MXPA00001590A - Films produced from substantially linear homogeneous olefin polymer compositions - Google Patents

Abstract

The subject invention provides a film having at least one layer comprising an interpolymer of ethylene and at least one comonomer selected from the group consisting of C3-C20 a-olefins, dienes, and cycloalkenes, wherein the interpolymer is characterized as having a high degree of processability, good optical performance, and good mechanical properties. The subject invention further provides film fabrication processes and polymer compositions which are useful in preparing the subject films.

Description

.__ MOVIES PRODUCED FROM POLYMERIC COMPOSITIONS OF HOMOGENEOUS OLEFIN SUBSTANTIALLY LINEAR The subject of the invention relates to polymeric ethylene compositions which are useful in film applications. In particular, the object of the invention relates to polymeric ethylene compositions which exhibit the processing capacity of highly branched low density polyethylene, while exhibiting improved mechanical properties, and to films prepared therefrom. Historically speaking, highly branched low density polyethylene has found great utility in blown film applications, which can be attributed, in part, to its unique processing capacity. The large amounts of long chain branching and broad molecular weight distribution give this polymer the shear thinning and melting strength properties unmatched by heterogeneously branched linear low density polyethylene. The thinning of non-Newtonian shear stress provides high shear stress, low melt viscosity for good extruder processing capacity and low shear, high melt viscosity for superior bubble film bubble stability. Low density polyethylene has found utility in a variety of film applications. Markets, which require a combination of high processing capacity resins, but do not require high transparency film, include industrial liners, heavy-duty shipping sacks, non-transparent bags for shelves and counters, straw films, and separators. rubber. Markets that require a combination of high processing capacity resins and high transparency films include clear liners, baking films, compression films, and cloth bags. The requirements for demisting vary depending on the application, but include elements of (1) "extrudability" of the polymer (high shear rheology) and melting strength (low shear rheology); (2) mechanical properties of the manufactured article; and (3) optical properties of the manufactured article. The actual performance requirements are given in terms of (1) film bubble stability, polymer output rate (kg / hr) and extruder performance (pressure, melting temperature and motor amperes); (2) resistance of the manufactured article (such as stresses, resistance to rupture, resistance to puncture); and (3) transparency, fogging and gloss of the manufactured article. The heterogeneously branched ethylene / α-olefin interpolymers, which are referred to in the industry as linear low density polyethylene (LDPE), have similarly found utility in blowing film applications. In many aspects, such resins are preferred for low density polyethylene, as well as leading to blowing films exhibiting breaking and stiffening properties. However, such polymers are more difficult to process and have optical properties, such as fogging and transparency, lower than those of films prepared with highly branched low density polyethylene. In developing markets, the demand for polyolefins is growing, which exhibits low density polyethylene processing capacity. However, the demand is currently exceeding the investment in new low density polyethylene plants. The industry will find advantages in olefin polymer compositions which are useful for preparing blowing films having stiffness and impact properties comparable to those of heterogeneously branched ethylene / alpha olefin interpolymers, which exhibit the processing capacity and properties Highly branched low density polyethylene optics. Preferably, such polymer compositions will be produced in low pressure, slurry or gas phase polymerization solution reactions. The Patent of E.U.A. No. 5,539,076 discloses a particulate polymer composition which is a mixture catalytically produced in situ having a broad bimodal molecular pitch distribution. Molecular weight distributions of 2.5 to 60 are widely claimed, with molecular weight distributions being preferred from 10 to 50, and 15 to 30 being more preferred.

The Patent of E.U.A. No. 5,420,220 discloses a film comprising a metallocene-catalyzed ethylene polymer having a density of 0.900 to 0.929 g / cm3, a l21 / l2 of 15 to 25, a Mp / n from 2.5 to 3.0, and a melting point of 95 ° C to 135 ° C. Illustrated is a polymer that has a l2? / L2 of 18 and an Mp / Mn of 2.6. The Patent of E.U.A. No. 4,205,021 describes a copolymer of ethylene and a C5-C18 α-olefin, whose polymer has a density of 0.90 to 0.94 g / cm3. The compositions described are such that they have a large chain branching, and are described as having preferably two or more DSC melting points. The E.U.A. 4,205,021 describes the use of the polymers described in blowing films. The E.U.A. No. 08 / 858,684 (PCT Publication WO 93 / 13,143), describes the in situ preparation of a mixture of two ethylene polymers prepared with a catalyst of restricted geometry, wherein each of the polymers is such that it has an index of fusion (l2) from 0.05 to 50 g / 10 minutes. The polymers can be prepared in a single reactor with two species of active catalysts, or can be produced in a double reactor configuration with the same or different catalysts of restricted geometry being provided in each reactor. The industry will find advantage in olefin polymer compositions which usefully replace high pressure low density polyethylene, without requiring film manufacturers to couple in significant reconstruction and retrofitting of their manufacturing lines. The desired olefin polymer compositions should have processing capacity and optical properties which are at least approximately equivalent to the highly branched low density polyethylene. Preferably, the desired olefin polymer compositions will also exhibit stiffness and impact properties which are improved over the low density polyethylene properties. Preferably, such polymer compositions will be produced in low pressure solution reactions, slurry, or gas phase polymerization. Accordingly, the object of the invention provides a film having at least one layer comprising an interpolymer of ethylene and at least one comonomer selected from the group consisting of C3-C20 α-olefins, dienes, and cycloalkanes, wherein The interpolymer is characterized by having: a. a density of 0.910 to 0.930 g / cm3, b. a melt index (12) of 0.2 to 10 g / 10 minutes, c. a 0 / l2 from 9 to 20, and d. a molecular weight distribution, Mp / Mn from 2.1 to 5. In an especially preferred embodiment, such polymer will also have from one to two crystallization peaks as determined by FEET, each occurring between 45 ° C and 98 ° C, with each having an IATC less than 18 ° C. In a preferred embodiment, the interpolymer will have a l2 of 1.0 to 7 g / 10 minutes. In a more preferred embodiment, the interpolymer will be prepared in two polymerization reactors, each of which contains a metallocene catalyst with geometry restricted to a single site. In such a more preferred embodiment, the interpolymer, when fractionated by gel permeation chromatography, will be more preferably characterized by comprising: a. from 25 to 90 percent of a first polymer fraction that has a melt index (12) of 0.05 to 1.0 g / 10 minutes, and a single crystallization peak between 45 ° C and 98 ° C that has a lower IATC value than 18 ° C as determined by FEET; and b. from 10 to 75 percent of a second polymer fraction having a melt index (12) of at least 30 g / 10 minutes, and a single crystallization peak between 45 ° C and 98 ° C having an IATC value less than 18 ° C as determined by FEET. In another preferred embodiment, the polymer will have a l2 of 0.05 to less than 2.5 g / 10 minutes, a 0 / l2 of at least 12.5, and an Mp / Mn of 2.1 to 3.0. In this alternate preferred embodiment, the polymer will be more preferably characterized by having a single crystallization peak between 45 ° C and 98 ° C having an IATC less than 18 ° C as determined by FEET. The object of the invention further provides a process for preparing a blow film comprising: a. Melt an ether polymer at a temperature of 149 to 177 ° C, b. extrude the interpolymer in the regime of 6.8 to 23 kg / hr through a die having die openings of 1 to 20 mm, c. blow the film in a bubble, in a blow ratio of 1.3 to 2, to form a film with a caliber of 0.01 to 0.1 mm. d. cooling the film by means external to the bubble, wherein the interpolymer is an interpolymer of ethylene and at least one comonomer selected from the group consisting of α-olefins, dienes, and cycloalkanes which are characterized by having: i. a density of 0.910 to 0.930 g / cm3, ii. a melt index (12) of 0.2 to 10 g / 10 minutes, iii. a l? 0 / l2 from 9 to 20, and iv. a molecular weight distribution, Mp / Mn from 2.1 to 5.

