,933; 5,290,745; 5,093,415; and 6,562,905; and U.S. Patent Application Publication No. 2008/0194780. Examples of such catalysts include those comprising Group 4, 5 or 6 transition metal oxides, alkoxides and halides, or titanium, zirconium or vanadium oxides, alkoxides and halide compounds; optionally in combination with a magnesium compound, internal and / or external electron donors (alcohols, ethers, siloxanes, etc.), alkyl and alkyl aluminum or boron halides, and inorganic oxide supports.
[0156] Illustrative examples of chromium based polymerization catalysts include Phillps polymerization catalysts, chromium oxide catalysts, silyl chromate catalysts, and chromocene catalysts, examples of which are described, for example, in Pats. U.S. Nos. 4,077,904, 4,115,639, 2,825,721, 3,023,203, 3,622,251, 4,011,382, 3,704,287, 4,100,105 and in the Pub. of Pat. US No. US20120302707 and references therein.
[0157] Single site catalysts include, for example, phosphinimine catalysts (which have at least one phosphinimine linker), metallocene catalysts (which have two cyclopentadienyl type ligands), and restricted geometry catalysts ( which have a starch-type binder and a cyclopentadienyl-type binder).
[0158] Some non-limiting examples of phosphinimine catalysts can be found in Pats. U.S. Nos. 6,342,463; 6,235,672; 6,372,864; 6,984,695; 6,063,879; 6,777,509 and 6,277,931, all of which are incorporated by reference in this document.
[0159] Some non-limiting examples of metallocene catalysts, which may or may not be useful, can be found in Pats. 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 by reference in this document.
[0160] Some non-limiting examples of restricted geometry catalysts, which may or may not be useful, can be found in Pats. 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 by reference in this document in their entirety.
[0161] In some embodiments, an activator can be used with the catalyst compound. As used herein, the term "activator" refers to any compound or combination of compounds, supported or unsupported, that can activate a catalyst component or component, such as creating a cationic species of the catalyst component. Illustrative activators include, but are not limited to, aluminoxane (eg, methylaluminoxane "MAO"), modified aluminoxane (eg, modified methylaluminoxane "MMAO" and / or tetraisobutyldialuminoxane "TIBAO"), alkylaluminum compounds, ionization activators (neutral or ionic), such as tri (n-butyl) ammonium tetrakis (pentafluorfenyl) boron and their combinations.
[0162] The catalyst compositions can include a carrier material or vehicle. As used herein, the terms "support" and "vehicle" are used interchangeably and are any support material, including a porous support material, for example, talc, inorganic oxides, and inorganic chlorides. The catalyst activator (s) and / or catalyst activator (s) may be deposited on, contacted with, vaporized with, attached to, or incorporated into, adsorbed or absorbed into, or over, one or more more supports or vehicles. The other support materials may include resinous support materials, such as polystyrene, functionalized or cross-linked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic support material or inorganic and the like, or mixtures thereof. Suitable catalyst supports are discussed and described, for example, in Hlatky, Chem. Rev. (2000), 100, 1347 1376 and Fink et al, Chem. Rev. (2000), 100, 1377 1390, in U.S. Patent Nos. 4,701,432; 4,808,561; 4,912,075; 4,925,821; 4,937,217; 5,008,228; 5,238,892; 5,240,894; 5,332,706; 5,346,925; 5,422,325; 5,466,649; 5,466,766; 5,468,702; 5,529,965; 5,554,704; 5,629,253; 5,639,835; 5,625,015; 5,643,847; 5,665,665; 5,698,487; 5,714,424; 5,723,400; 5,723,402; 5,731,261; 5,759,940; 5,767,032; 5,770,664; and 5,972,510; and PCT Publications Nos. WO 95/32995; WO 95/14044; WO 96/06187; WO 97/02297; WO 99/47598; WO 99/48605; and WO 99/50311.
[0163] In one embodiment of the invention, the first polyethylene copolymer is prepared with a polymerization catalyst system comprising a phosphinimine catalyst.
[0164] In one embodiment of the invention, the first polyethylene copolymer is prepared using a catalyst system that comprises a phosphinimine catalyst, a support and a catalyst activator.
[0165] In one embodiment of the invention, the first polyethylene copolymer is prepared in the gas phase, using a catalyst system comprising a phosphinimine catalyst, a support, and a catalyst activator.
[0166] In one embodiment of the invention, the first polyethylene copolymer is prepared in a single gas phase reactor, using a catalyst system comprising a phosphinimine catalyst, a support, and a catalyst activator.
[0167] Preferably, the phosphinimine catalyst is based on group 4 metals, which includes titanium, hafnium and zirconium. The most preferred phosphinimine catalysts are group 4 metal complexes in their highest oxidation state.
[0168] The phosphinfinine catalysts described in this document typically require activation by one or more cocatalytic or activator species, to provide the polymer from olefins.
[0169] A phosphinimine catalyst is a compound (typically an organometallic compound) based on a group 3, 4 or 5 metal and which is characterized as having at least one phosphinimine binder. Any compounds / complexes having a phosphinimine linker and which show catalytic activity for ethylene (co) polymerization can be called "phosphinimine catalysts".
[0170] In one embodiment of the invention, a phosphinimine catalyst is defined by the formula: (L) n (PI) mMXp, where M is a transition metal selected from Ti, Hf, Zr, PI is a phosphinimine ligand ; L is a cyclopentadienyl type ligand; X is an activable ligand; m is 1 or 2; n is 0 or 1; and p is determined by the valence of the metal M. Preferably, m is 1, n is 1 and p is 2.
[0171] In one embodiment of the invention, a phosphinimine catalyst is defined by the formula: (L) (PI) MX2, where M is a transition metal selected from Ti, Hf, Zr; PI is a phosphinimine linker; L is a cyclopentadienyl type ligand; and X is an activable ligand.
[0172] In one embodiment of the invention, the phosphinimine catalyst will have a phosphinimine ligand that is not bridged to, or does not bridge with, another ligand within the metal coordination sphere of the phosphinimine catalyst, such as, for example, a cyclopentadienyl-type ligand.
[0173] In one embodiment of the invention, the phosphinimine catalyst will have a cyclopentadienyl-type ligand that is not bridged to, or does not bridge with, another ligand within the metal coordination sphere of the phosphinimine catalyst, such as , for example, a phosphinimine linker.
[0174] The phosphinimine ligand is defined by the formula: R13P = N-, where each R1 is independently selected from the group consisting of a hydrogen atom; a halogen atom; a C1-30 hydrocarbyl radical that is unsubstituted or additionally substituted by one or more halogen atoms; a C1-20 alkyl radical; a C1-8 alkoxy radical; a C6-10 aryl or aryloxy radical; a starch radical; a silyl radical; and a Germanyl radical; P is phosphorus and N is nitrogen (and it binds to metal M).
[0175] In one 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 the tri- (butyl tertiary) phosphinimine (i.e., where each R1 is a tertiary butyl group).
[0176] As used in this document, the term "cyclopentadienyl type" binder is intended to include binders that contain at least one five-carbon ring that is attached to the metal by means of the eta-5 bond (or, in some cases, eta -3). Thus, the term "cyclopentadienyl type" includes, for example, unsubstituted cyclopentadienyl, individual or multiply substituted cyclopentadienyl, unsubstituted indenyl, individual or multiply substituted indenyl, unsubstituted fluorenyl and individual or multiply substituted fluorenyl. The hydrogenated versions of the indenyl and fluorenyl binders are also contemplated for use in the present invention, as long as the five-carbon ring that bonds to the metal via the eta-5 bond (or, in some cases, eta-3) remains intact . Substituents for a cyclopentadienyl ligand, an indenyl ligand (or its hydrogenated version) and a fluorenyl ligand (or its hydrogenated version) can be selected from the group consisting of a C1-30 hydrocarbyl radical (this hydrocarbyl radical which can be unsubstituted or additionally substituted, for example, by a halide and / or a hydrocarbyl group, for example, a suitable substituted C1-30 hydrocarbyl radical is a pentafluorbenzyl 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); a starch radical that is unsubstituted or substituted by up to two C 1-8 alkyl radicals; a phosphide radical, which is unsubstituted or substituted by up to two C1-8 alkyl radicals; a silyl radical of the formula -Si (R ') 3, where 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.
[0177] The term "perfluorinated aryl group" means that each hydrogen atom attached to a carbon atom in an aryl group has been replaced by a fluorine atom, as is well understood in the art (eg, a perfluorinated phenyl group or substituent has the formula -C6F5).
[0178] In one embodiment of the invention, the phosphinimine catalyst will have an individual or multiply substituted indenyl linker and a phosphinimine linker that is replaced by three tertiary butyl substituents.
[0179] An indenyl linker (or "Ind" for short) as defined in the present invention will have carbon atoms of structure with the numbering scheme provided below, so that the position of a substituent can be readily identified.