In an especially preferred process, the interpolymer employed will have from one to two crystallization peaks between 45 ° C and 98 ° C, each having an IATC less than 18 ° C, as determined by FEET. The object of the invention further provides a process for preparing a blow film comprising: a. melt an interpolymer at a temperature of 149 ° C to 204 ° C, b. Extrude the interpolymer in the regime of 6.8 to 23 kg / hr through a die having a die opening of 1 to 2 mm, c. blow the film in a bubble, in a blown ratio above 2 to 4, to form a film of caliber from 0.05 to 0.13, and d. cooling the film by means external to the bubble, wherein the ether polymer is an interpolymer of ethylene and at least one comonomer selected from the group consisting of α-olefin, dienes, and cycloalkanes which are characterized as having: i. a density of 0.910 to 0.930 g / cm, ii. a melt index (12) of 0.05 to 2.5 g / 10 minutes, iv. a molecular weight distribution, p / Mn from 2.1 to 3. In an especially preferred process, the interpolymer employed will have from one to two crystallization peaks between 45 ° C and 98 ° C, each having an IATC less than 18 ° C , as determined by FEET. The object of the invention further provides a polymer composition consisting essentially of an interpolymer of ethylene and at least one comonomer selected from the group consisting of C3-C20 α-olefins, dienes, and cycloalkenes, wherein the interpolymer is characterized by have: a. a density of 0.910 to 0.930 g / cm3, b. a melt index (12) of 0.2 to 10 g / 10 minutes, c. one l10 / l2 from 9 to 20, d. a molecular weight distribution, Mp / Mn from 2.1 to 5, e. a molecular weight distribution, Mp / Mn, as determined by gel permeation chromatography and defined by the equation: (Mp / Mn) < (l10 / l2) -4.63, and f. a rheology of gas extrusion in such a way that the critical shear rate at the start of the surface fusion fracture for the interpolymer is at least 50 percent greater than the critical shear rate at the start of the melt fracture of surface for a linear ethylene polymer, wherein the interpolymer and the linear ethylene polymer comprise the same comonomer or comonomers, wherein the linear ethylene polymer has a l2, Mp / Mn and density, within ten percent of the interpolymer , and wherein the critical shear rates of the interpolymer and the linear ethylene polymer are measured at the same melt temperature using a gas extrusion rheometer. In an especially preferred embodiment, the objective of the polymer composition will be characterized as having one to two crystallization peaks between 45 ° C and 98 ° C, each having an IATC less than 18 ° C, as determined by FEET. These and other embodiments are described more fully in the following detailed description, wherein: FIGURE 1 is a plot of Mp against the melt index (12) for polymers of the Examples and Comparative Examples, FIGURE 2 is a graph of Mp / Mn against l10 / l2 for polymers of the Examples and Comparative Examples, and FIGURE 3, is a diagrammatic representation of the calculation of the Crystallization Temperature Amplitude Index (IATC), for a peak of general crystallization that occurs in a Fractional Analysis of Temperature Elevation Elution, FEET. Test Methods Unless stated otherwise, the following procedures are employed: Density is measured according to ASTM D-792. The samples are annealed at ambient conditions for 24 hours before the measurement is taken. The Fusion index (12) is measured according to ASTM D-1238, condition 190 ° C / 2.16 kg (formally known as "Condition (E)"). I10, is measured in accordance with ASTM D-1238, Condition 190 ° C / 10 kg (formally known as "Condition N"). The molecular weight is determined using gel permeation chromatography (CPG) in a Waters 150 ° C high temperature chromatographic unit equipped with three columns of mixed porosity (Polymer Labs 103)., 104, 105, and 106), operating in a temperature system of 140 ° C. The solvent is 1, 2,4-trichlorobenzene, of which 0.14 weight percent solutions of the samples are prepared by injection. The flow rate is 1.0 mL / min. and the size of the injection is 100 microliters. The molecular weight determination is deduced using polystyrene standards of narrow molecular weight distribution (from Polymer Laboratories) in conjunction with their elution volumes, the equivalent polyethylene molecular weights are determined using appropriate Mark-Houwink coefficients for polyethylene and polystyrene ( as described by Williams and Word in Journal of Polymer Science, Polymer Letters, Vol. 6, (621) 1968) to derive the following equation: fjolietileno111 3 (Mpo | iestireno) D. In this equation, a = 0.4316 and b = 1.0. Weight average molecular weight, Mp, is calculated in the usual way according to the following formula: Mp =? w * M, where w, and M, are the fraction of weight and molecular weight, respectively, of the first fraction that is eluted from the CPG column. The percentage of melting temperature, crystallization temperature, and crystallinity were determined using differential scanning calorimetry (CBD). The differential scanning calorimetry (CBD) data were generated by placing each sample (5 mg) in an aluminum tray, the sample was heated to 160 ° C, cooled to 10 ° C / min and the endotherm was recorded by means of the sweep from -30 ° C to 140 ° C at 10 ° C / min using a Perkin Elmer CBD 7. The CBD exotherm (cooling curve) was also recorded by sweeping from 140 to -30 at 10 ° C / min. The percentage of crystallinity is calculated with the equation:% C = (A / 292 J / g) x 100 in which% C represents the percentage of crystallinity and A represents the heat of fusion of ethylene in Joules per gram (J / g) ) as determined by differential scanning calorimetry (CBD). The fogging is measured according to ASTM D-1003.

Elmendorf breakage is determined in accordance with ASTM D1922. Stress and stiffness resistance is determined in accordance with ASTM D638. The 45 ° brightness is measured according to ASTM D2457. Dart impact (A, B) is measured in accordance with ASTM D-882.

Clarity is measured in accordance with ASTM D-1746. The term "interpolymer" is used herein to mean a copolymer, or a terpolymer, or a higher order polymer. That is, at least one other comonomer is polymerized with ethylene to make the interpolymer. The ethylene / α-olefin interpolymer used in the films of the present invention is preferably a linear or substantially linear homogeneous ethylene / α-olefin interpolymer. By the term "homogeneous", it is understood that any comonomer is randomly distributed within a given interpolymer molecule and substantially all polymer molecules have the same ethylene / comonomer ratio within said interpolymer.

The melting peak of homogeneous linear and substantially linear ethylene polymers, obtained using differential scanning calorimetry, will be amplified as the density decreases and / or as long as the average molecular weight number decreases. However, unlike heterogeneous polymers, when a homogeneous polymer which has been prepared in a solution polymerization process has a melting peak greater than 115 ° C (such as is the case of polymers having a higher density at 0.940 g / cm3), it does not additionally have a different lower temperature melting peak. In addition, or alternatively, the homogeneity of the constituents of the interpolymer can be described by the Crystallization Temperature Amplitude Index, IATC. The IATC can be measured from the data obtained from techniques known in the art, such as, for example, temperature rise elution fractionation (abbreviated herein as "FEET"), which is described, for example, in Wild et al., Journal of Polymer Science, Poly. Phys. Ed., Vol. 20, p. 441 (1982), in the U.S. Patent. 4,798,081 (Hazlitt et al.). An example of how the IATC is obtained for a peak of crystallization given in the FEET experiment is shown in Figure 3. The calculation applies only to the distinct, individual crystallization peaks in the FEET analysis. The FEET data can be unconverted before the calculation. The calculation consists of: (1) measuring the height of the crystallization peak in question; then (2) measure the amplitude of the peak at half the height. The value is reported in ° C. The IATC for the homogeneous ethylene / α-olefin interpolymers useful in the invention is less than 18 ° C, preferably less than 15 ° C. An IATC value of less than 10 ° C can be obtained. The homogeneous ethylene interpolymer useful in the practice of the invention will preferably have an Mp / Mp of 1.5 to 3.5, more preferably 1.7 to 3.0. It is noted that in the embodiment of the invention, which comprises a reaction or physical mixture of two homogeneous polymers, the total composition can have an Mp / Mn greater than 3.5, although the individual components will have an Mp / Mn in the scale more narrow described above. The linear ethylene interpolymers are interpolymers characterized by having a structure of the interpolymer base substituted with less than 0.01 long chain branches per 1000 carbons. The substantially linear ethylene interpolymers are interpolymers characterized by having an interpolymer base structure substituted with 0.01 to 3 long chain branches per 1000 carbons. Due to the presence of such long chain branches, the substantially linear ethylene interpolymers are further characterized by having a melt flow ratio (o / l2) which can vary independently of the polydispersity index, alternatively referred to as the molecular weight distribution or Mp / Mn. This aspect matches the substantially linear ethylene polymers with a high degree of processability despite a narrow molecular weight distribution. It is noted that the substantially linear and linear interpolymers useful in the invention differ from the low density polyethylene prepared in a high pressure process. In this regard, while the low density polyethylene is an ethylene homopolymer having a density of 0.915 to 0.935 g / cm3, the homogeneous linear and substantially linear interpolymers useful in the invention require the presence of a comonomer to reduce the density to the scale of 0.900 to 0.935 g / cm3. The long chain branches of substantially linear ethylene interpolymers have the same comonomer distribution as the base structure of the interpolymer and may be as long as the length of the interpolymer base structure. In the preferred embodiment, where a substantially linear ethylene / α-olefin interpolymer is employed in the practice of the invention, such an interpolymer will be more preferably characterized by having a base structure of the interpolymer substituted with from 0.01 to 3 chain branches. long per 1000 carbons. Methods for determining the amount of long chain branches present, both qualitatively and quantitatively, are known in the art. To obtain qualitative methods for determining the presence of long chain branches, see, for example, U.S. Patents. Nos. 5,272,236 and 5,278,272. As shown herein, a gas extrusion rheometer (REG) can be used to determine the rheological processing index (IP), the rate of critical shear stress at the beginning of the surface melt fracture, and stress strain critical shear at the beginning of the gloss fusion fracture, which in turn indicates the presence or absence of long chain branching as shown above.