[0180] In one embodiment of the invention, the phosphinimine catalyst will have an individually substituted indenyl linker and a phosphinimine linker that is replaced by three tertiary butyl substituents.
[0181] In one embodiment of the invention, the phosphinimine catalyst will have an individual or multiply substituted indenyl linker, where the substituent is selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or an un-aryl group substituted, and a substituted or unsubstituted benzyl group (ie, 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, (eg, a benzyl group), arylalkyl groups and halide groups.
[0182] In one embodiment of the invention, the phosphinimine catalyst will have an individually substituted indenyl linker, R2-Indenyl, where the R2 substituent is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group; or an unsubstituted or substituted benzyl group. Suitable substituents for an R2 alkyl, R2 aryl or R2 benzyl group can be selected from the group consisting of alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylaryl groups (eg, a benzyl group), groups arylalkyl and halide groups.
[0183] In one embodiment of the invention, the phosphinimine catalyst will have an indenyl linker having at least one substituent in the 1 (1-R2) position, 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 R2 alkyl, R2 aryl or R2 benzyl group can be selected from the group consisting of alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylaryl groups (eg, a benzyl group), groups arylalkyl and halide groups.
[0184] In one embodiment of the invention, the phosphinimine catalyst will have an individually substituted indenyl linker, 1-R2-Indenyl, where the R2 substituent is in position 1 of the indenyl linker and is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted benzyl group or an unsubstituted one. Suitable substituents for an R2 alkyl, R2 aryl or R2 benzyl group can be selected from the group consisting of alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylaryl groups (eg, a benzyl group), groups arylalkyl and halide groups.
[0185] In one embodiment of the invention, the phosphinimine catalyst will have an individually substituted indenyl linker, 1-R2-Indenyl, where the R2 substituent is a halide-substituted alkyl group (partially / totally), a halogen-substituted benzyl group (partially / totally), or a halide substituted aryl group (partially / totally).
[0186] In one embodiment of the invention, the phosphinimine catalyst will have an individually substituted indenyl linker, 1-R2-Indenyl, where the R2 substituent is a benzyl group substituted with halide (partially / totally).
[0187] When present on an indenyl binder, a benzyl group can be partially or totally replaced by halide atoms, preferably fluoride atoms. The aryl group of the benzyl group can be a perfluorinated aryl group, a fluorine-substituted phenyl group at 2.6 (ie, ortho), a fluorine-substituted phenyl group at 2.4.6 (ie, ortho / para) or a fluorine-substituted phenyl group in 2,3,5,6 (ie, ortho / meta), respectively. The benzyl group is, in an embodiment of the invention, located at the position of the indenyl ligand.
[0188] In one embodiment of the invention, the phosphinimine catalyst will have an individually substituted indenyl linker, 1-R2-Indenyl, where the R2 substituent is a pentafluorbenzyl group (C6F5CH2-).
[0189] 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 , a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group, where the substituents for the alkyl, aryl or benzyl group are selected from the group consisting of alkyl, aryl, alkoxy, aryloxy, alkylaryl substituents , arylalkyl and halide; M is Ti, Zr or Hf; and X is an activable ligand.
[0190] 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 an alkyl group, an aryl group or a benzyl group and where each of the alkyl group, the aryl group, and the benzyl group can be unsubstituted or substituted by at least one fluorine atom; M is Ti, Zr or Hf; and X is an activable ligand.
[0191] 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 an alkyl group, an aryl group or a benzyl group and where each of the alkyl group, the aryl group, and the benzyl group can be unsubstituted or substituted by at least one halide atom; M is Ti, Zr or Hf; and X is an activable ligand.
[0192] In one 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, an aryl group or a benzyl group and where each of the alkyl group, the aryl group, and the benzyl group can be unsubstituted or substituted by at least one fluorine atom; and X is an activable ligand.
[0193] In one 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 activable ligand.
[0194] In one embodiment of the invention, the phosphinimine catalyst has the formula: (1-C6F5CH2-Ind) Ti (N = P (t-Bu) 3) X2, where X is an activable ligand.
[0195] In the present invention, the term "activable" means that ligand X can be cleaved from the center of metal M by means of a protonolysis reaction or separated from the center of metal M by suitable acid or electrophilic catalyst activating compounds (also known as "cocatalyst compounds"), respectively, the examples of which are described below. The activable linker X can also be transformed into another linker, which is cleaved or separated from the center of the metal M (eg, a halide can be converted to an alkyl group). Without wishing to be bound by any individual theory, the protonolysis or separation reactions generate a center of the active "cationic" metal, which can polymerize the olefins.
[0196] In the embodiments of the present invention, the activable 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, where each of the hydrocarbyl, alkoxy, aryl, or aryl oxide radicals can be unsubstituted or additionally substituted by one or more halogens or other groups; a C1-8 alkyl; a C1-8 alkoxy, a C6-10 aryl or aryloxy; a starch or a phosphide radical, but where X is not a cyclopentadienyl. Two X linkers can also be joined together and form, for example, a substituted or unsubstituted diene linker (eg, 1,3-butadiene); or a displaced 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 C 1-4 alkyl radical and a benzyl radical.
[0197] Particularly suitable activable binders are monoanionic, such as a halide (eg, chloride) or a hydrocarbyl (eg, methyl, benzyl).
[0198] The catalyst activator used to activate the phosphinimine 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.
[0199] Without wishing to be bound by theory, it is believed that the alkylaluminoxanes are complex aluminum compounds of the formula: R32Al1O (R3Al1O) mAl1R32, where each R3 is independently selected from the group consisting of C1-20 hydrocarbyl radicals in 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.
[0200] In one embodiment of the invention, R3 of the alkylaluminoxane is a methyl radical and m is 10 to 40.
[0201] In one embodiment of the invention, the cocatalyst is methylaluminoxane (MAO).
[0202] In one embodiment of the invention, the cocatalyst is modified methylaluminoxane (MMAO).
[0203] Alkylaluminoxanes are typically used in substantial molar excess compared to the amount of the group 4 transition metal in the phosphinimine catalyst. The molar ratios of Al1: transition metal of group 4 can be from about 10: 1 to about 10,000: 1, preferably from about 30: 1 to about 500: 1.
[0204] It is well known in the art that alkylaluminoxane can serve dual roles, both as an alkylating agent and as an activator. Consequently, an alkylaluminoxane activator is often used in combination with activable binders, such as halogens.
[0205] Alternatively, the catalyst activator of the present invention can be a combination of an alkylating agent (which can also act as a remover) with an activator capable of ionizing the group 4 of the phosphinimine catalyst metal catalyst (ie, a ionic activator). In this context, the activator can be chosen from one or more alkylaluminoxanes and / or an ionic activator, since an alkylaluminoxane can act both as an activator and as an alkylating agent.
[0206] When present, the alkylating agent can be selected from the group consisting of (R4) p MgX22-p, where 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, where R4 is as defined above, (R4) qZnX22-q, where R4 is as defined above, X2 is halogen and q is 1 or 2; (R4) s Al2X23-s, where R4 is as defined above, X2 is halogen and s is an integer from 1 to 3. Preferably, in the compounds described above, 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). Alkylaluminoxanes can also be used as alkylating agents.
[0207] 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 an aromatic cation of Cyclic C5-7 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 an atom fluorine, a C14 alkyl or alkoxy radical that is unsubstituted or substituted by a fluorine atom; and a silyl radical of the formula --Si - (R7) 3; where 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] -, where 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, considered together with the nitrogen atom, can form an anilinium radical and R6 is as defined above; and (iii) compounds of the formula B (R6) 3, where R6 is as defined above.
[0208] In the aforementioned compounds, preferably R6 is a pentafluorphenyl radical, and R5 is a triphenylmethyl cation, Z is a nitrogen atom and R8 is a C1-4 or R8 alkyl radical, considered together with the nitrogen atom , forms an anilinium radical that is replaced by two C1-4 alkyl radicals.
[0209] Examples of compounds capable of ionizing the phosphinimine 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 (pentafluorfenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammon tetra (p-trifluoro) boron, tributylammonium tetra (pentafluorfenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron, N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N- diethylanilinium tetra (phenyl) n-butylboro, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron, di- (isopropyl) ammonium tetra (pentafluorfenyl) boron, dicyclohexylammonium tetra (phenyl) boron, triphenylphosphonium tetra) phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, tri (dimethylphenyl) phosphonium tetra (phenyl) boron, tetraquispentafluorfenyl borate, tetraquispentafluorfenil bora triphenylmethylene, benzene tetraquispentafluorfenyl borate (diazonium), tropilium phenyltrispentafluorfenyl borate, phenyltrispentafluorphenyl borate, benzene (diazonium), tetraphenyltril (2,5), tetraphenyl (2,5), tetrachen (2,5). tetrakis (2,3,5,6-tetrafluorfenil) triphenylmethyl borate, tetrakis (3,4,5-trifluorfenil) benzene (diazonium) borate, tetrakis (3,4,5-trifluorfenil) tropilium borate, tetrakis (3 , 4,5-trifluorphenyl) benzene (diazonium) borate, tetrakis (1,2,2-trifluorethenyl) tropilium borate, tetrakis (1,2,2-trifluorethenyl) trophenylmethyl borate, tetrakis (1,2,2- trifluorethenyl) benzene (diazonium) borate, tetrakis (2,3,4,5-tetrafluorfenyl) tropilium borate, tetrakis (2,3,4,5-tetrafluorfenil) triphenylmethyl borate, and tetrakis (2,3,4, Benzene 5-tetrafluorfenyl) borate (diazonium).
[0210] Commercially available activators that are capable of ionizing the phosphinimine catalyst include: N, N-dimethylanilinium tetraquispentafluorfenyl borate ("[Me2NHPh] [B (C6F5) 4]"); triphenylmethyl tetraquispentafluorfenyl borate ("[Ph3C] [B (C6F5) 4]"); and trispentafluorfenil boron.
[0211] In one embodiment of the invention, the ion activating compounds can be used in amounts that provide a molar ratio of transition metal from group 4 to boron that will be from 1: 1 to 1: 6.
[0212] Optionally, mixtures of alkylaluminoxanes and ionic activators can be used as activators for the phosphinimine catalyst.
[0213] 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 that is supported on an inert support.
[0214] The inert support used in the present invention can be any support that is known in the art to be 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.). Consequently, the supports include metal oxides of Groups 2, 3, 4, 5, 13 and 14, in general, such as silica, alumina, silica-alumina, magnesium oxide, magnesium chloride, zirconia, titania, clay (eg montmorillonite) and their mixtures.
[0215] Agglomerate supports, such as silica and clay agglomerates, can also be used as a support in the present invention.
[0216] The supports are, in general, used in the calcined form. An inorganic oxide support, for example, will contain acidic surface hydroxyl groups, which will react with a polymerization catalyst. Before use, inorganic oxide can be dehydrated to remove water and 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 mmoles / g of support, or 0.5 to 3 mmoles / 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.
[0217] 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 cm3 / 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 m2 / g, a pore volume in the range of about 0.5 to about 3.5 cm3 / g and a size 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 m2 / g, a pore volume in the range of about 0.8 to about 3.0 cm3 / g and a size average particle size of about 5 to about 100 μm.
[0218] The support material, especially an inorganic oxide, typically has an average pore size (i.e., pore diameter) of about 10 to about 1000 Angstroms (Â). In a more specific embodiment, the support material has an average pore size of about 50 to about 500Â °. In another more specific embodiment, the support material has an average pore size of about 75 to about 350Â °.
[0219] 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 the Journal of the American Chemical Society, 1938, v 60, pages 309-319.
[0220] 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 of Sylopol® 958, 955 and 2408 by Davison Catalysts, a Division of W. R. Grace and Company, and ES-70W by Ineos Silica.
[0221] Agglomerate supports comprising a clay mineral and an inorganic oxide can be prepared using various practices well known in the art, including pelletizing, extrusion, drying or precipitation, spray drying, molding into globules in a rotating coating drum, and the like. A lump-turning technique can also be used. Methods for preparing agglomerate supports comprising a clay mineral and an inorganic oxide include spray drying a slurry of a clay mineral and an inorganic oxide. Methods for preparing agglomerate supports comprising a clay mineral 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.
[0222] An agglomerate of clay and inorganic oxide, which is useful in the present invention, can have the following properties: a surface area of about 20 to about 800 m2 / g, preferably 50 to about 600 m2 / g ; particles with an apparent density of about 0.15 to about 1 g / ml, preferably from about 0.20 to about 0.75 g / ml; an average pore diameter of about 30 to about 300 Angstroms (A), preferably about 60 to about 150 A; a total pore volume of about 0.10 to about 2.0 cm 3 / g, preferably about 0.5 to about 1.8 cm 3 / g; and an average particle size of about 4 to 250 microns (μm), preferably about 8 to 100 microns.
[0223] Alternatively, a support, for example, a silica support, can be treated with one or more salts of the type: Zr (SO4> 4H2O, ZrO (NO3) 2, and Fe (NO3) 3, as taught in the Order Canadian Copending Patent 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.
[0224] The present invention is not limited to any particular procedure for supporting a phosphinimine catalyst or other components of the catalyst system. The processes for depositing such catalysts, as well as an activator, on a support are well known in the art (for some non-limiting examples of methods of supporting catalysts, see "Supported Catalysts" by James H. Clark and Duncan J. Macquarrie, published online November 15, 2002 at Kirk-Othmer Encyclopedia of Chemical Technology Copyright © 2001 by John Wiley & Sons, Inc .; for some non-limiting methods for supporting a single site catalyst, see US Patent No. 5,965 .677). For example, a phosphinimine catalyst can be added to a support by coprecipitation with the support material. The activator can be added to the support before and / or after the phosphinimine catalyst or together with the phosphinimine catalyst. Optionally, the activator can be added to a phosphinimine catalyst supported in situ or a phosphinimine catalyst can be added to the support in situ or a phosphinimine catalyst can be added to an activator supported in situ. A phosphinimine catalyst can be converted to a slurry or dissolved in a suitable diluent or solvent and then added to the support. Suitable solvents or thinners include, but are not limited to, hydrocarbons and mineral oil. A phosphinimine catalyst, for example, can be added to the solid support, in the form of a solid, solution or slurry, followed by the addition of the activator in solid form or as a solution or slurry. The phosphinimine catalyst, the activator, and the support can be mixed together, in the presence or absence of a solvent.
[0225] A "catalyst modifier" can also be added to the phosphinimine based catalyst system and is a compound that, when added to a polymerization catalyst system or used in the presence of it in appropriate amounts, can reduce, prevent or slow down at least one: fouling, plaque formation, and rapid and sudden rise in temperature, and static level of a material in the polymerization reactor; it can change the kinetics of the catalyst; and / or can change the properties of the copolymer product obtained in a polymerization process.
[0226] Non-limiting examples of catalyst modifiers that can be used in the present invention are Kemamine AS-990®, Kemamine AS-650®, Armostat-1800®, bis-hydroxy-cocoamine, 2,2'-octadecyl-amino -bisethanol, and Atmer-163®.
[0227] Other catalyst modifiers can be used in the present invention and include compounds, such as salts of carboxylate metals (see U.S. Patent Nos. 6,562,924; 6,022,935 and 5,283,278 for the examples). Polyoxyethylenealkylamines, which are described, for example, in Ped. of Pat. European No. 107.127, can also be used. Additional catalyst modifiers include aluminum stearate and aluminum oleate. The catalyst modifiers are supplied commercially under the trademarks OCTASTAT® and STADIS®. The 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 polysulfone copolymer, a polymeric amine and an oil-soluble sulfonic acid.
[0228] A long chain amine 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 Ped. of Pat. Copending CA No. 2,742,461. The long chain amine can be a long chain substituted monoalkanolamine, or a long chain substituted dialcanolamine, as described in Ped. of Pat. Copending CA No. 2,742,461, which is incorporated herein in its entirety.
[0229] Detailed descriptions of the polymerization processes in slurry are widely described in the patent literature. For example, particle polymerization, or a slurry process, where the temperature is kept below the temperature at which the polymer enters the solution, is described in U.S. Patent No. 3,248,179. The other slurry processes include those that employ a loop reactor and those that use a plurality of parallel, series stirred reactors, or combinations thereof. Non-limiting examples of slurry processes include continuous loop or agitated tank processes. Additional examples of slurry processes are described in U.S. Patent No. 4,613,484.
[0230] The slurry phase polymerization processes are carried out 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., normal butane and / or isobutane), pentanes, hexanes, heptanes and octanes. The monomers can be soluble in (or miscible with) the diluent, however the polymer is not (under the conditions of polymerization). The polymerization temperature is preferably from about 5 ° C to about 200 ° C, more 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 in the form of solid particles. The reaction pressure is influenced by the choice of the diluent and the reaction temperature. For example, pressures can range from 1500 to 4600 kPa (about 220 to 660 psi or about 15 to about 45 atmospheres), when isobutane is used as the diluent (see, for example, US Patent No. 4,325 .849), approximately twice that (ie, 3000 to 9100 kPa - about 440 to 1300 psi or about 30-90 atmospheres). The pressure in a slurry process must be kept high enough to keep at least part of the ethylene monomer in the liquid phase. The reaction typically takes place in a closed-circuit, jacketed reactor, having an internal stirrer (eg, an impeller) and at least one deposition support. The catalyst, monomers and diluents are fed to the reactor as liquids or suspensions. The slurry circulates through the reactor and the jacket is used to control the temperature of the reactor. Through a series of reduction valves, the slurry enters a deposition support and is then reduced in pressure to instantly vaporize the unreacted diluent and monomers and recover the polymer, in general, in a cyclone. The diluent and unreacted monomers are recovered and recycled back to the reactor.
[0231] Solution processes for homopolymerization or copolymerization of ethylene are well known in the art. These processes are conducted in the presence of an inert hydrocarbon solvent, typically a C5-12 hydrocarbon, which can be unsubstituted or substituted by a C1-4 alkyl group, such as pentane, methyl pentane, hexane, heptane, octane , cyclohexane, methylcyclohexane and hydrogenated naphtha. An example of a suitable solvent that is commercially available is "Isopar E" (C812 aliphatic solvent, Exxon Chemical Co.).
[0232] The polymerization temperature in a conventional solution process is about 80 to about 300 ° C (preferably about 120 to 250 ° C). However, as shown in the Examples, the polymerization temperature for the process of this invention is preferably above 160 ° C. The upper temperature limit will be influenced by considerations that are well known to those skilled in the art, such as a desire to maximize the operating temperature (in order to reduce the viscosity of the solution), while still maintaining good properties of the polymer ( since the increased polymerization temperatures generally reduce the molecular weight of the polymer). In general, the upper polymerization temperature will preferably be between 200 and 300 ° C (especially 220 to 250 ° C). The most preferred reaction process is a "medium pressure process", meaning that the pressure in the reactor is preferably less than about 42,000 kiloPascals or kPa (about 6,000 psi). Preferred pressures are 10,000 to 40,000 kPa, more preferably about 14,000 to 22,000 kPa (about 2,000 - 3,000 psi).
[0233] 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 polymerization reactor employs a polymer and catalyst "bed", which is fluidized by a flow of monomer, comonomer and other optional components, which are at least partially gaseous. The heat is generated by the polymerization enthalpy of the monomer (and comonomers) that flows through the bed. The unreacted monomer, comonomer and other optional gaseous components leave the fluidized bed and are contacted with a cooling system to remove this heat. The cooled gas stream, including the monomer, comonomer and other optional components (such as condensable liquids), is then circulated again through the polymerization zone, together with the "forming" monomer (and the comonomer), to replace the one that was polymerized in the previous step. Simultaneously, the polymer product is removed from the reactor. As will be appreciated by those skilled in the art, the "fluidized" nature of the polymerization bed helps to uniformly distribute / mix the reaction heat and thereby minimize the formation of localized temperature gradients.
[0234] The reactor pressure in a gas phase process can vary from approximately atmospheric to about 4137 kPa (600 psig). In a more specific embodiment, the pressure can vary from about 690 kPa (100 psig) to about 3448 kPa (500 psig). In another more specific embodiment, the pressure can vary from about 1379 kPa (200 psig) to about 2759 kPa (400 psig). In yet another more specific embodiment, the pressure can vary from about 1724 kPa (250 psig) to about 2414 kPa (350 psig).
[0235] The temperature of the reactor in a gas phase process can vary according to the heat of polymerization, as described above. In a specific embodiment, the temperature of the reactor can be from about 30 ° C to about 130 ° C. In another specific embodiment, the temperature of the reactor can be from about 60 ° C to about 120 ° C. In yet another specific embodiment, the temperature of the reactor 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.
[0236] The fluidized bed process described above is well adapted for the preparation of polyethylene, however other monomers (i.e., comonomers) can also be employed. Monomers and comonomers 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, the aromatic C8- vinyl monomers 12 which are unsubstituted or substituted by up to two substituents selected from the group consisting of C1-4 alkyl radicals, the C4-12 straight or cyclic diolefins, which are unsubstituted or substituted by an alkyl radical of C1-4. 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, alpha methyl styrene, p-tert-butyl styrene, and cyclic restricted ring olefins, such as cyclobutene, cyclopentene, norbornene dicyclopentadiene, alkyl-substituted norbornenes, alkenyl-substituted norbornenes and the like (eg, 5-methylene-2-norbornene and 5-ethylidene-2-norbornene, bicycles - (2,2,1) - hepta-2,5-diene).
[0237] In one embodiment, the invention is directed to a polymerization process that involves the polymerization of ethylene with one or more of the comonomer (s), including the linear or branched comonomer (s) having 3 to 30 carbon atoms, preferably 3-12 carbon atoms, more preferably 3 to 8 carbon atoms.
[0238] The process is particularly well suited for copolymerization reactions involving the polymerization of ethylene in combination with one or more of the comonomers, for example, the alpha-olefin comonomers, 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. The other comonomers 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 monomers unsaturated, including acetylene and aldehyde monomers. Higher alpha-olefins and polyenes or macromers can be used as well.
[0239] Preferably, the first polyethylene copolymer comprises ethylene and an alpha-olefin having 3 to 15 carbon atoms, preferably 4 to 12 carbon atoms and more preferably 4 to 10 carbon atoms.
[0240] In an 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) which is fed to a polymerization reactor.
[0241] 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) which is fed to a polymerization reactor.
[0242] In one embodiment of the invention, the first polyethylene copolymer is an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms and is prepared in a single reactor, in the presence of a polymerization catalyst system comprising a phosphinimine catalyst, a support and a catalyst activator.
[0243] In one embodiment of the invention, the first polyethylene copolymer is an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms and is prepared in a single gas phase reactor, in the presence of a catalyst system polymerization comprising a phosphinimine catalyst, a support and a catalyst activator, where the phosphinimine catalyst has the formula: (1-R2-Indenyl) Ti (N = P (t-Bu) 3) X2; where R2 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted benzyl group, where the substituents for the alkyl, aryl or benzyl group are selected from the group consisting of substituents alkyl, aryl, alkoxy, aryloxy, alkylaryl, arylalkyl and halide; and where X is an activable ligand.
[0244] In one embodiment of the invention, the first polyethylene copolymer is an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms and is prepared in a single gas phase reactor with a polymerization catalyst system that comprises: a phosphinimine catalyst; an alkylaluminoxane cocatalyst; and a support.
[0245] In one embodiment of the invention, the first polyethylene copolymer is an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms and is prepared in a single gas phase reactor with a polymerization catalyst system that comprises: a phosphinimine catalyst; an alkylaluminoxane cocatalyst; a support; and a catalyst modifier.
[0246] In one embodiment of the invention, the first polyethylene copolymer is an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms and is prepared in a single gas phase reactor with a polymerization catalyst system that comprises: 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, where each of the group alkyl, of the aryl group, or of the benzyl group can be unsubstituted or substituted by at least one halide atom, and where X is an activable linker; and an activator.
[0247] In one embodiment of the invention, the first polyethylene copolymer is an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms and is prepared in a single gas phase reactor with a polymerization catalyst system that comprises: 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, where each of the group alkyl, of the aryl group, or of the benzyl group can be unsubstituted or substituted by at least one halide atom, where X is an activable linker; an activator; and an inert support.
[0248] In one embodiment of the invention, the first polyethylene copolymer is an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms and is prepared in a single gas phase reactor with a polymerization catalyst system that comprises: 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, where each of the group alkyl, of the aryl group, or of the benzyl group can be unsubstituted or substituted by at least one halide atom, where X is an activable linker; an activator; an inert support; and a catalyst modifier.
[0249] In one embodiment of the invention, the first polyethylene copolymer is an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms and is prepared in a single gas phase reactor with a polymerization catalyst system that it comprises: a phosphinimine catalyst having the formula (1- C6F5CH2-Ind) Ti (N = P (t-Bu) 3) X2, where X is an activable ligand; an activator; and an inert support.
[0250] In one embodiment of the invention, the first polyethylene copolymer is an ethylene copolymer and an alpha-olefin having 3-8 carbon atoms and is prepared in a single gas phase reactor with a polymerization catalyst system that it comprises: a phosphinimine catalyst having the formula (1- C6F5CH2-Ind) Ti (N = P (t-Bu) 3) X2, where X is an activable ligand; an activator; an inert support; and a catalyst modifier.
[0251] The polymerization catalyst system can be fed to a reactor system in several ways. If the phosphinimine catalyst is supported on a suitable support, the catalyst can be fed to a reactor in dry mode, using a catalyst feeder, examples of which are well known in the art. Alternatively, a supported phosphinimine catalyst can be fed to a reactor as a slurry in a suitable diluent. If the phosphinimine catalyst is not supported, the catalyst can be fed to a reactor as a solution or as a slurry in a suitable solvent or diluents. The components of the polymerization catalyst system, which can include a phosphinimine catalyst, an activator, a remover, an inert support, and a catalyst modifier, can be combined before being added to a polymerization zone, or they can be combined on the way to a polymerization zone. To combine the components of the polymerization catalyst system on the way to a polymerization zone, they can be fed as solutions or slurries (in suitable solvents or diluents) using various feed line configurations, which can become coextensive before reach the reactor. Such configurations can be designed to provide areas in which the components of the catalyst system flowing into a reactor can mix and react with each other during various "delay" times, which can be restricted by changing the flow rates of the solution. or the slurry of the components of the catalyst system.
[0252] Optionally, the removers are added to a polymerization process. Removers are well known in the art.
[0253] In one embodiment of the invention, the removers are composed of organoaluminium 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 aryl oxide, any of which having 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, where each R3 is independently selected from the group consisting of C1-20 hydrocarbyl radicals and is 3 to 50. Some preferred, non-limiting removers useful in the present invention, include triisobutylaluminum, triethylalumin, trimethylalumin or other trialkylaluminium compounds.
[0254] The remover can be used in any suitable amount, however, by way of non-limiting examples only, it can be present in an amount to provide a molar ratio of Al: M (where M is the metal of the organometallic compound) of about from 20 to about 2000, or from about 50 to about 1000, or from about 100 to about 500. In general, the remover is added to the reactor before the catalyst and in the absence of additional poisons and over time decreases to 0, or is added continuously.
[0255] Optionally, removers can be independently supported. For example, an inorganic oxide that has been treated with an organoaluminium compound or alkylaluminoxane can be added to the polymerization reactor. The method of adding the organoaluminium or alkylaluminoxane compounds to the support is not specifically defined and is carried out by procedures well known in the art. PREPARATION OF THE POLYMER MIXTURE
[0256] The polymer blend can be formed using conventional equipment and methods, such as by dry mixing the individual components and subsequently mixing the fusion in a mixer, or by mixing the components together, directly in a mixer, such as by For example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or double helix extruder, which can include a mixing extruder and a side arm extruder used directly downstream from a polymerization process. A mixture or combination of the first and the second polyethylene copolymers can be indicated by the uniformity of the composition's morphology. In another example, the polymer blend can be produced in situ using a multistage polymerization reactor arrangement and a process. In a multistage reactor arrangement, two or more reactors can be joined in series, where a mixture of a first polymer and the catalyst can be transferred from a first reactor to a second reactor, where a second polymer can be produced and mixed in situ with the first polymer. A multistage polymerization reactor and the methods for using it can be similar to that discussed and described, for example, in Pat. No. 5,677,375. The mixing of the polymer components while in solution is also contemplated for use in the present invention.
[0257] The polymer blend can include at least 1 weight percent (% by weight) and up to 99 weight percent of the first polyethylene copolymer and at least 1 weight percent and up to 99% by weight of the second polyethylene copolymer. , based on the total weight of the first and second polyethylene copolymers.
[0258] In the embodiments of the invention, the amount of the first polyethylene copolymer in the polymer mixture will be in the range of a minimum of about 5% by weight, or about 10% by weight, or about 15% by weight, or about 20% by weight, or about 30% by weight, or about 40% by weight up to a maximum of about 60% by weight, or about 70% by weight, or about 80% by weight, or about 90% by weight, or about 95% by weight, based on the total weight of the first and second polyethylene copolymers.
[0259] In the embodiments of the invention, the amount of the first polyethylene copolymer in the polymer mixture will be in the range of about 1% by weight to about 50% by weight, or from about 5% by weight to about 50% by weight, or from about 7.5% by weight to about 50% by weight, or from about 10% by weight to about 50% by weight, or from about 12.5% by weight to about 50% by weight, or from about 12.5% by weight to about 40% by weight, or from about 15% by weight to about 40% by weight, or from about 10% by weight to about 35% by weight, or from about 10% by weight to about 45% by weight, or from about 10% by weight to about 30% by weight, or from about 7.5% by weight to about 30% by weight, or from about 5% by weight to about 35% by weight, or from about 5% by weight to about 30% by weight, or from about 5% by weight to about 25% by weight, or from about 1% by weight to about 25% by weight, based on the total weight of the first and second polyethylene copolymers. In the additional embodiments of the invention, the amount of the first polyethylene copolymer in the polymer mixture can be at least 5% by weight, or at least 10% by weight, at least 15% by weight, or at least 20% by weight, or at least 25% by weight, or at least 30% by weight, or at least 35% by weight, but less than about 50% by weight, based on the total weight of the first and second polyethylene copolymers.
[0260] In one embodiment of the invention, the amount of the first polyethylene copolymer in the polymer mixture can be at least 50% by weight, or at least 60% by weight, at least 70% by weight, or at least 80% by weight. weight, or at least 90% by weight, but less than 100% by weight, based on the total weight of the first and second polyethylene copolymers.
[0261] In one embodiment of the invention, the polymer blend comprises 1-99% by weight of a first polyethylene copolymer and 99-1% by weight of a second polyethylene copolymer, based on the total weight of the first and second polyethylene copolymers.
[0262] In one embodiment of the invention, the polymer blend comprises 5-95% by weight of a first polyethylene copolymer and 95-5% by weight of a second polyethylene copolymer, based on the total weight of the first and second polyethylene copolymers.
[0263] In one embodiment of the invention, the polymer blend comprises 1-50% by weight of a first polyethylene copolymer and 99-50% by weight of a second polyethylene copolymer, based on the total weight of the first and second polyethylene copolymers.
[0264] In one embodiment of the invention, the polymer blend comprises 5-50% by weight of a first polyethylene copolymer and 95-50% by weight of a second polyethylene copolymer, based on the total weight of the first and second polyethylene copolymers.
[0265] In one embodiment of the invention, the polymer blend comprises 95-50% by weight of a first polyethylene copolymer and 5-50% by weight of a second polyethylene copolymer, based on the total weight of the first and second polyethylene copolymers.
[0266] In one embodiment of the invention, the polymer blend comprises 95-60% by weight of a first polyethylene copolymer and 5-40% by weight of a second polyethylene copolymer, based on the total weight of the first and second polyethylene copolymers.
[0267] In one embodiment of the invention, the polymer blend comprises 90-50% by weight of a first polyethylene copolymer and 10-50% by weight of a second polyethylene copolymer, based on the total weight of the first and second polyethylene copolymers. ADDITIONS
[0268] The polymer blend or the polymer blend components (ie, the first and / or second polyethylene copolymers) of the present invention may also contain additives, such as, for example, primary antioxidants (such as hindered phenols, including vitamin E); secondary antioxidants (such as phosphites and phosphonites); nucleating agents, plasticizers or process aids (such as fluorelastomer and / or polyethylene glycol process aids), acid removers, stabilizers, anti-corrosion agents, blowing agents, other ultraviolet light absorbers, such as antioxidants that break down chain, etc., finishers, antistatic agents, gliding agents, anti-blocking agents, pigments, dyes and fillers and curing agents, such as peroxide.
[0269] These and other additives common in the polyolefin industry can be present in the polymer blend (and / or the first and / or the second polyethylene copolymers) at 0.01 to 50% by weight in one embodiment, and from 0 , 1 to 20% by weight in another embodiment, and 1 to 5% by weight in yet another embodiment, where a desirable range may comprise any combination of any upper limit of% by weight with any lower limit of% by weight.
[0270] In one embodiment of the invention, antioxidants and stabilizers, such as organic phosphites and phenolic antioxidants, can be present in the polymer mixture (and / or the first and / or the second polyethylene copolymers) in 0.001 at 5% by weight in one modality, and from 0.01 to 0.8% by weight in another modality, and from 0.02 to 0.5% by weight in yet another modality. Non-limiting examples of organic phosphites that are suitable 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-hydroxy-hydrocinamate (IRGANOX 1076) and tetrakis (3,5-di-tert-butyl-4-hydroxyphenyl) pentaerythrityl propionate (IRGANOX 1010); and 1,3,5-Tri (3,5-di-tert-butyl-4-hydroxybenzyl-isocyanurate (IRGANOX 3114).
[0271] The fillers can be present in the polymer mixture (and / or the first and / or the second polyethylene copolymers) in 0.1 to 50% by weight in one embodiment, and from 0.1 to 25% in weight of the composition in another embodiment, and from 0.2 to 10% by weight in yet another embodiment. The charges include, but are not limited to, titanium dioxide, silicon carbide, silica (and other silica oxides, precipitated or not), antimony oxide, lead carbonate, zinc whitening, lithopone, zirconite, corundum, spinel , apatite, barite powder, barium sulfate, magnesite, carbon black, dolomite, calcium carbonate, talc and hydrotalcite compounds 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, phosphorous and brominated flame retardants, antimony trioxide, silica, silicone, and mixtures thereof. These fillers can particularly include any other fillers and porous fillers and supports that are known in the art.