The gas extrusion rheometer useful in determining the rheological processing index (IP), the rate of critical shear stress at the beginning of the surface melt fracture, and the critical shear stress at the beginning of the melt fracture. Thickness, is described by M. Shida, RN Shroff, and LV Cancio in Polymer Engineering Science, Vol. 17, No. 11, p. 770 (1977), and in "Rheometers for Molten Plastics" by John Dealy, published by Van Nostrand Reinhold Co. (1982) on pp. 97-99. The REG experiments are performed at a temperature of 190 ° C, at nitrogen pressures between 1.72 and 37.9 MPa using a diameter of 0.0754 mm, given 20: 1 L / D with an entry angle of 180 °. For substantially linear ethylene interpolymers, the IP is the apparent viscosity (in kpoise) of a material measured by REG at an apparent shear stress of 0.215 MPa. The substantially linear ethylene interpolymers useful in the invention will have an IP in the range of 0.01 kpoise to 50 kpoise, preferably 15 kpoise or less. The substantially linear ethylene interpolymers have an IP which is less than or equal to 70 percent of the IP of a linear ethylene interpolymer (a Ziegler polymerized polymer or a linear homogeneous ethylene interpolymer) having the same comonomer or comonomers, and it has a l2, Mp / Mn, and density, each of which is within 10 percent of the substantially linear ethylene interpolymer. An apparent shear stress versus an apparent shear rate graph can be used to identify the melting fracture phenomenon and to quantify the critical shear rate and critical shear stress of ethylene polymers. According to Pamamurthy, in the Journal of Rheology, 30 (2), 1986, pages 337-357, before a certain critical flow regime, the observed extrudate irregularities can be broadly classified into two main types: surface fusion fracture and thick fusion fracture. The surface fusion fracture occurs under seemingly stable flow conditions and varies in detail from loss of specular film brightness to the more severe form of "shark skin". At present, as determined using the gas extrusion rheometer described above, the onset of the surface melt fracture is characterized as the principle of extrudate gloss loss at which the rigidity of the extrudate surface can only be detected for the increase to 40 times. The rate of critical shear stress at the beginning of the surface melt fracture for a substantially linear ethylene interpolymer is at least 50 percent greater than the critical shear rate at the beginning of the surface melt fracture for a polymer linear ethylene having the same comonomer or comonomers and having a l2, Mp / Mn and density within ten percent of the substantially linear ethylene polymer. The melt fracture of thickness occurs in non-stable extrusion flow conditions and varies from regular (alternating rough and uniform, helical, etc.) to random distortions. The critical shear stress at the start of the melt fracture thickness of substantially linear ethylene interpolymers, especially those having a density greater than 0.910 g / cm 3, is greater than 0.4 MPa. The presence of long chain branching can also be determined qualitatively by the Dow Rheology Index (IRD), which expresses "a normalized relaxation time as the result of long chain branching" of the polymer. (See, S. Lai and GW Knight, ANTEC '93 Proceedings, INSITE ™ Technology Polyolefins (SLEP) - New Rules in the Structure / Rheology Relationship of Ethylene to-Olefin Copolymers, New Orleans, La., May 1993. Values of IRD vary from 0 for polymers that do not have any measurable long chain branching, such as Tafmer ™ products available from Mitsui Petrochemical Industries and Exact ™ products available from Exxon Chemical Company) to 15, and are independent of the melt index. In general, for low to medium pressure ethylene polymers, particularly at low densities, the IRD provides improved correlations for melt elasticity and high shear flow capacity in relation to intended correlations thereof with melt flow ratios. The substantially linear ethylene interpolymers will have an IRD preferably of at least 0.1, more preferably of at least 0.5, and even more preferably of at least 0.8.

The IRD can be calculated by the equation: IRD = (3.652879 * t? 1.00649 / ?? - 1) / 10 Where to is the characteristic relaxation time of the interpolymer and? O is the shear viscosity of zero of the interpolymer. Both the to and the? O are the values "best suited" to the crossed equation:? /? o = 1 / (1 + (? * t?) 1"n) where n is the index of the power law of the material, and? and? are the measured viscosity and shear rate, respectively. The base determination of the viscosity data and the shear rate are obtained using a Rheometric Mechanical Spectrometer (SMR-800) under a dynamic sweep mode of 0.1 to 100 radians / second at 160 ° C and a gas extrusion rheometer ( REG) at extrusion pressures of 6.89 to 34.5 MPa, which corresponds to a shear stress of 0.086 to 0.43 MPa, using a diameter of 0.0754 mm, given from 20: 1 L / D at 190 ° C. Specific materials can perform from 140 to 190 ° C as required to adapt the variations of the melt index For quantitative methods to determine the presence of long chain branches, see, for example, U.S. Patent Nos. 5,272,236 and 5,278,272 Randall (Rev. Macromol. Chem. Phys., C29 (2 and 3), pp. 285-297), which discuss the measurement of long chain branching using a C13 nuclear magnetic resonance spectroscope, Zimm, G.H. and Stockmayer, W.H., J. Chem. Phys., 17, 1301 (1949); and Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991) pages 103-112, which discusses the use of gel permeation chromatography coupled with a low-angle laser light scattering detector (CPG-DLLBA) and gel permeation chromatography coupled to a detector differential viscometer (CPG-VD). A. Willem deGroot and P. Steve Chum, both of The Dow Chemical Company, at the October 14, 1994 conference of the Federation of Analytical Chemistry and Spectroscopy Society (FACSS) in St. Louis, Missouri, data presented demonstrating that the CPG-VD is a useful technique for quantifying the presence of long chain branches in substantially linear ethylene polymers. In particular, deGroot and Chum found that in substantially linear ethylene polymers, the measured values for long chain branches obtained by this method were well correlated with the level of long chain branches measured using C13 NMR. In addition, deGroot and Chum found that the presence of octene does not change the hydrodynamic volume of the polyethylene samples in solution and, as such, one can count for the molecular weight increase that can be attributed to the short chain branches of octene knowing the percentage by moles of octene in the sample. By deconvoluining the contribution to the molecular weight increase attributable to the short chain branches of 1-octene, deGroot and Chum showed that the CPG-VD can be used to quantify the level of long chain branches in substantially linear ethylene / octene copolymers. deGroot and Chum also showed that a plot of log (l2, melt index) as a function of log (CPG, average molecular weight per weight), as determined by CPG-VD, illustrates that aspects of long-chain branching ( but not to the degree of long-chain branching) of the substantially linear ethylene polymers are comparable to high-pressure polyethylene, highly branched low density polyethylene (PEBDAR) and are clearly distinct from the heterogeneously branched ethylene polymers produced using catalysts Ziegler type (such as linear low density polyethylene and ultra low density polyethylene) as well as homogeneous linear ethylene polymers (such as Tafmer ™ products available from Mitsui Petrochemical Industries and Exact ™ products available from Exxon Chemical Company). The illustrative C3-C20 α-olefins used in the preparation of ethylene interpolymers for use herein, include propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, and 1-octene. Preferred C3-C20 α-olefins include 1. butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, and 1-octene, more preferably 1-hexene and 1-octene. Exemplary cycloalkenes include cyclopentene, cyclohexene, and cyclooctene. Suitable dienes as comonomers, particularly in the manufacture of α-olefin / diene / ethylene interpolymers, are usually non-conjugated dienes having 6 to 15 carbon atoms. Representative examples of suitable non-conjugated dienes include: (a) Straight chain acyclic dienes such as 1,4-hexadiene; 1,5-heptadiene; and 1, 6-octadiene; (b) Branched chain acyclic dienes such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; and 3,7-dimethyl-1,7-octadiene; (c) Single ring alicyclic dienes such as 4-vinylcyclohexene; 1-allyl-4-isopropylidene cyclohexane; 3-allylcyclopentene; 4-allylcyclohexene; and 1-isopropenyl-4-butenylcyclohexene; and (d) Ring-fused and multi-ring alicyclic ring dienes such as dicyclopentadiene; norbornens substituted with alkenyl, alkylidene, cycloalkenyl, and cycloalkylidene, such as 5-methylene-2-norbornene; 5-methylene-5-methyl-2-norbornene; 5-methylene-6,6-dimethyl-2-norbornene; 5-propenyl-2-norbornene; 5- (3-cyclopentenyl) -2-norbornene; 5-ethylidene-2-norbornene; and 5-cyclohexylidene-2-norbornene. A preferred diene is piperylene. Preferred dienes are selected from the group consisting of 1,4-hexadiene; dicyclopentadiene; 5-ethyllidene-2-norbonene; 5-methylene-2-norbornene; 7-methyl-1,6 octadiene; piperylene; and 4-vinylcyclohexene.