[0272] Fatty acid salts can also be present in polymer mixtures (and / or the first and / or the second polyethylene copolymers). Such salts can be present from 0.001 to 2% by weight in the polymer mixture or in the components of the polymer mixture 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, stearyl lactic acid, 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.
[0273] Regarding the physical process of introducing into the polymer mixture (and / or the first and / or the second polyethylene copolymers) one or more additives, sufficient mixing must occur to ensure that a uniform mixture will be produced before conversion in a finished product. The polymer blend (and / or the first and / or the second polyethylene copolymers) can be in any physical form when used to combine with one or more additives. In one embodiment, reactor granules, defined as granules from the polymer mixture (and / or the first and / or the second polyethylene copolymers) that are isolated and used to mix with the additives. The reactor granules have an average diameter of 10 μm to 5 mm, and 50 μm to 10 mm in another modality. Alternatively, the polymer mixture or its components may be in the form of pellets, such as, for example, having an average diameter of 1 mm to 6 mm, which are formed from the melt extrusion of the reactor granules.
[0274] One method of mixing the additives with the polymer mixture (and / or the first and / or the second polyethylene copolymers) is to contact the components in a drum or other physical mixing medium, the copolymer being in the form of granules of the reactor. Another method of mixing the components is to mix the polymer mixture or the pellets of the polymer mixture components with the additives in the melt directly in an extruder, or any other mixing medium in the melt. FILM PRODUCTION
[0275] The extrusion blown film process is a well-known process for preparing plastic film. The process employs an extruder that heats, melts and conveys the molten plastic (eg, the polymer mixture) and forces it through an annular matrix. Typical extrusion temperatures are 165.6 to 260 ° F (330 to 500 ° F), especially 176.7 to 237.8 ° F (350 to 460 ° F).
[0276] The polyethylene film is removed from the matrix and molded into a tube shape and, at the end, passed through a pair of extraction cylinders or tweezers. The compressed internal air is then introduced from a mandrel, causing the tube to increase in diameter, forming a "bubble" of the desired size. In this way, the blown film is stretched in two directions, namely, in the axial direction (by using forced air that "pops" the bubble diameter) and in the direction of the bubble length (by the action of a winding element that pulls bubble through the device). External air is also introduced around the bubble's circumference to cool the melt as it exits the matrix. The width of the film is varied by introducing more or less internal air into the bubble, thereby increasing or decreasing the size of the bubble. The thickness of the film is mainly controlled by increasing or decreasing the speed of the extraction cylinder or the clamp cylinder to control the rate of decrease.
[0277] The bubble is then collapsed into two folded layers of film immediately after passing through the extraction cylinders or tweezers. The cooled film can then be further processed by cutting or sealing to produce a variety of consumer products. Although not wishing to be bound by theory, it is generally believed by those skilled in the technique of making blown films that the physical properties of finished films are influenced both by the molecular structure of a polyethylene copolymer and by the processing conditions. For example, it is believed that the processing conditions influence the degree of molecular orientation (both in the machine direction, as well as in the axial or transversal direction).
[0278] A balance of molecular orientation in the "machine direction" ("MD") and in the "transverse direction" ("TD" - which is perpendicular to the MD) is generally considered desirable for the films associated with the invention (for example , Resistance to impact by throwing, tearing properties in the machine direction and in the transversal direction).
[0279] Thus, it is recognized that these stretching forces on the "bubble" can affect the physical properties of the finished film. In particular, it is known that the "decrease ratio" (ie, the ratio of the diameter of the blown bubble to the diameter of the annular matrix) can have a significant effect on the resistance to impact by throwing and the tear resistance of the finished film. .
[0280] The aforementioned description refers to the preparation of monolayer films. Multilayer films can be prepared by 1) a "coextrusion" process that allows more than one stream of molten polymer to be introduced into an annular matrix, resulting in a multilayer film membrane, or 2) a process lamination process in which the film layers are laminated together.
[0281] In one embodiment of the invention, the films of this invention are prepared using the blown film process described above.
[0282] An alternative process is the so-called molded film process, where a polyethylene copolymer (or mixture of polymers) is melted in an extruder, then forced through a linear slit matrix, thereby "molding" a flat film thin. The extrusion temperature for the molded film is typically somewhat hotter than used in the blown film process (with typically operating temperatures of 232.2 to 287.8 ° C (450 to 550 ° F)). In general, molded film is cooled (tempered) more quickly than blown film.
[0283] In one embodiment of the invention, the films of this invention are prepared using a molded film process.
[0284] The films of the invention can be single-layer or multiple-layer films. Multilayer films can comprise one or more layers formed from the polymer mixture. The films may also have one or more additional layers formed from other materials, such as other polymers, linear low density polyethylene (LLDPE), medium density polyethylene, polypropylene, polyester, low density polyethylene (HPLDPE), high density polyethylene (HDPE), ethylene vinyl acetate, ethylene vinyl alcohol and the like.
[0285] Multilayer films can be formed by methods well known in the art. If all layers are polymer, the polymers can be coextruded through a coextrusion feed block and matrix assembly to produce a film with two or more layers adhered together, but differing in composition. Multilayer films can also be formed by coextrusion coating, whereby a substrate material is contacted with the hot molten polymer as it exits the matrix. PROPERTIES OF POLYMER MIXTURES FILMS
[0286] The films of the present invention are prepared from the polymer mixtures as defined above. In general, an additive as described above is mixed with the polymer mixtures prior to the production of the films. Mixtures of polymers and films have a balance of processing and mechanical properties, as well as good optical properties. Consequently, in one embodiment of the invention, a 2.5 x 10-3 cm (1 mil) monolayer film will have a throw resistance of> 250 g / 2.5 x 10-3 cm (1 mil) and a secant modulus in the MD at 1% of more than 140 MPa, in combination with good optical properties of the film.
[0287] In the modalities of the invention, the film will have a throwing impact of> 220 g / 2.5 x 10-3 cm (1 mil), or> 230 g / 2.5 x 10-3 cm (1 mil) , or> 240 g / 2.5 x 10-3 cm (1 mil), or> 250 g / 2.5 x 10-3 cm (1 mil), or> 350 g / 2.5 x 10-3 cm (1 mil), or> 400 g / 2.5 x 10-3 cm (1 mil), or> 450 g / 2.5 x 10-3 cm (1 mil), or> 500 g / 2.5 x 10-3 cm (1 mil), or> 550 g / 2.5 x 10-3 cm (1 mil), or> 600 g / 2.5 x 10-3 cm (1 mil), or> 650 g / 2.5 x 10-3 cm (1 mil), or> 700 g / 2.5 x 10-3 cm (1 mil). In another embodiment of the invention, the film will have an impact per pitch from 230 g / 2.5 x 10-3 cm (1 mil) to 900 g / 2.5 x 103 cm (1 mil). In another embodiment of the invention, the film will have an impact per pitch from 230 g / 2.5 x 10-3 cm (1 mil) to 800 g / 2.5 x 10-3 cm (1 mil). In another embodiment of the invention, the film will have an impact per pitch from 250 g / 2.5 x 10-3 cm (1 mil) to 750 g / 2.5 x 10-3 cm (1 mil). In an additional embodiment of the invention, the film will have an impact per pitch from 300 g / 2.5 x 10-3 cm (1 mil) to 750 g / 2.5 x 10-3 cm (1 mil). In a further embodiment of the invention, the film will have an impact per pitch from 350 g / 2.5 x 10-3 cm (1 mil) to 750 g / 2.5 x 10-3 cm (1 mil). In an additional embodiment of the invention, the film will have an impact per throw from 400 g / 2.5 x 10-3 cm (1 mil) to 750 g / 2.5 x 10-3 cm (1 mil). In a further embodiment of the invention, the film will have an impact per throw from 450 g / 2.5 x 10-3 cm (1 mil) to 750 g / 2.5 x 10-3 cm (1 mil). In yet another embodiment of the invention, the film will have an impact per pitch from 500 g / 2.5 x 10-3 cm (1 mil) to 750 g / 2.5 x 10-3 cm (1 mil). In yet another embodiment of the invention, the film will have an impact per pitch from 550 g / 2.5 x 10-3 cm (1 mil) to 750 g / 2.5 x 10-3 cm (1 mil). In yet another embodiment of the invention, the film will have an impact per pitch from 600 g / 2.5 x 10-3 cm (1 mil) to 750 g / 2.5 x 10-3 cm (1 mil). In an additional embodiment of the invention, the film will have an impact per throw from 650 g / 2.5 x 10-3 cm (1 mil) to 750 g / 2.5 x 10-3 cm (1 mil). In a further embodiment of the invention, the film will have an impact per pitch from 650 g / 2.5 x 10-3 cm (1 mil) to 800 g / 2.5 x 10-3 cm (1 mil).
[0288] In the modalities of the invention, the film will have a tear ratio in the MD to tear in the TD (tear in the MD / tear in the TD) of less than 0.95, but more than 0.10, or less than 0.80, but more than 0.10. In another embodiment of the invention, the film will have a tear ratio in the MD to tear in the TD of 0.10 to 0.95. In another embodiment of the invention, the film will have a tear ratio in the MD to tear in the TD of 0.10 to 0.80. In another embodiment of the invention, the film will have a tear ratio in the MD to tear in the TD of 0.10 to 0.75. In yet another embodiment of the invention, the film will have a tear ratio in the MD to tear in the TD of 0.1 to 0.70. In yet another embodiment of the invention, the film will have a tear ratio in the MD to tear in the TD of 0.2 to 0.70. In yet another embodiment of the invention, the film will have a tear ratio in the MD to tear in the TD of 0.25 to 0.65.
[0289] In the modalities of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant module in the machine direction (MD) at 1% deformation of> 120 MPa, or> 130 MPa, or> 140 MPa, or> 150 MPa, or> 160 MPa. In one embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant module in the machine direction (MD) at 1% deformation from 120 MPa to 260 MPa. In one embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant module in the machine direction (MD) at 1% deformation from 130 MPa to 230 MPa. In another embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant module in the machine direction (MD) at 1% deformation from 130 MPa to 210 MPa. In another embodiment of the invention, a cm (1 mil) film will have a secant module in the machine direction (MD) at 1% deformation from 120 MPa to 200 MPa. In another embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant module in the machine direction (MD) at 1% deformation from 120 MPa to 190 MPa. In another embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant module in the machine direction (MD) at 1% deformation from 130 MPa to 180 MPa.
[0290] In one embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant modulus in the transverse direction (TD) at 1% deformation of> 130 MPa, or> 140 MPa, or> 150 MPa, or> 160 MPa, or> 170 MPa, or> 180 MPa, or> 190 MPa. In one embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant modulus in the transverse direction (TD) at 1% deformation from 120 MPa to 280 MPa. In one embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant modulus in the transverse direction (TD) at 1% deformation from 120 MPa to 270 MPa. In another embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant modulus in the transverse direction (TD) at 1% deformation from 120 MPa to 260 MPa. In another embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant modulus in the transverse direction (TD) at 1% deformation from 130 MPa to 240 MPa. In another embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant modulus in the transverse direction (TD) at 1% deformation from 130 MPa to 220 MPa. In another embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant modulus in the transverse direction (TD) at 1% deformation from 120 MPa to 220 MPa. In yet another embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant modulus in the transverse direction (TD) at 1% deformation from 130 MPa to 210 MPa. In yet another embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant modulus in the transversal direction (TD) at 1% deformation from 130 MPa to 200 MPa. In yet another embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a secant modulus in the transversal direction (TD) at 1% deformation from 130 MPa to 190 MPa.
[0291] In one embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a turbidity of less than 15% and a 45 ° brightness of at least 40. In one embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a turbidity of less than 15% and a 45 ° brightness of at least 45. In one embodiment of the invention, a 2.5 x 10- 3 cm (1 mil) will have a turbidity of less than 12% and a 45 ° brightness of at least 50. In one embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a turbidity less than 12% and a 45 ° brightness of at least 55. In one embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a turbidity of less than 10% and a brightness at 45 ° of at least 50. In one embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a turbidity of less than 10% and a 45 ° brightness of at least 55. In one embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a turbidity of less than 10% and a 45 ° brightness of at least 60. In another embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a turbidity of less than 7% and a 45 ° brightness of at least 55. In another embodiment of the invention, a 2.5 mm film x 10-3 cm (1 mil) will have a turbidity of less than 7% and a 45 ° brightness of at least 60. In another embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a turbidity of less than 7% and a 45 ° brightness of at least 65. In another embodiment of the invention, a 2.5 x 10-3 cm (1 mil) film will have a turbidity of less than 7% and a 45 ° brightness of at least 70.
[0292] The film can, by way of non-limiting example, have a total thickness ranging from 1.3 x 10-3 cm to 10-2 cm (0.5 thousand to 4 thousand), which will depend, for example, on the span of the matrix used during the molding of the film or the blowing of the film.
[0293] 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 prepared using a coextrusion process or a lamination process. In coextrusion, a plurality of molten polymer streams are fed to an annular matrix (or flat mold), resulting in a multilayer film on cooling. In lamination, a plurality of films are bonded together, using, for example, adhesives, heat and pressure bonding and the like. A multilayer film structure can, for example, contain bonding layers and / or sealing layers.
[0294] The film of the present invention can be a cover 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 term "core layer" refers to any inner film layer in a multilayer film. The term "cover layer" refers to an outermost layer of a multilayer film (for example, as used in the production of product packaging). The term "sealing layer" refers to a film that is involved in sealing the film on itself or on another layer in a multilayer film. The "bonding layer" refers to any inner layer that adheres two layers together.
[0295] As a non-limiting example only, the thickness of the multilayer films can be from about 1.3 x 10-3 cm (0.5 mil) to about 2.5 x 10-2 cm (10 thousand) of total thickness.
[0296] In one embodiment of the invention, a monolayer or multilayer film structure comprises at least one layer comprising a mixture of polymers comprising the first and second polyethylene copolymers described above.
[0297] By way of non-limiting examples, films can be used for heavy duty bags, shrink film, stretch film, agricultural film, garbage bags and shopping bags. The films can be produced by blowing extrusion, modeling extrusion, coextrusion and can also be incorporated into laminated structures.
[0298] In one embodiment of the invention, a blown film is provided, which comprises the polymer blend described above.
[0299] In one embodiment of the invention, a molded film is provided, which comprises the polymer blend described above.
[0300] In the embodiments of the invention, an elongation film or shrink film is provided, which comprises the polymer blend described above.
[0301] In the embodiments of the invention, a blown film, or a molded film having a turbidity of less than 10% and a 45 ° gloss of more than 55, is provided, which comprises the polymer blend described above. GENERAL EXAMPLES
[0302] All reactions involving compounds sensitive to air and / or moisture were conducted under nitrogen, using standard Schlenk and cannula techniques, or in a glovebox. The reaction solvents were purified using the system described by Pangborn et al. in Organometallics 1996, v15, p.1518, or used directly after being stored on activated 4 Â 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 from W.R. Grace & Co. The support was calcined by fluidizing with air at 200 ° C for 2 hours, followed by nitrogen at 600 ° C for 6 hours, and stored under nitrogen.
[0303] The hot flow index, I2, in g / 10, min was determined on a Tinius Olsen Plastomer (Model MP993), according to ASTM D1238 condition F, at 190 ° C, with a weight of 2.16 kilograms. The hot flow index, I10, was determined according to ASTM D1238 condition F, at 190 ° C, with a weight of 10 kilograms. The hot flow rate at high load, I21, in g / 10 min, was determined according to ASTM D1238 condition E, at 190 ° C, with a weight of 21.6 kilograms. The hot flow rate or "MFR" for short (also sometimes called the hot flow rate ratio) is I21 / I2.
[0304] The density of the polymer was determined in grams per cubic centimeter (g / cm3), according to ASTM D792.
[0305] The information on the molecular weight (Mw, Mn and Mz in g / mol) and the molecular weight distribution (Mw / Mn), and the average molecular weight distribution z (MZ / MW) were analyzed using chromatography gel permeation (GPC), using an instrument sold under the trade name "Waters 150c", with 1,2,4-trichlorobenzene as the mobile phase, at 140 ° C. The samples were prepared by dissolving the polymer in this solvent and were run without filtration. The molecular weights are expressed as polyethylene equivalent, with a relative standard deviation of 2.9% for the numerical average molecular weight ("Mn") and 5.0% for the average weight molecular weight ("Mw"). The polymer sample solutions (1 to 2 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a disc for 4 hours, at 150oC, in an oven. The antioxidant 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture to stabilize the polymer against oxidative degradation. The BHT concentration was 250 ppm. The sample solutions were chromatographed at 140oC on a PL 220 high temperature chromatography unit, equipped with four Shodex columns (HT803, HT804, HT805 and HT806), using the 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 injection volume of the sample was 200 ml. The raw data were processed using the Cirrus GPC software. The columns were calibrated with polystyrene standards of narrow distribution. The molecular weights of polystyrenes were converted to molecular weights of polyethylenes, using a Mark-Houwink equation, as described in the standard test method ASTM D6474.
[0306] The frequency of branching of the polymer samples (ie, the short chain branching, SCB per 1000 carbons) and the content of C6 comonomers (in% by weight) were determined by Fourier Transform Infrared Spectroscopy (FTIR ) according to the ASTM D6645-01 method. A Thermo-Nicolet 750 Magna IR Spectrometer was used for the measurements, equipped with OMNIC software version 7.2a.
[0307] The determination of the branching frequency as a function of the molecular weight (and, consequently, the distribution of comonomers) was performed using Gel Permeation Chromatography (GPC) at high temperature and the FT-IR of the eluant. Polyethylene standards with a known branching content, polystyrene and hydrocarbons with a known molecular weight were used for calibration.
[0308] The compression molded plates of the hexane extractables were determined according to ASTM D5227.
[0309] To determine the distribution amplitude index of the CDBI50 composition, which is also specified CDBI (50) in the present invention, a solubility distribution curve is first generated for the copolymer. This is done using data acquired from the TREF technique. This solubility distribution curve is a graph of the weight fraction of the copolymer that is solubilized as a function of temperature. This is converted into a cumulative distribution curve of the fraction by weight versus the comonomer content, from which the CDBI50 is determined by establishing the weight percentage of a sample of copolymers that has a comonomer content within 50% of the intermediate comonomer content on each side of the median (see WO 93/03093 for the definition of CDBI50). The weight percentage of copolymer that elutes at 90-105 ° C is determined by calculating the area under the TREF curve at an elution temperature of 90 to 105 ° C. The weight percentage of copolymer eluting below, or at, 40 ° C and above 100 ° C was similarly determined. For the purpose of simplifying the correlation of the composition with the elution temperature, it is assumed that all fractions have an Mn> 15,000, where Mn is the numerical average molecular weight of the fraction. Any low weight fractions present generally represent an insignificant part of the polymer. The remainder of this description and the attached claims maintain this convention of assuming all fractions having Mn> 15,000 in the measurement of the CDBI50.
[0310] The specific temperature rise elution fractionation (TREF) method used in this document was as follows. Samples of homogeneous polymers (pelleted, 50 to 150 mg) were introduced into the reactor vessel of a crystallization unit-TREF (ChAR® Polymer). 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 globules. After equilibrating at a given 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 to 30 ° C (0 , 1 or 0.2 ° C / minute). After equilibration at 30 ° C for 30 minutes, the crystallized sample was eluted with TCB (0.5 or 0.75 mL / minute), with a temperature jump of 30 ° C to the stabilization temperature (0.25 or 1 , 0 ° C / minute). The TREF column was cleaned at the end of the run, for 30 minutes, at the dissolution temperature. The data were processed using the Polymer ChAR software, the Excel spreadsheet and the TREF software developed locally.
[0311] The TREF procedures described above are well known to those skilled in the art and can be used to determine the modality of a TREF profile, a CDBI50, a% by weight of copolymer eluting at or below 40 ° C, a% by weight of copolymer eluting at above 100 ° C, a% by weight of copolymer eluting from 90 ° C to 105 ° C, a value of T (75) - T (25), as well as the temperatures or temperature ranges where the maximum elution intensity occurs (elution peaks).
[0312] Melting points, including a peak melting point (Tm), and the percentage of crystallinity of the copolymers are determined using a TA Instrument DSC Q1000 Thermal Analyzer, at 10 ° C / min. In a DSC measurement, a heating-cooling-heating cycle is applied to the polymers from room temperature to 200 ° C or vice versa, to minimize the thermomechanical history associated with them. The melting point and the percentage of 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 peak temperature, when two peaks are present in a bimodal DSC profile (typically also having the highest peak height).
[0313] The melting strength of a polymer is measured on a Rosand RH-7 capillary rheometer (barrel diameter = 15 mm) with a flat matrix of 2 mm in diameter, L / D ratio 10: 1 at 190 ° C , Pressure Transducer: (68.95 MPa) (10,000 psi), Piston Speed: 5.33 mm / min, Drag Angle: 52 °, Gradual Drag Speed: 50 - 80 m / min2 or 65 ± 15 m / min2. A polymer melt is extruded through a capillary matrix, at a constant rate, and then the polymer strip is removed at an increasing drag speed until it breaks. The maximum constant value of the force in the stabilization region of a force versus time curve is defined as the melt strength for the polymer.
[0314] Dynamic Mechanical Analysis (DMA). Rheological measurements (eg, measurements of small voltage oscillatory shear (10%)) were carried out on a Rheometrics SR5 Stress dynamic rotational rheometer, with parallel plates 25 mm in diameter, in a frequency scanning mode, under total nitrogen layer. The polymer samples are appropriately stabilized with the antioxidant additives and then inserted into the test device for at least one minute, preheating to ensure the normal strength decreases back to zero. All DMA experiments are conducted at 10% tension, 0.05 at 100 rad / s and 190 ° C. The Orchestrator Software is used to determine the viscoelastic parameters, including the modulus in storage (G '), the modulus in loss (G "), the phase angle (δ), the complex modulus (G *) and the complex viscosity ( n *).
[0315] Complex viscosity data | n * (w) | versus frequency (w) were then adapted to the curve using the modified three-parameter empirical Carreau-Yasuda (CY) model to obtain zero shear viscosity at, the characteristic viscous relaxation time Tn, and the amount of rheology a. The simplified Carreau-Yasuda (CY) empirical model is as follows: | n * (w) | = n0 / [1 + (Tn w) a] (1 - n) / a where: | n * (w) | = magnitude of the complex shear viscosity; n0 = zero shear viscosity; Tn = characteristic relaxation time; a = "quantity" of rheology parameter (which is also called the "Carreau-Yasuda shear exponent" or "CY parameter a" or simply the "parameter a" in the present invention); n = fixes the slope of the final power law, set at 2/11; and w = angular frequency of the oscillatory shear deformation. Details on the meaning and interpretation of the CY model and derived parameters can be found at: C. A. Hieber and H. H. Chiang, Rheol. Acta, 28, 321 (1989); C. A. Hieber and H. H. Chiang, Polym. 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 into this document by reference in its entirety.
[0316] The Shear Tuning Index (SHI) was determined according to the method provided in Ped. of Pat. US No. 2011/0212315: SHI is defined as SHI (w) = n * (w) / n0 for any frequency (w) given for the measurement of dynamic viscosity, where n0 is the zero shear viscosity at 190 ° C , determined using Cox-Merz's rule of thumb. n * is the complex viscosity at 190 ° C, determinable in the shear or dynamic (sinusoidal) deformation of a copolymer, as determined on a Rheometrics SR5 Stress rotational rheometer, using parallel plate geometry. According to the Cox-Merz rule, when the frequency (w) is expressed in Radiant units, at low shear rates, the numerical value of n * is equal to that of the conventional, intrinsic viscosity, based on measurements in capillary tubes low shear. The person skilled in the field of rheology is quite adept at determining n0 in this mode. The shear thinning ratio (q * o, i / q * io) can be determined similarly using DMA, determining the complex viscosity at frequencies of 0.1 and 10 rad / s.
[0317] The films of the present examples were prepared on a blown film line, manufactured by Battenfeld Gloucester Engineering Company of Gloucester, Mass, using a matrix diameter of 10.2 centimeters (4 inches), and a matrix gap of 0 , 1 or 0.3 cm (35 or 100 thousand). This blown film line has a standard production of more than 45.4 kilograms (100 pounds) per hour and is equipped with a 29.8 kWatt motor (40 horsepower). The thread speed was 35 to 50 RPM. The extender thread has a diameter of 6.4 x 10-3 cm (2.5 mil) and a length / diameter (L / D) ratio of 24/1. The Melting Temperature and the Height of Freezing Depth (FLH) are 215.6 to 221.1 ° C (420 to 430 ° F) and 40.6 to 45.7 centimeters (16 to 18 inches), respectively. The blown film bubble is cooled with air. The typical burst ratio (BUR) for blown films prepared on this line is 1.5 / 1 to 4/1. An annular matrix having a span of 0.1 cm (35 mils) was used for three experiments. The films in this example were prepared using a 2.5: 1 BUR purpose point and a 2.5 x 10-3 cm (1.0 mil) film thickness purpose point.
[0318] Turbidity (%) was measured according to the procedures specified in ASTM D 1003-07, using a BYK-Gardner Turbidity Meter (Model Haze-gard plus).
[0319] Thrust impact resistance was measured on a pitch impact tester (Model D2085AB / P), manufactured by Kayeness Inc. in accordance with ASTM D-1709-04 (method A).
[0320] Elmendorf's tear resistance in the machine (MD) and transverse (TD) direction were measured on a ProTear® Tear Tester manufactured by Thwing-Albert Instrument Co., according to ASTM D-1922.
[0321] Puncture resistance was measured on an MTS Systems Universal Tester (Model SMT (ALTA) -500N-192), according to ASTM D-5748.
[0322] The secant module in the MD or TD was measured on a Universal 5-Head Tester Instrument (Model TTC-102), at a crosshead speed of 0.5 cm (0.2 in.) / Min, up to 10% deformation, according to ASTM D-882-10. The secant modulus in the MD or TD was determined by an initial slope of the stress-strain curve from an origin up to 1% strain.
[0323] The film tensile test was conducted on a Universal 5-Head Tester Instrument (Model TTC-102), according to ASTM D-882-10.
[0324] Gloss was measured on a BYK-Gardner 45 ° Micro-Gloss unit, according to ASTM D2457-03.
[0325] A seal was prepared by attaching two strips of 5.1 x 10-3 cm (2.0 mil) film between the upper and lower heated sealing bars, on an SL-5 Sealer manufactured by Lako Tool, for 0 , 5 seconds, clamping pressure on the seal bar of 275.8 kPa (40 psi) for each temperature in the range from the beginning of the seal to fully melt. The sealing resistance parameter or sealing ability was measured as a function of the sealing temperature, on a 5 Head Universal Tester Instrument (Model TTC-102), according to ASTM F88-09. COMPONENTS OF POLYMER MIXTURES
[0326] RESINS 1A-1F: THE FIRST POLYETHYLENE COPOLYMER. These resins were prepared using a supported catalyst, having the formula (1- C6F5CH2-Indenyl) ((t-Bu) 3P = N) TiCl2, as further described below.
[0327] SYNTHESIS OF (1-C6F5CH2-Indenyl) ((t-Bu) 3P = N) TiCl2. BuLi (82 ml, 131 mmoles, 1.6 M in hexanes) was added to the distilled indene (15.0 g, 129 mmoles) in heptane (200 ml), 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 give lithium indenyl (15.62 g, 99% yield). Indenyl lithium (6.387 g, 52.4 mmoles) was added as a solid over 5 minutes to a stirred solution of C6F5CH2-Br (13.65 g, 52.3 mmoles) in toluene (100 mL) at room temperature environment. 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 provide 1-C6F5CH2-indene (13.58 g, 88%). To a stirred slurry of TiCl4.2THF (1.72 g, 5.15 mmol) in toluene (15 mL) was added (t-Bu) 3P = solid N-Li (1.12 g, 5 mmol), at room temperature. The resulting reaction mixture was heated to 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 mmoles) was used in the next reaction. The n-butyl lithium (3.28 mL, 5 mmol, 1.6 M in hexanes) was added to a THF solution (10 mL) of 1-C6F5CH2-indene (1.48 g, 5 mmol), cooled to -78 ° C for 10 minutes. The resulting dark orange solution was stirred for 20 minutes and then transferred via a double-tipped needle to a toluene slurry of ((t-Bu) 3P = N) TiCl3 (1.85 g, 5 mmoles) Cooling was removed from the reaction mixture, which was stirred for another 30 minutes. The solvents were evaporated to provide a yellow pasty residue. The solid was redissolved in toluene (70 ml) at 80 ° C and filtered hot. Toluene was evaporated to provide pure (1-C6F5CH2-Indenyl) ((t-Bu) 3P = N) TiCl2 (2.35 g, 74%).
[0328] DRYING THE CATALYST MODIFIER. 950 g of commercially available Armostat® 1800 (mp 50 ° C, eg> 300 ° C), which was used as a catalyst modifier, was loaded into a 2 L round-bottom flask and melted in an 80 ° C oil bath. ° C. The temperature of the oil bath was then raised to 110 ° C and a high vacuum was applied, while maintaining agitation. First, a large number of bubbles were seen due to the release of gas and moisture vapor. Approximately two hours later, the gas evolution slowed and the 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.
[0329] To determine the moisture level in Armostat 1800, some 15% by weight of a solution of Armostat in pre-dried toluene was prepared and the moisture of the solution was determined by the Karl-Fischer titration method. The moisture levels in Armostat 1800 were determined as received from the commercial supplier, as well as that dried by traditional methods (i.e., drying the solution over molecular sieves) and using low pressure water distillation. The unpurified catalyst modifier was found to produce a 15 wt% toluene solution having 138 ppm H2O. The catalyst modifier, which was dried over molecular sieves, was found to produce a solution in toluene at 15% by weight having 15-20 ppm H2O. The catalyst modifier which was dried by vacuum distillation of water was found to produce a solution in toluene at 15% by weight having 14-16 ppm H2O. It has thus been shown that simple vacuum distillation to remove water is as effective as drying methods that employ molecular sieves. In reality, vacuum distillation has an advantage over using molecular sieves as a drying agent in that it is by far less time consuming (molecular sieves take more than 2 days to dry the catalyst modifier sufficiently and multiple batches of sieves were required), and more cost-effective (the use of sieves resulted in a decrease in the concentration of the catalyst modifier in the toluene solution, due to the absorption of the catalyst modifier in the sieves, and required large amounts of solvent for sufficiently solubilize the catalyst modifier to make efficient contact with the sieves).
[0330] PREPARATION OF THE SUPPORTED CATALYST. The Sylopol 2408 silica purchased from Grace Davison was calcined by fluidizing 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 were added to 620 mL of toluene. 312.993 g of an MAO solution containing 4.5 wt% Al, purchased from Albermarle, was added quantitatively to the silica slurry. The mixture was stirred for 2 hours at room temperature. The rate of agitation should be such that it does not fragment the silica particles. 2.742 grams of (1-C6F5CH2-Indenyl) ((t-Bu) 3P = N) TiCl2 (prepared as described above in Example 1) were weighed in a 500 ml Pyrex flask and 300 ml of added toluene. The complex metal solution was added to the silica slurry quantitatively. The resulting slurry was stirred for 2 hours at room temperature. 21.958 g of 18.55 wt% toluene solution of Armostat® 1800 were weighed into a small vessel and transferred quantitatively to the silica slurry. The resulting mixture was stirred for an additional 30 minutes, after which the slurry was filtered, producing 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 to between 0.5 and 0.2 mm Hg (450 and 200 mtorr) and stored under nitrogen, until used. The finished catalyst was light yellow to light orange in color. The catalyst had 2.7% by weight of Armostat present. POLYMERIZATION - TSR
[0331] The continuous gas phase copolymerization experiments with ethylene / 1-hexene were conducted in a 56.4 L Technical Scale Reactor (TSR), in continuous gas phase operation (as for an example of an installation of the TSR reactor, see Eur. No. Ped. No. 659.773A1). Polymerizations of ethylene were run at 75 ° C-90 ° C, with a total operating pressure of 2,068.4 kPascals gauge (300 pounds per square inch gauge (psig)). The gas phase compositions for ethylene and 1-hexene were controlled by means of closed-loop process control for the values of 65.0 and 0.5-2.0 mol%, respectively. Hydrogen was dosed in the reactor at a molar feed rate of 0.0008-0.0020 in relation to the ethylene feed, during polymerization. Nitrogen constituted the remainder of the mixture in the gas phase (approximately 3464 mol%). A typical production rate for these conditions is 2.0 to 3.0 kg of polyethylene per hour. A seed bed was used and, before starting the polymerization, it was washed with a small amount of triethyl aluminum, TEAL, to remove impurities. Before the introduction of the catalyst, TEAL was removed from the reactor. The catalyst was fed to the reactor together with a small amount of diluted TEAL solution (0.25% by weight) during the starting phase. The addition of TEAL was discontinued as soon as the desired polymer production rate was reached. Alternatively, the reactor can be started with the catalyst feed line alone during the polymerization start-up phase (that is, without initially feeding the TEAL solution). The polymerization reaction was initiated under conditions of low comonomer concentration, followed by gradual adjustment of the comonomer to ethylene ratio to provide a targeted polymer density.
[0332] PELLETIZING GRANULAR RESINS. 500 ppm of Irganox 1076 and 1000 ppm of Irgafos 168 were mixed dry with the granular resin, before pelletizing. The resulting powder mixture was extruded on a two-screw Leistritz extruder with a 38 mm helix diameter and a 33/1 L / D ratio under nitrogen atmosphere to minimize polymer degradation. The pelletizing conditions of the extruder were adjusted at a melting temperature of 210 ° C, a production rate of 9.1 to 11.3 kg (20 to 25 lb) / h, a propeller speed of 120 rpm and a speed of the pelletizer from 30 to 40 rpm. The pelleted resin was cooled and then collected to characterize the resin and evaluate the film.
[0333] Information on the composition of the catalyst and the polymerization conditions at steady state are provided in Table 1 for examples 1A and 1B (C2 = ethylene; C6 = 1-hexene; H2 = hydrogen; and C6 / C2 for the example is the molar feed rate of each component to the reactor). The polymer data for the resulting resins 1A and 1B are provided in Table 2. POLYMERIZATION PILOT PLANT
[0334] The ethylene / 1-hexene copolymerization experiments were conducted in a pilot plant scale reactor, gas phase, fluidized bed, continuous. An example of a reactor configuration and typical process operating parameters is given, for example, in Pat. No. 8,338,551 and in Ped. of Pat. Eur. No. 1,308,464 A1 (see Examples 10 and 11). Polymerizations of ethylene were run at 80 ° C-85 ° C, with a total operating pressure of 2,068.4 kPascals gauge (300 pounds per square inch gauge (psig)). The gas phase compositions for ethylene and 1-hexene were controlled by means of closed-loop process control for values of 35 - 50.0 and 0.5-2.0 mole%, respectively. Hydrogen was dosed in the reactor at a molar feed rate of 0.0008-0.0015 in relation to the ethylene feed, during polymerization. Nitrogen constituted the remainder of the gas phase mixture (approximately 34 - 49 moles%). A typical production rate for these conditions is 100 to 250 kg of polyethylene per hour. A seed bed was used and, before starting the polymerization, it was washed with a small amount of triethyl aluminum, TEAL, to remove impurities. The required gas composition of ethylene, 1-hexene, hydrogen, nitrogen and pentane / isopentane in the reactor is established for target quantities, prior to the injection of the catalyst. The level of pentane / isopentane can vary from 9 - 17 mol% in the reactor. The reactor was started with the catalyst feed line alone, without additional removal with TEAL during the polymerization start. The polymerization reaction was initiated under conditions of lower comonomer concentration and higher hydrogen concentration, followed by gradual adjustment of the comonomer to ethylene ratio and the hydrogen to ethylene ratio, to achieve the polymer density and the hot flow index targeted. The pelletization of the granular resin was performed according to the TSR scale (see above).
[0335] Information on the composition of the catalyst and the conditions of polymerization at steady state are provided in Table 1 for examples 1C-1F (C2 = ethylene; C6 = 1-hexene; H2 = hydrogen; and C6 / C2 for the example is the molar feed rate of each component to the reactor). The polymer data for the resulting 1C-1F resins are provided in Table 2. TABLE 1