The linear or substantially linear ethylene interpolymer preferably is an interpolymer of ethylene with at least one C3-C20 α-olefin comonomer. While not wishing to be bound by a theory, it is believed that the compositions useful in the practice of the claimed invention owe their properties of stiffness and impact improved, at least in part, to the presence of bound molecules. A tied chain is that portion of the polyethylene chain which is ejected from the laminar crystal due to a short chain branching imperfection. See, for example, S. Krimm and T.C. Cheam, Faraday Discuss., Volume 68, page 244 (1979); P.H. Geil, Polymer Single Crystals, published by Wiley, Inc., New York (1963); and P.J. Flory, J. Am Chem. Soc, Volume 84, page 2837 (1962). This chain expelled later can be reincorporated in another crystal, connecting the two crystals together. Since the short chain branching is increased, more strings attached to the segments are formed between the short chain branches are not long enough to bend. In addition, the concentration of bound chains is proportional to the molecular weight and can be influenced by the type and amount of comonomer. The effectiveness of an α-olefin to produce bound chains is proportional to its molecular size. For example, 1-octene is a very efficient comonomer for promoting the formation of attached chains, as its hexyl group interrupts crystal formation more than the butyl or ethyl groups of hexene and butene comonomers, respectively. Accordingly, it is believed that the ethylene / octene polymer has higher bound chain levels than the shorter chain comonomer copolymers, which are thought to improve stiffness. However, if the products are produced by themselves in the gas phase or are directed to competition with polymers produced in the gas phase, usually a C4-Cβ α-olefin will be used as the comonomer.

The homogeneously branched substantially linear ethylene polymer can be suitably prepared using a catalyst of restricted geometry. Metal complexes of restricted geometry and methods for their preparation are described in the application of E.U.A. Series No. 545,403, filed July 3, 1990 (EP-A-4 6.8 5); The Application of E.U.A. Series No. 702,475, filed May 20, 1991 (EP-A-514,828); as well as E.U.A.-A-5,470,993, 5,374,696, 5,231,106, 5,055,438, 5,057,475, 5,096,867, 5,064,802, and 5,132,380. In US-A-5,721,185, certain borate derivatives of the above restricted geometry catalysts are described and a method for their preparation is taught and claimed. In EUA-A-5,453,410, combinations of catalysts of cationic restricted geometry with an alumoxane were described as suitable olefin polymerization catalysts. Exemplary restricted geometry metal complexes in which titanium is present, in the +4 oxidation state include but are not limited to the following: (n-butylamido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (n-butylamido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (t-butylamido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (t-butylamido) dimethyl (? 5 -tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (cyclododecylamido) dimethyl (? 5 -tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (2,4,6-trimethylantalid) dimethyl (5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (l-adamantyl-amido) dimethyl I (? 5- tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (t-butylamido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (t-butylamido) dimethyl (? 5- tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (1-adamantylamido) dimethyl (? 5 -tetramethylcyclopentadyl) -silanetitanium (IV) dimethyl; (n-butylamido) diisoprop oxy (5- tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (n-butylamido or) diisopropoxy (? 5- tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (cyclododecylamido) -diisopropoxy (5-tetramethylcyclopentadyl) -silanetitanium (IV) dimethyl; (cyclododecylamido) diisopropoxy (5-tetramethylcyclopentadienyl) -silanetitanium (IV) dibenzyl; (2,4,6-trimethylanilido) diisopropoxy - (? 5- tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (2,4,6-trimethylanilido) diisopropoxy (5-tetramethyl-cyclopentadienyl) silanetitanium (IV) dibenzyl; (cyclododecylamido) dimethoxy (5-tetramethylcyclopentadienyl) silane titanium (IV) dimethyl; (cyclododecylamido) -dimethoxy (5-tetramethylcyclopentadienyl) silane titanium (IV) dibenzyl; (1-adamantylamido) diisopropoxy (5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (1-adaman ti lamido) diisopropoxy (5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (n-butylamido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (n-butylamido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (2,4,6-trimethylanilido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (2,4,6-trimethylanilido) dimethoxy (5-tetramethylcyclopentadienyl) silane-titanium (IV) dibenzyl; (1-adamantylamido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (1 -admantylamido) d i methoxy (5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (n-butylamido) -ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (n-butylamido) ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (cyclododecylamido) ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (cyclododecylamido) ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl; (2,4,6-trimethylanilido) ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (2,4,6-trimethylanilido) ethoxymethyl (? 5-tetramethylcyclopentadienyl) silane-titanium (IV) dibenzyl; (cyclododecylamido) d -methyl (5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (1-adamantylamido) -ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; and (1-adamantylamido) ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (IV) dibenzyl.