TABLE 2 PROPERTIES OF COPOLYMERS




[0336] RESIN 2A: THE SECOND POLYETHYLENE COPOLYMER. This resin was prepared using a supported catalyst having the formula (1,2- (n-propyl) (C6F5) Cp) Ti (N = P (t-Bu) 3) Cl2, as is further described below.
[0337] PREPARATION OF THE SUPPORTED CATALYST: To a dehydrated silica slurry (122.42 g) in toluene (490 mL) was added a 10% by weight MAO solution (233.84 g, 4.5% in weight of Al in toluene) for 10 minutes. The vessel containing the MAO was rinsed with toluene (2x 10 mL) and added to the reaction mixture. The resulting slurry was stirred with a suspended stirrer assembly (200 rpm) for 1 hour at room temperature. To this slurry was added a solution in toluene (46 mL) of (1,2- (n-propyl) (C6F5) Cp) Ti (N = P (t-Bu) 3) Cl2 (2.28 g), for 10 minutes. This solution may need to be gently heated to 45 ° C for a brief period (5 minutes), to fully dissolve the molecule. The vessel 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 method described above for "Drying a Catalyst Modifier"), at 8 , 55% by weight, was added to the slurry, which was further stirred for 30 minutes. The slurry was filtered and rinsed with toluene (2 x 100 ml) and then with pentane (2 x 100 ml). The catalyst was dried in vacuo to less than 1.5% by weight of residual volatiles. The solid catalyst was isolated and stored under nitrogen, until further use. The catalyst had 2.7% by weight of Armostat present. POLYMERIZATION
[0338] The continuous gas phase copolymerization experiments, of ethylene / 1-hexene, were conducted in a TSR Technical Scale Reactor of 56.4 L, in continuous gas phase operation. Polymerizations of ethylene were run at 75 ° C-90 ° C, with a total operating pressure of 2,068.4 kPascals gauge (300 pounds per square inch gauge (psig)). The gas phase compositions for ethylene and 1-hexene were controlled using closed-loop process control for values of 65.0 and 0.5-2.0 mole%, respectively. Hydrogen was dosed in the reactor at a molar feed rate of 0.0008-0.0015 in relation to the ethylene feed, during polymerization. Nitrogen constituted the remainder of the gas phase mixture (approximately 38 moles%). A typical production rate for these conditions is 2.0 to 3.0 kg of polyethylene per hour.
[0339] PELLETIZING GRANULAR RESINS. 500 ppm of Irganox 1076 and 1000 ppm of Irgafos 168 were mixed dry with the granular resin, before pelletizing. The resulting powder mixture was extruded on a two-screw Leistritz extruder with a 38 mm helix diameter and a 33/1 L / D ratio under nitrogen atmosphere to minimize polymer degradation. The pelletizing conditions of the extruder were adjusted at a melting temperature of 210 ° C, a production rate of 9.1 to 11.3 kg (20 to 25 lb) / h, a propeller speed of 120 rpm and a speed of the pelletizer from 30 to 40 rpm. The pelleted resin was cooled and then collected to characterize the resin and evaluate the film.
[0340] The polymerization conditions at steady state are given in Table 3 (C2 = ethylene; C6 = 1-hexene; C6 / C2 is the molar feed rate of each component to the reactor) for example 2A. The polymer data for the resulting 2A resin is provided in Table 4. TABLE 3


[0341] Also included in Table 4 are resins 2B, 2B *, 2C, and 2D, each of which can be used as the second polyethylene copolymer in the mixtures of the present invention. Resin 2B is an Exceed 1018DA® 1-hexene ethylene copolymer, which is commercially available from ExxonMobil. 2B * resin is an Exceed 1018JA® 1-hexene ethylene copolymer, which is commercially available from ExxonMobil. 2C resin is a linear low density polyethylene having an I2 hot melt index of 0.93 g / 0 min and a density of 0.917 g / cm3, which is available from NOVA Chemicals as FPs-117-C®. 2D resin is a linear low density polyethylene having an I2 hot melt index of 1 g / 10 min and a density of 0.92 g / cm3, which is available from NOVA Chemicals as FP-120-C®. TABLE 4 PROPERTIES OF COPOLYMERS



[0342] As shown in Tables 2 and 4, the first polyethylene copolymers, resins 1A-1F, have a hot flow rate that is different from resins 2A-2D. Resins 1A-1F have an MFR (I21 / I2) of more than 32, while resins 2A, 2B and 2B * each have a hot flow rate of less than 16.5 and resins 2C and 2D have an MFR (I21 / I2) close to 30.
[0343] As can be seen in Table 2, all resins 1A-1E have an inverted comonomer distribution, a multimodal TREF profile, a CDBI50 within a range of 45% by weight to 75% by weight, an MFR ( I21 / I2) within a range of 32 to 50, an Mw / Mn within a range of 3.5 to 6.0 and a fractional hot flow rate (I2 of less than 1.0 g / 10 min ). Also shown in Table 2 is resin 1F, which has an inverted comonomer distribution, a multimodal TREF profile, a CDBI50 within a range of 45% by weight to 75% by weight, an MFR (I21 / I2) within from a range of 32 to 50, an Mw / Mn within a range of 3.5 to 6.0 and a hot flow index I2 of about 1.2 g / 10 min. Each of the 1A-1F resins shown in Table 2 has a wide unimodal molecular weight distribution.
[0344] A representative TREF curve is shown in Figure 1A for resin 1A. A representative TREF curve is shown in Figure 1B for resin 1B. A representative GPC curve is shown for resin 1A in Figure 2. A representative GPC-FTIR curve is shown for resin 1A in Figure 3.
[0345] A Van Gurp-Palmen analysis is a means by which to study a polymer structure (eg, molecular weight distribution, linearity, etc.), as reflected by the polymer's fusion morphology. A VGP curve is simply a graph of the phase angle (δ) versus the complex module (G *), where the two rheology parameters are obtained using the frequency sweep test in dynamic mechanical analysis (DMA). A displacement of a VGP curve from a baseline curve or a decrease in phase angles in the middle range of the complex module may indicate changes in the melting morphology of the polymer.
[0346] A VGP graph allows a determination of the intersection rheology parameter, which is defined as the point of intersection obtained between the phase angle graph (δ) vs. complex modulus (G *) and a phase angle graph (δ) vs. complex viscosity (n *). Based on a theory of linear viscoelasticity, the VGP intersection rheology parameter or the "intersection phase angle" (n *) occurs at a frequency (w) that is equal to the unit. It is the phase angle at which the numerical values of G * and n * are equivalent. Consequently, the VGP intersection rheology parameter can be determined in a single DMA test.
[0347] The VGP intersection graphs for resin 2A and for a resin sold under the trade name Exceed 1018DA® (resin 2B) are included in Figure 4A. The VGP intersection graphs for resin 1A are shown in Figure 4B. The points of intersection of VGP are dependent on the structure of the copolymer. In general, for resins that are easier to process, such as resin 1A, the VGP phase angle at which the intersection occurs, defined as δXO, is smaller than for resins that are more difficult to process, such as resins 2A and 2B (compare Figures 4A and 4B). Without wishing to be bound by any individual theory, this may be due to the fact that 1A resin has a higher hot flow rate (I21 / 2) or a wider molecular weight distribution (Mw / Mn) than Resin 2A or 2B. For resins that are easier to process, the shape of the complex phase-viscosity angle curves and the shape of the complex phase-module angle curves are somewhat deformed and more closely resemble mirror images of each other, in regarding the curves obtained for the resins that are more difficult to process (compare the curves in Figure 4A with the curves in Figure 4B).
[0348] As shown in Tables 2, the first polyethylene copolymers, resins 1A-1F, have a value of δXO which is less than about 70 °. In reality, resins 1A-1F have a value of δXO which is between about 55 ° and about 70 °.
[0349] Table 2 also shows the fact that all 1A-1F ethylene copolymers satisfy the following relationships: (Mw / Mn)> 72 [(I21 / I2) "1 + 10—6 (Mn)], where Mw, Mn, I21, I2 and CDBI50 are all as defined as above, Resins 1A, 1B and 1D-1F also satisfy the following relationship: δXO <80.7 - (CDBI50) / (Mw / Mn) in an δXO of 55 ° to 70 °, where δXO is the transverse phase angle, Mw, Mn, I21, I2 and CDBI50 are all as defined above, Resins 1A, 1B, 1D, and 1E also satisfy the following relationship: δXO <83 , 0 - 1.25 (CDBI50) / (Mw / Mn), where δXO is the transverse phase angle, Mw, Mn, I21, I2 and CDBI50 are all as defined above, in contrast, the data provided in Table 4 shows that none of the 2A-2D resins meets any of the conditions: (Mw / Mn)> 72 [(I21 / I2) "1 + 10-6 (Mn)]; (δXO <83.0 - 1.25 (CDBI50) / (Mw / Mn); or δXO <80.7 - (CDBI50) / (Mw / Mn) in an δXO from 55 ° to 70 °.
[0350] For purposes of further comparison, ethylene copolymers 1A-1F were plotted against several known commercial resins, in Figure 5. Figure 5 shows a graph of the equation: (Mw / Mn) = 72 [(I21 / I2) -1 + 10-6 (Mn)], as well as a graph of the values of Mw / Mn vs. 72 [(I21 / I2) -1 + 10-6 (Mn)] for resins 1A-1F, as well as several known commercial resins. The commercial resins included in Figure 5 for comparison purposes are all resins having an I2 hot melt index of 1.5 g / 10 min or less and a density of between 0.916 and 0.930 g / cm3 and which are sold under the names such as Elite®, Exceed®, Marflex®, Starflex®, Dowlex®, SURPASS®, SCLAIR®, NOVAPOL® and Enable®. As can be seen from Figure 5, none of these commercial grades satisfy the condition: (Mw / Mn)> 72 [(I21 / I2) "1 + 10-6 (Mn)]. In contrast, all resins 1A- 1F satisfy the condition: (Mw / Mn)> 72 [(I21 / I2) -1 + 10—6 (Mn)] This work demonstrates the distinct structure of the resins used as the first polyethylene copolymer in the mixtures of the present invention.
[0351] For purposes of further comparison, ethylene copolymers 1A-1F were plotted against several known commercial resins, in Figure 6. Figure 6 shows a graph of the equation: δXO = 83.0 - 1.25 (CDBI50) / (Mw / Mn), as well as a graph of the values of δXOvs. 83.0 - 1.25 (CDBI50) / (Mw / Mn) for resins 1A-1F and several known commercial resins. The commercial resins included in Figure 6 for comparison purposes are all resins having a hot melt index I2 of 1.5 g / 10 min or less and a density of between 0.916 and 0.930 g / cm3 and which are sold under the names such as Elite®, Exceed®, Marflex®, Starflex®, Dowlex®, SURPASS®, SCLAIR®, NOVAPOL® and Enable®. As can be seen from the figure, none of these commercial grades satisfy the condition: δXO <83.0 - 1.25 (CDBI50) / (Mw / Mn). In contrast, resins 1A, 1B, 1D, and 1E satisfy the condition: δXO <83.0 - 1.25 (CDBI50) / (Mw / Mn). This work additionally demonstrates the distinct structure of the resins used as the first polyethylene copolymer in the mixtures of the present invention.
[0352] For comparison purposes, ethylene copolymers 1A-1F were plotted against several known commercial resins, in Figure 7. Figure 7 shows a graph of the equation: δXO = 80.7 - (CDBI50) / (Mw / Mn), as well as a graph of the values of δXO vs. 80.7 - (CDBI50) / (Mw / Mn) for resins 1A-1F and several known commercial resins. Figure 7 also shows which of the 1A-1F resins and which of the commercial resins have a δXO of 55 ° to 70 °. The commercial resins included in Figure 7 for comparison purposes are all resins having a hot melt index I2 of 1.5 g / 10 min or less and a density of between 0.916 and 0.930 g / cm3 and which are sold under the names such as Elite®, Exceed®, Marflex®, Starflex®, Dowlex®, SURPASS®, SCLAIR®, NOVAPOL® and Enable®. As can be seen from Figure 7, none of these commercial grades satisfies the condition where δXO = 80.7 - (CDBI50) / (Mw / Mn) in an δXO of 55o to 70o. In contrast, resins 1A, 1B and 1D-1F satisfy the condition where δXO = 80.7 - (CDBI50) / (Mw / Mn) in an δXO from 55o to 70o. This work additionally demonstrates the distinct structure of the resins used as the first polyethylene copolymer in the mixtures of the present invention. POLYMER MIXTURES
[0353] The inventive polymer mixtures were prepared by mixing a first polyethylene copolymer (eg, resins 1A or 1C) with a second polyethylene copolymer (eg, resins 2A-2D). The mixtures were prepared by dry mixing the components in appropriate quantities, using a dosing device upstream of an extruder used to feed a line of blowing film. Tables 5-8 show the properties of the film of 2.5 x 10-3 cm (1 mil) films (thick) comprising 100% by weight of the first or second polyethylene copolymer, as well as the properties of the film for the polymer mixtures at 15% by weight: 85% by weight.
[0354] Comparative polymer mixtures were prepared by mixing LF-Y819-A® (a high pressure low density polyethylene material (HPLDPE) having an I2 hot melt index of 0.75 g / 10 min and a density of 0.919 g / cm3, available from NOVA Chemicals) with the second polyethylene copolymer (eg, resins 2B, 2C and 2D). The film properties of these comparative mixtures at 15% by weight: 85% by weight are provided in Tables 6-8. TABLE 5 FILM PROPERTIES (RESIN 1A, 2A AND 1A / 2A INVENTIVE MIXTURE)


TABLE 6 FILM PROPERTIES (RESIN 1A, 1C, 2B, 2B *, INVENTIVE MIXTURES 1A / 2B, 1C / 2B * AND COMPARATIVE MIXTURE HPLDPE / 2B)




TABLE 7 FILM PROPERTIES (RESIN 1A, 1C, 2C, INVENTIVE MIXTURES 1A / 2C, 1C / 2C AND HPLDPE / 2C COMPARATIVE MIXTURE




TABLE 8 FILM PROPERTIES (RESIN 1A, 1C, 2D, 1A / 2D, 1C / 2D INVENTIVE MIXTURE AND HPLDPE / 2D COMPARATIVE MIXTURE




[0355] As shown in Table 5, a mixture of resin 1A and resin 2A (a linear low density polyethylene with relatively low MFR (I21 / I2) and having a narrow MWD (Mw / Mn) and a hot flow index I2 of 0.95 g / 10 min) at a weight percentage ratio of 15/85 has an improved pitch impact in relation to any of the components of the mixture. The mixture also has a tear value in the TD that is more than 10% higher than the weighted average of the components of the mixture. That is, the so-called "Mixture Rule" indicates a positive synergistic effect on the tear property in TD in the mixture (note: without wishing to be bound by any individual theory, the mixing rule indicates a positive synergism where a property of the mixture is better than expected, based on the weighted average of the components of the mixture; a negative synergism where a property of the mixture is worse than expected, based on the weighted average of the components of the mixture; the mixing rule is followed where a property of the mixture mixture is approximately what a person skilled in the art would expect, based on the weighted average of the components of the mixture). In addition, the mixture has a 4.7% turbidity and a 45 ° gloss of 75, each of which is significantly enhanced over any of the components of the mixture. Finally, the tear in the MD, and the secant module in the MD and 1% TD, which roughly follow the Mixture Rule or are at least comparable to that of resin 2A, are not impacted in a negative way. The mixture of 1A with 2A can be extruded with a specific production of 1.1 kg (2.38 lb) / hour / rpm, at a pressure in the extruder head of about 33,094.8 to 33,370.6 kPa (4800 a 4840 psi), suggesting an improvement in the processing of the film on resin 2A.
[0356] With reference to Table 6, a mixture of resin 1A and resin 2B (a linear low density polyethylene having a relatively low MFR (I21 / I2) and having a narrow MWD (Mw / Mn) and a fluidity index at hot I2 of about 1.0 g / 10 min), in a 15/85 weight percentage ratio, demonstrates the synergies in the film properties of the mixture. The mixture has impact and thrust resistance values that are greater than the weighted average of the mixture components, a tear in the TD that increases more than 10% over the weighted average of the mixture components, and turbidity values and brightness that improved to levels beyond that expected for the weighted average of the mixture components. In addition, when compared to a mixture containing HPLDPE (eg, LF-Y819-A) in the same amount as the first polyethylene copolymer 1A, the film prepared from the inventive mixture comprising 15% by weight of 1A and 85% in weight of 2B it has better properties of resistance to tear in the MD, to the impact by throwing and to the perforation. Although a mixture of resin 1C and resin 2B * (a linear low density polyethylene having a relatively low MFR (I21 / I2) and having a narrow MWD (Mw / Mn) and an I2 hot melt index of about 1, 0 g / 10 min), in a 15/85 weight percentage ratio, has an impact by depreciated pitch, the tears in the MD and TD are greater than the weighted average of the components of the mixture. The blend also demonstrates synergistic improvements in turbidity and brightness (i.e., the turbidity and brightness values improve even further than the expected weighted average). Furthermore, when compared to a mixture containing HPLDPE (eg, LF-Y819-A) in the same amount as the first 1C polyethylene copolymer, the film prepared from the inventive mixture comprising 15% by weight of 1C and 85% in weight of 2B * it has better properties of resistance to tear in the MD, to the impact by throwing and to the perforation. Mixtures 1A with 2B or 1C with 2B * can be extruded with a specific production of 1.2 kg (2.7 lb) / hour / rpm, at an extruder head pressure of 36,921.4-37,162.8 kPa ( 5355-5390 psi) or 33,094.8-33,405.1 kPa (4800-4845 psi), respectively, which is at least comparable to a mixture comprising equivalent amounts of HPLDPE.
[0357] With reference to Table 7, a mixture of resin 1A with 2C (a linear low density polyethylene having an I2 hot melt index of 0.93 g / 10 min and a density of 0.917 g / cm3), in a weight percentage ratio of 15/85, has tear values in TD, puncture resistance, turbidity and gloss that are all improved beyond that expected for a weighted average of the blended components, demonstrating the same positive synergies in the blending film . In addition, the addition of resin 1A improves optical properties, without reducing the impact on the pitch and the tear in the MD as much as using HPLDPE (eg, LF-Y819-A) as a component of the mixture in equivalent amounts. Thus, compared to a mixture containing HPLDPE in the same amount as the first polyethylene copolymer 1A, the film prepared from the inventive mixture comprising 15% by weight of 1A and 85% by weight of 2C has better tear resistance properties in the MD, pitching and punching. A mixture of 1C and 2C resin, in a 15/85 weight percentage ratio, shows positive synergy with regard to turbidity and brightness values, each of which is further improved than expected for a weighted average of the mixed components. The tear in the MD and the TD, as well as the module in the MD and the TD of the mixture prepared with resin 1C and resin 2C, in a weight percentage ratio of 15/85, are comparable to the expected values according to Mixing rule and are not impacted in an immensely negative way. In addition, the addition of 1C resin improves the optical properties, without reducing the impact to the pitch and the tear in the MD, as much as when using the HPLDPE (eg, LF-Y819-A) as a component of the mixture in quantities equivalent. Mixtures of 1A with 2C or 1C with 2C can be extruded with a specific production of 1.08 or 1.11 kg (2.38 or 2.44 lb) / hour / rpm, respectively, at a pressure in the extruder head 27,785.9-28,027.2 kPa (4030-4065 psi) or 26,717.2-26,958.5 kPa (3875-3910 psi), respectively, which is at least comparable to the mixture comprising equivalent amounts of HPLDPE.
[0358] Table 8 shows that a mixture of resin 1A with 2D resin (a linear low density polyethylene having an I2 hot melt index of 1 g / 10 min and a density of 0.92 g / cm3), in a weight percentage ratio of 15/85, has tear resistance values in TD and perforation that are greater than the weighted average expected for the mixed components. Mixtures of resin 1A with 2D resin or resin 1C with 2D resin, in a weight percentage ratio of 15/85, also demonstrate positive synergy in elongation in MD and in TD at rupture, since the values for each mixture are higher than the expected weighted average. The impact to pitch and the secant modulus at 1% of mixtures consisting of resin 1A with 2D resin or resin 1C with 2D resin, in a weight percentage ratio of 15/85, are comparable to the expected values of the Mixing Rule. It is also evident that the addition of 1A resin improves the optical properties, without reducing the impact to the pitch and the tear in the MD as much as the addition of HPLDPE (eg, LF-Y819-A) in equivalent amounts. Similar trends are observed for a mixture of 1C with 2D at a weight percentage ratio of 15/85. Thus, when compared to a mixture containing HPLDPE in the same amount as the first polyethylene copolymer 1A, or 1C, the film prepared from the inventive mixtures has much better properties of tear resistance in MD, impact by throwing and perforation . Mixtures of 1A with 2D or 1C with 2D can be extruded with a specific production of 1.11 or 1.13 kg (2.44 or 2.50 lb) / hour / rpm, respectively, at a pressure in the extruder head 27,923.8-28,234 kPa (4050-4095 psi) or 25,200,3-27,372.2 kPa (3655-3970 psi), respectively, which is at least comparable to the mixture comprising equivalent amounts of HPLDPE.
[0359] In total, Tables 6-8 show that the films prepared from the polymer mixtures of the present invention, and that they are rich in the second polyethylene copolymer (e.g., 15% by weight of 1A or 1C / 85% by weight of 2A, 2B, 2B *, 2C or 2D), have throw impact values of at least 250 g / 2.5 x 10-3 cm (1 mil), have tear strengths in the MD of more than 190 g / 2.5 x 10-3 cm (1 mil), a tear ratio in the MD to tear in the TD of at least 0.4, a secant modulus in the MD or TD at 1% deformation of at least 130 MPa, a turbidity of less than 10%, and a 45 ° gloss of at least 55. The inventive blends in Tables 6-8 demonstrate a good balance of strength, hardness and optical properties for use in film applications .
[0360] Figure 8 shows that the use of the first polyethylene copolymer (eg, resin 1A) in mixtures with a linear low density polyethylene material (eg, resins 2B, 2C or 2D) improves the shear thinning ratio ( * 0.1 /  * 10), as determined by dynamic mechanical analysis, which is a measure of processability, as the amount of the first polyethylene copolymer is increased in the mixture. The synergy in the shear-thinning ratio for the inventive mixtures indicates improvements in the tendency to melt fracture and, consequently, in the processability.
[0361] Figure 9 shows how the melt strength (in centiNewtons, cN) of a mixture with a linear low density material (eg, resins 2B, 2C or 2D) also increases as the amount of first polyethylene copolymer (eg, resin 1A) is increased in the mixture. The improvement can be as much as 20 to 45%, depending on the nature of the first and second polyethylene copolymer components.
[0362] In view of the aforementioned data, the resin mixtures of the present invention have improved optical properties in relation to any of the components of the mixture, when each is blown on film. See Tables 5, 6, 7 and 8. As shown in Tables 6, 7 and 8, mixing HPLDPE in a linear low density polyethylene can also improve the optical properties, but this comes at the expense of other properties of the film, namely, the value of the impact per pitch, the resistance to perforation and the tears in the MD direction.
[0363] For this reason, the present invention provides mixtures of polymers having good processability which, when blown on film, provide good physical properties, such as impact resistance, puncture resistance, tear resistance and hardness, as well as good optical properties .
[0364] In addition, the use of an equivalent amount of the first polyethylene copolymer, instead of a linear low density material at high pressure, results in mixtures having by far tear resistance in the MD, resistance to impact by throwing, and better puncture resistance, without significant loss in other properties, including modulus in MD and elongation in MD and TD at break.
[0365] In view of the foregoing, the first polyethylene copolymers described in this document (eg, resins 1A-1F) can be used as a highly successful alternative blend component for an HPLDPE material to relieve the processing deficiencies of a linear low density polyethylene material (such as, for example, those having narrow molecular weight distributions and / or fractional flow rates) with better conservation and balance of the properties of the film in the MD and TD of the than the HPLDPE material.
[0366] Table 9 shows the properties of the blending film that are rich in the first polyethylene copolymer, instead of the second ethylene copolymer (eg 85% by weight of 1C / 15% by weight of 2B *, 2C or 2D). TABLE 9 FILM PROPERTIES (1C / 2B *, 1C / 2C AND 1C / 1D INVENTIVE MIXTURES RICH IN 1C)