Exemplary constrained geometry metal cexes in which titanium occurs in the +3 oxidation state, include but are not limited to the following: (n-butylamido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (t-butylamido) d i m ethyl (? 5-tetramethylcyclopentadiene i) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (cyclododecylamino) dimethyl (? 5- tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (2,4,6-trimethylanilido) dimethyl (? 5- tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (1-adamantylamido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (t-bu ti lamido) dimethyl (? 5- tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (n-butylamido) diisopropoxy (5- tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (cyclododecylamino) diisopropoxy (η 5 -tetramethylcyanopentadienyl) silanetitanium (III) 2- (N 1 N -dimethylamino) benzyl; (214,6-trimethylanilido) diisopropoxy (? 5-2-methylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (1-adamantylamido) diisopropoxy (? 5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (n-butylamido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (cyclododecylamino) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (1-adamantylamido) d i methoxy (? 5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (2,4,6-trimethylanilido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (n-butylamido) ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (cyclododecylamino) ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; (2,4,6-trimethylanilido) ethoxymethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl; and (1-adamanty lamido) ethoxymethyl (5-tetramethylcyclopentadienyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl. Exemplary restricted geometry metal complexes, in which titanium is present in the oxidation state +2, include but are not limited to the following: (n-butylamido) -dimet i I- (? 5- tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (n-butylamido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (t-butylamido) dimeti I (? 5-tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (t-butylamido) dimethyl I ([beta] 5-metho-I-pentadienyl) -silanetitanium (II) 1,3-pentadiene; (cyclododecylamido) dimethyl (5- tetramethylcyclopentadienyl) silanetitanium (II), 4-difnyl-1,3-butadiene; (cyclododecylamido) dimethyl (? 5 -tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (2,4,6-trimethylanilido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (II) 1,4-difyl enyl-1,3-butadiene; (2,4,6-trimethylanilido) dimethyl (? 5- tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (2,4,6-trimethylanilido) dimethyl (? 5 -tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl; (1-adaman ti lamido) dimethyl (? 5- tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphen-l, 3-butadiene; (1-adamantylamido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (t-butylamido) dime thi (5- Tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (t-butylamido) dimethyl (5- tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (n-butylamido) diisoprop oxy (5- tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (n-butylamido) diisopropoxy (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (cyclododecylamido) -diisopropoxy (5- tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (cyclododecylamido) diisopropoxy (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (2,4,6-trimethylanilido) diisopropoxy (? 5-2-methyl-indenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (2,4,6-trimethylanilide) -diisopropoxy (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (l-adamantylamido) d i i sop ropoxy (γ-tetramethylcyclopentadienyl) silane-titanium (II) 1,4-diphenyl-1,3-butadiene; (1-adamantylamido) diisopropoxy (? D -tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (n-butylamido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (n-butylamido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (cyclododecylamido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (cyclododecylamido) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene; (2,4,6-trimethylanilide) dimethoxy (5-tetramethylcyclopentadienyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene; (2,4,6-trimethylanilido) dimethoxy (5-tetramethylcyclopentadienyl) silane titanium (II) 1,3-pentadiene; (1-adamantyl-amido) dimethoxy (? 5-tetramethylcyclopentadienyl) silane titanium (II) 1,4-difyl enyl-1,3-butadiene; (l-adamantylamido) dimet oxy (5- tetramethylcyclopentadienyl) silanol titanium (11) 1,3-pentadiene; (n-butyl lamido) ethoxy methyl (? 5-tetramethylcyclopentadienyl) silanol titanium (II) 1,4-diphenyl-1,3-butadiene; (n-butylamido) ethoxymethyl (γ-tetramethylcyclopentadienyl) silane titanium (II) 1,3-pentadiene; (cyclododecylamido) ethoxymethyl (α-tetramethylcyclopentadienyl) silane tlitanium (II) 1,4-diphenyl-1,3-butadiene; (cyclododecylamido) ethoxymethyl (5-tetramethylcyclopentadienyl) silane tlitanium (II) 1,3-pentadiene; (2,4,6-trimethylanilido) ethoxymethyl (? 5-tetramethylcyclopentadienyl) silane ttitanium (II) 1,4-dif eni I-1,3-butadiene; (2,4,6-trimethylanilido) ethoxymethyl (5-tetramethylcyclopentadienyl) silane tithitanium (II) 1,3-pentadiene; (1-adamantylamido) ethoxymethyl (5-tetramethyl-cyclopentadienyl) silane titanium (II) 1,4-diphenyl-1,3-butadiene; and (l-adamantylamido) ethoxy methyl (5- tetramethylcyclopentadienyl) silane tlitanium (II) 1,3-pentadiene. The complexes can be prepared by the use of well-known synthetic techniques. The reactions are carried out in a suitable non-interfering solvent at a temperature of -100 to 300 ° C, preferably -78 to 100 ° C, even more preferably 0 to 50 ° C. A reducing agent can be used to cause the metal to be reduced from a larger state to a lower state of oxidation. Examples of suitable reducing agents are alkali metals, alkaline earth metals, aluminum and zinc, alkali metal or alkaline earth metal alloys such as sodium / mercury amalgam and sodium / potassium alloy, sodium naphthalenide, potassium graphite, lithium alkyls , lithium or potassium alkadienyls, and Grignard reagents. The reaction medium suitable for the formation of the complexes includes aliphatic and aromatic hydrocarbons, ethers, and cyclic ethers, particularly branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; aromatic and aromatic compounds suchated with hydrocarbyl such as benzene, toluene, and xylene, dialkyl ethers of C? -, dialkyl ether derivatives of C? -4 of (poly) alkylene glycols, and tetrahydrofuran. Mixtures of the above are also suitable. Suitable activating cocatalysts and activation techniques have previously been taught with respect to different metal complexes in the following references: EP-A-277,033, US-A-5,153,157, US-A-5,064,802, EP-A-468,651 (equivalent to the EUA Series No. 07 / 547,718), EP-A-520,732 (equivalent to the EUA Series No. 07 / 876,268), WO 95/00683 (equivalent to the EUA Series No. 08 / 82,201), WO 97/35893 (equivalent to the EUA Series No. 08 / 818,530), and EP-A-520,732 (equivalent to the EUA Series No. 07 / 884,966 filed on May 1, 1992). Activation cocatalysts suitable for use herein include perfluorinated tri (aryl) boron compounds, and more especially tris (pentafluorophenyl) borate; non-polymeric, compatible, non-coordinated, ion-forming compounds (which include the use of such compounds under oxidation conditions), especially the use of