[0367] Table 9 shows that mixtures of resin 1C with resin 2B *, resin 1C with resin 2C and resin 1C with 2D resin, in a weight percentage ratio of 85/15, have impact by pitch, tear in the MD and in TD, puncture resistance, secant modulus in MD and TD, similar tensile, turbidity and gloss properties. The three inventive blends consisting of 85% by weight of the first polyethylene copolymer and 15% by weight of the second polyethylene copolymer also show similar extrusion parameters in the conversion of the film. Such trends indicate that the properties of the film and the processability of mixtures that are rich in the first polyethylene copolymer, such as 1C, do not change significantly, regardless of the type of the second copolymer (eg, a linear low density polyethylene, LLDPE) used in mixtures. The first polyethylene copolymer described in this document (eg, resins 1A-1F) can be used with a wide range of the second polyethylene copolymers in mixtures, to achieve a good balance of processability and physical properties of the resin in applications of movies. INDUSTRIAL APPLICABILITY
[0368] Plastic film prepared from ethylene copolymers is used commercially in several industrial applications, such as, for example, food packaging. The present invention provides a mixture of polymers comprising a first polyethylene copolymer and a second polyethylene copolymer, which, when transformed into a film, has a balance of good mechanical and optical properties.

权利要求:
Claims (28)
[0001]
1. Mixture of polymers CHARACTERIZED by the fact that it comprises: a) from 5 to 95% by weight of a first polyethylene copolymer having a density of 0.916 to 0.936 g / cm3, a hot flow index (I2) of 0, 1 to 2.0 g / 10 min, a fluidity ratio (I21 / I2) of 32 to 50, a molecular weight distribution (Mw / Mn) of 3.6 to 6.5, an inverted comonomer distribution profile , as determined by GPC-FTIR, a multimodal TREF profile, a distribution amplitude index of the CDBI50 composition from 50% by weight to 75% by weight, as determined by TREF, and which still satisfies the relationship: (Mw / Mn )> 72 [(I21 / I2) -1 + 10—6 (Mn)]; and b) from 95 to 5% by weight of a second polyethylene copolymer which is a linear low density polyethylene (LLDPE) different from the first polyethylene copolymer and having a density of 0.910 to 0.940 g / cm3, a hot flow index (I2) from 0.2 to 5.0 g / 10 min, and a hot flow rate (I21 / I2) of less than 35.
[0002]
2. Mixture of polymers, according to claim 1, CHARACTERIZED by the fact that the first polyethylene copolymer has an δXO of 55 ° to 70 °, where δXO is the phase angle in which the complex module (G *) and the complex viscosity (n *) are numerically equivalent on a graph of phase angle versus complex modulus and complex viscosity as determined by dynamic mechanical analysis.
[0003]
3. Mixture of polymers, according to claim 1, CHARACTERIZED by the fact that the first polyethylene copolymer satisfies the ratio: δXO <80.7 - (CDBI50) / (Mw / Mn) in an δXO of 55 ° to 70 °, where δXO is the phase angle at which the complex modulus (G *) and the complex viscosity (n *) are numerically equivalent in a graph of phase angle versus complex modulus and complex viscosity as determined by dynamic mechanical analysis.
[0004]
4. Mixture of polymers, according to claim 1, CHARACTERIZED by the fact that the first polyethylene copolymer satisfies the ratio: δXO <83.0 - 1.25 (CDBl5o) / (Mw / Mn), where δXO is the phase angle at which the complex modulus (G *) and the complex viscosity (n *) are numerically equivalent on a graph of phase angle versus complex modulus and complex viscosity as determined by dynamic mechanical analysis.
[0005]
5. Mixture of polymers, according to claim 1, CHARACTERIZED by the fact that the first polyethylene copolymer has a multimodal TREF profile comprising two maximum intensities at elution temperatures T (low) and T (high); where T (low) is 65 ° C to 85 ° C, and T (high) is 9 ° C to 98 ° C.
[0006]
6. Mixture of polymers according to claim 1, CHARACTERIZED by the fact that the mixture comprises from 5 to 5% by weight of the first polyethylene copolymer and from 95 to 5% by weight of the second polyethylene copolymer.
[0007]
7. Mixture of polymers according to claim 1, CHARACTERIZED by the fact that the first polyethylene copolymer has a molecular weight distribution (Mw / Mn) of 4, o to 6, o.
[0008]
8. Mixture of polymers, according to claim 1, CHARACTERIZED by the fact that the first polyethylene copolymer has a hot melt index (l2) of o, 25 to o, 8th g / 1st min.
[0009]
Mixture of polymers according to claim 1, CHARACTERIZED by the fact that the first polyethylene copolymer has a density of 0.917 to 0.927 g / cm3.
[0010]
10. Mixture of polymers according to claim 1, CHARACTERIZED by the fact that the first polyethylene copolymer has an average molecular weight distribution Z (Mz / Mw) of 2, o to 4, o.
[0011]
11. Mixture of polymers according to claim 1, CHARACTERIZED by the fact that the first polyethylene copolymer has an amount eluting at a temperature of 90 ° C to 105 ° C from 5 to 30 weight percent, as determined by TREF.
[0012]
12. Mixture of polymers according to claim 1, CHARACTERIZED by the fact that the first polyethylene copolymer has an amount eluting at a temperature above 100 ° C of 0 weight percent, as determined by TREF.
[0013]
13. Mixture of polymers according to claim 1, CHARACTERIZED by the fact that the second polyethylene copolymer has a density of 0.916 to 0.930 g / cm3.
[0014]
14. Mixture of polymers according to claim 1, CHARACTERIZED by the fact that the second polyethylene copolymer has a CDBI50 of at least 50% by weight.
[0015]
15. Mixture of polymers, according to claim 1, CHARACTERIZED by the fact that the second polyethylene copolymer has a molecular weight distribution (Mw / Mn) of 1.7 to 5.0.
[0016]
16. Film structure CHARACTERIZED by the fact that it comprises at least one layer comprising the mixture of polymers as defined in claim 1.
[0017]
17. Blown film CHARACTERIZED by the fact that it comprises the mixture of polymers, as defined in claim 1, the film having a turbidity of less than 10% and a brightness at 45 ° of more than 55.
[0018]
18. Molded film CHARACTERIZED by the fact that it comprises the mixture of polymers, as defined in claim 1, the film having a turbidity of less than 10% and a brightness at 45 ° of more than 55.
[0019]
19. Mixture of polymers CHARACTERIZED by the fact that it comprises: a)) from 5 to 95% by weight of a first polyethylene copolymer having a density of 0.916 to 0.936 g / cm3, a hot flow index (I2) of 0 , 1 to 1.0 g / 10 min, a hot flow rate (I21 / I2) of 32 to 50, a molecular weight distribution (Mw / Mn) of 3.6 to 6.5, a distribution profile inverted comonomer, as determined by GPC-FTIR, a multimodal TREF profile, a distribution amplitude index of the CDBI50 composition from 50% by weight to 75% by weight, as determined by TREF, and which further satisfies the relationship: ( Mw / Mn)> 72 [(I21 / I2) -1 + 10-6 (Mn)]; and b) 95 to 5% by weight of a second polyethylene copolymer which is a linear low density polyethylene (LLDPE) having a density of 0.910 to 0.940 g / cm3, a hot flow index (I2) of 0.2 at 5.0 g / 10 min, and a hot flow rate (I21 / I2) of less than 32.
[0020]
20. Mixture of polymers, according to claim 19, CHARACTERIZED by the fact that the first polyethylene copolymer has an δXO of 55 ° to 70 °, where δXO is the phase angle in which the complex module (G *) and the complex viscosity (n *) are numerically equivalent on a graph of phase angle versus complex modulus and complex viscosity as determined by dynamic mechanical analysis.
[0021]
21. Film structure CHARACTERIZED by the fact that it comprises at least one layer comprising the mixture of polymers as defined in claim 19.
[0022]
22. Blown film CHARACTERIZED by the fact that it comprises the polymer blend as defined in claim 19, the film having a turbidity of less than 10% and a 45 ° gloss of more than 55.
[0023]
23. Molded film CHARACTERIZED by the fact that it comprises the mixture of polymers, as defined in claim 19, the film having a turbidity of less than 10% and a gloss at 45 ° of more than 55.
[0024]
24. Mixture of polymers CHARACTERIZED by the fact that it comprises: a) from 5 to 95% by weight of a first polyethylene copolymer having a density of 0.916 to 0.936 g / cm3, a hot flow index (I2) of 0, 1 to 1.0 g / 10 min, a hot flow rate (I21 / I2) of at least 30, a molecular weight distribution (Mw / Mn) of 3.6 to 6.5, a distribution profile of inverted comonomer, as determined by GPC-FTIR, a multimodal TREF profile, a distribution amplitude index of the CDBI50 composition from 50% by weight to 75% by weight, as determined by TREF, and which further satisfies the relationship: (Mw / Mn)> 72 [(I21 / I2) -1 + 10-6 (Mn)]; and b) 95 to 5% by weight of a second polyethylene copolymer which is a linear low density polyethylene (LLDPE) having a density of 0.910 to 0.940 g / cm3, a hot flow index (I2) of 0.2 at 5.0 g / 10 min, and a hot flow rate (I21 / I2) of less than 35.
[0025]
25. Mixture of polymers according to claim 24, CHARACTERIZED by the fact that the first polyethylene copolymer has an δXO of 55 ° to 70 °, where δXO is the phase angle at which the complex module (G *) and the complex viscosity (n *) are numerically equivalent on a graph of phase angle versus complex modulus and complex viscosity as determined by dynamic mechanical analysis.
[0026]
26. Film structure CHARACTERIZED by the fact that it comprises at least one layer comprising the mixture of polymers as defined in claim 24.
[0027]
27. Blown film CHARACTERIZED by the fact that it comprises the mixture of polymers, as defined in claim 24, the film having a turbidity of less than 10% and a gloss of more than 55. 28 Molded film CHARACTERIZED by the fact that it comprises the polymer blend, as defined in claim 24, the film having a turbidity of less than 10% and a 45 ° gloss of more than 55.
[0028]
28. Molded film CHARACTERIZED by the fact that it comprises the mixture of polymers, as defined in claim 24, the film having a turbidity of less than 10% and a gloss at 45 of more than 55.

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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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2020-05-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-03-09| B09A| Decision: intention to grant|

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2021-03-30| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/12/2013, 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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CA2800056|2012-12-24|

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CA2800056A|CA2800056A1|2012-12-24|2012-12-24|Polyethylene blend compositions|

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PCT/CA2013/001024|WO2014100889A1|2012-12-24|2013-12-12|Polyethylene blend compositions and film|

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