ammonium, phosphonium, oxonium, carbonium, silylium or sulfonium salts of compatible anions, coordinated, and ferrocenium salts of compatible, uncoordinated anions. Suitable activation techniques include the use of volume electrolysis (explained in more detail hereafter). A combination of the above activating cocatalysts and techniques can also be employed. Illustrative, but not limited, examples of boron compounds which can be used as activating cocatalysts are: tri-substituted ammonium salts such as: trimethylammonium borate tetrakis (pentafluorophenyl); triethylammonium borate tetrakis (pentafluorophenyl); tripropylammonium borate tetrakis (pentafluorophenyl); tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate; tri (sec-butyl) ammonium tetrakis (pentafluoro-phenyl) borate; N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate; N, N-dimethylanilinium n-butyltris borate (pentafluorophenyl); N, N-dimethylanilinium benzyltris borate (pentafluorophenyl); N, N-dimethylanilinium tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate; N, N-dimethylanilinium tetrakis (4- (triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) borate; borate of N, N-dimethylanilinium pentafluorophenoxyrtris (pentafluorophenyl); N.N-dimethylanilinium tetrakis (pentafluorophenyl) borate; N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate; trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate; triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate; tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate; tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate; di-methyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate; N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate; N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate; and N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate; disubstituted ammonium salts such as: di- (isopropyl) ammonium tetrakis (pentafluorophenyl) borate; and dicyclohexylammonium borate tetrakis (pentafluorophenyl); trisubstituted phosphonium salts such as: triphenylphosphonium tetrakis (pentafluorophenyl) borate; tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate; and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate; disubstituted oxonium salts such as: diphenyloxonium borate tetrakis (pentafluorophenyl); di (o-tolyl) oxonium tetrakis (pentafluorophenyl) borate; and di (2,6-dimethyl-phenyl) -oxonium tetrakis (pentafluorophenyl) borate; and disubstituted sulfonium salts such as: diphenylsulfonium borate tetrakis (pentafluorophenyl); di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate; and bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate. Alternate preferred catalysts may be represented by the following general formula: (L * -H) (A ') d-wherein: L * is a neutral Lewis base: (L * -H) + is a Bronsted acid; A 'd' is an uncoordinated, compatible anion having a charge of d, and d is an integer from 1 to 3. More preferably A 'd "corresponds to the formula: [M * Q]"; wherein: M * is a boron or aluminum in the formal +3 oxidation state; Y Q each time it occurs, is independently selected from hydride, dialkylamido, halide, hydrocarbyl, halohydrocarbyl, halocarbyl, hydrocarbyloxy, hydrocarbyl substituted hydrocarbyl, substituted hydrocarbyl organometal, substituted hydrocarbyl organometalloid, halohydrocarbyloxy, hydrocarbyl substituted with halohydrocarbyloxy, hydrocarbyl substituted with halocarbyl, and halo substituted with silylhydrocarbyl radicals (including perhalogenated hydrocarbyl, perhalogenated hydrocarbyloxy and perhalogenated silylhydrocarbyl radicals) whose Q has more than 20 carbons with the proviso that in not more than one occurrence Q is halide. Examples of suitable hydrocarbyloxy Q groups are described in the U.S. Patent. 5,296,433. In a more preferred embodiment, d is one, that is, the counter-ion has a single negative charge and is A '. Activation cocatalysts comprising boron which are particularly useful can be represented by the following general formula: (L * -H) + (BQ4) "; where: L * is as previously defined; B is boron in a formal oxidation state of 3; and Q is a hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy, or fluorinated silylhydrocarbyl group of greater than 20 non-hydrogen atoms, with the proviso that on no more than one occasion Q is hydrocarbyl. More preferably, Q is each occurrence of a fluorinated aryl group, especially, a pentafluorophenyl group. illustrative, but not limited, examples of boron compounds which can be used as a cocatalyst are tri-substituted amino salts such as: trimethylammonium tetraphenyl borate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tetraphenylborate tri ( n-butyl) ammonium, methyltetradecyloctadecylammonium tetraphenylborate, N, N-dimethylanilide tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylanilini) tetraphenyl borate, trimethylammonium tetrarate borate ( pentafluorophenyl), methylditetradecylammonium tetrakis (pentafluorophenyl) borate, methyclooctadecylammonium tetrakis (pentafluorophenyl) borate, triethylammonium borate tetrakis (pentafluorophenyl), tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, borate of tri (sec-butyl) ammonium tetrakis (pentafluorophenyl), N, N-dimethylanilinum borate tetrakis (pent afluorophenyl), N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate ), triethyl ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis borate (2,3,4) , 6-tetrafluorophenyl), dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl), and N, N-dimethyl (2,4,6-trimethylanilinium) tetrakis- (2, 3,4,6-tetrafluorophenyl) borate. Dialkyl ammonium salts such as: dioctadecylammonium borate tetrakis (pentafluorophenyl), ditetradecylammonium tetrakis (pentafluorophenyl) borate, and dicyclohexylammonium borate tetrakis (pentafluorophenyl). Tri-substituted phosphonium salts such as: triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium borate tetrakis (pentafluorophenyl), and tri (2,6-dimethylphenyl) phosphonotetrakis- (pentafluorophenyl) borate. The preferred are the salts of tetrakis ( pentafluorophenyl) long-chain alkyl borate mono- and di-substituted ammonium complexes, especially C-alkyl ammonium complexes? -C2_, especially methyldi (octadecyl) ammonium tetrakis (pentafluorophenyl) borate and methyldi (tetradecyl) -ammonium tetrakis (pentafluorophenyl) borate, or mixtures including the same. Such mixtures include protonated ammonium cations derived from amines comprising two C? 4, Cíe,, or Cis alquilo alkyl groups and a methyl group. Such amines are available from Witco Corp., under the tradename Kemamine ™ T9701, and by Akzo-Nobei under the trade name Armeen ™ M2HT. Another suitable ammonium salt, especially for use in heterogeneous catalyst systems, is formed to the reaction of an organometal compound, especially a tri (C? -6) aluminum alkyl compound with an ammonium salt of a borate compound. of hydroxyaryltris (fluoroaryl). The resulting compound is a compound of organometal-oxyaryltris (fluoroaryl) borate which is generally insoluble in aliphatic liquids. Usually, such compounds are advantageously precipitated on support materials, such as silicon, alumina or passive trialkylaluminum silicon. To form a supported cocatalyst mixture. Examples of suitable compounds include the reaction product of a tri (alkyl d-6) compound with the ammonium salt of hydroxyaryl borate (aryl) borate. Hydroxyaryl borate (aryl) borates include ammonium salts, especially the above long chain alkyl ammonium salts of: (4-dimethylaluminum-1-phenyl) tris (pentafluorophenyl) borate, (4-dimethylaluminum-3-borate) , 5-di (trimethylsilyl) -1-phenyl) tris (pentafluorophenyl), borate (4-dimethylaluminioxy-3,5-di (t-butyl) -1-phenyl) tris (pentafluorophenyl), (4-dimethylaluminium-1-benzyl) tris (pentafluorophenyl) borate, (4-dimethylaluminium-3-methyl-1-phenyl) tris (pentafluoro phenyl), borate (4-dimethylaluminium) tetrafluoro-1-phenyl) tris (pentafluorophenyl), (5-dimethylaluminium-2-naphthyl) tris (pentafluorophenyl) borate, 4- (4-dimethylaluminumxy-1-phenyl) phenyltris (pentafluorophenyl) borate, 4- (2- (4- ( dimethylaluminumxyphenyl) propane-2-yl) phenyloxy) tris (pentafluorophenyl), (4-diethylaluminum-1-phenyl) tris (pentafluorophenyl) borate, (4-diethylaluminium-3,5-di (trimethylsilyl) -1-phenyl) borate (pentafluorophenyl), borate (4-) diethylaluminum-3,5-di (t-butyl) -1-phenyl) tris (pentafluorophenyl), (4-diethylaluminum-1-benzyl) tris (pentafluorophenyl) borate, (4-diethylaluminium-3-methyl-phenyl) tris (pentafluorophenyl) borate, (4-diethylaluminophenoxy-tetrafluoride) borate -1-phenyl) tris (pentafluorophenyl), (5-diethylaluminum-2-naphthyl) tris (pentafluorophenyl) borate, 4- (4-diethylaluminum-1-phenyl) phenyltris (pentaf luorofenyl) borate, 4- borate (2- (4- (diethylaluminiumxyphenyl) propane-2-yl) phenyloxy) tris (pentafluorophenyl), (4-diisopropylaluminum-1-phenyl) tris (pentafluorophenyl) borate, (4-diisopropylaluminum-3-di (trimethylsilyl) -1-phenyl) borate. (pentafluorophenyl), borate of (4-disopropylaluminum-3,5-d i (t-butyl) -1-f in i I) tris (pentafluorophenyl), (4-diisopropylaluminum-1-benzyl) tris (pentafluorophenyl) borate, (4-diisopropylaluminum-3-methyl-1-phenyl) borate tris (pentafluorophenyl), (4-diisopropylaluminium-tetrafluoro-1-phenyl) borate tris (pentafluorophenyl), (5-diisopropylaluminum-2-naphthyl) tris (pentafluorophenyl) borate, 4- (4-diisopropylaluminum-1-phenyl) phenyltris borate (pentaf luorofenil), and borate of 4- (2- (4- (diisopropylaluminiumxyphenyl) propane-2-yl) phenyloxy) tris (pentafluorophenyl). An especially preferred ammonium compound is methylditetradecylammonium (4-diethylaluminum-1-phenyl) tris (pentaf luorofenyl) borate, methyldhexadecylammonium (4-diethylaluminoxy-1-phenyl) tris (pentafluorophenyl) borate, methyldioctadecyl-ammonium ( 4-diethylaluminoxy-1-phenyl) tris (pentafluorophenyl) borate, and mixtures thereof. The above complexes are described in WO 96/28480, which is equivalent to EUA SN 08 / 610,647, filed on March 4, 1996, and in US SN 08 / 768,518, filed on December 18, 1996. Alumoxanes, especially Methylalumoxane or modified triisobutylaluminum methylalumoxane are also suitable activators and can be used to activate the metal complexes present. The molar ratio of metal complex: activating cocatalysts preferably employed range from 1: 1000 to 2: 1, more preferably from 1: 5 to 1.5: 1, even more preferably from 1: 2 to 1: 1. In the preferred case in which the metal complex is activated by trispentafluorophenylborane and modified triisobutylamininum methylalumoxane, the molar ratio of titanium: boron: aluminum is usually from 1:10:50 to 1: 0.5: 0.1, more usually from 1: 3: 5 An even more preferred activating cocatalyst is trispentafluorofinylborane (FAB), optionally in combination with an alumoxane, the molar ratio of metal complex: FAB: alumoxane which is from 1: 1: 5 to 1:10:50. A support, especially silicon, alumina, or a polymer (especially poly (tetrafluoroethylene) or a polyolefin) may be employed, and is desirably employed when the catalysts are used in a gas phase or slurry polymerization process. The support is preferably employed in an amount to provide a weight ratio of catalyst (based on metal): support from 1: 100,000 to 1:10, more preferably from 1: 50,000 to 1:20, and more preferably from 1: 10,000 at 1:30. All the times the individual ingredients as well as the recovered catalyst components must be protected from oxygen and moisture. Therefore, catalyst components and catalysts must be prepared and recovered in an atmosphere free of oxygen and moisture. Preferably, therefore, the reactions are carried out in the presence of an inert, dry gas such as, for example, nitrogen. The polymerization will preferably be conducted in a continuous polymerization process. In a continuous process, ethylene, comonomer, optionally solvent and diene are continually supplied to the reaction zone and the polymer product thereof is continuously removed. In general, the first polymer can be polymerized at conditions for polymerization reactions of the Ziegler-Natta or Kaminsky-Sinn type, that is, reactor pressures ranging from atmospheric pressure to 3500 atmospheres (355 MPa). The temperature of the reactor should be greater than 80 ° C, usually from 100 ° C to 250 ° C, and preferably from 100 ° C to 150 ° C, with temperatures at the highest end of the scale, temperatures above 100 ° C that favor the formation of polymers of lower molecular weight. Along with the reactor temperature, hydrogen: the molar ratio of ethylene influences the molecular weight of the polymer, with higher hydrogen levels allowing lower molecular weight polymers. The molar scale of hydrogen: ethylene will usually be from 0.0: 1 to 2.5: 1. Generally, the polymerization process is carried out at a pressure of 70 to 7000 kPa, more preferably 280 to 5500 kPa. The polymerization is generally conducted at a temperature of 80 ° C to 250 ° C, preferably 90 ° C to 170 ° C, and even more preferably more than 95 ° C to 140 ° C. In most polymerization reactions the molar ratio of catalyst: polymerizable compounds employed is from 10-12: 1 to 10-1: 1, more preferably from 10-9: 1 to 10-5: 1. The solution polymerization conditions use a solvent for the respective components of the reaction. Preferred solvents include mineral oils and the various hydrocarbons which are liquid at reaction temperatures. Illustrative examples of useful solvents include alkanes such as pentane, iso-pentane, hexane, heptane, octane and nonane, as well as mixtures of alkanes including kerosene and Isopar-E ™, available from Exxon Chemicals Inc.; cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene, xylenes, ethylbenzene and diethylbenzene. The solvent will be present in an amount sufficient to prevent phase separation in the reactor. As the solvent works to absorb heat, less solvent leads to a less adiabatic reactor. The solvent ratio: ethylene (base in weight) in the feed will usually be from 2.5: 1 to 12: 1, beyond said solvent ratio: ethylene (base in weight) in the feed is in the range of 2.5: 1 to 6 :1. The ethylene / α-olefin interpolymer can alternatively be prepared in a gas phase polymerization process, using the catalysts as described above as supported on an inert support, such as silicon. The ethylene / α-olefin interpolymer can also be made in a slurry polymerization process, using the catalysts as described above as supported on an inert support, such as silicon. As a practical limitation, slurry polymerizations take place in liquid diluents in which the polymer product is substantially insoluble. Preferably, the diluent for slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or in part as the diluent. Similarly, the α-olefin monomer or mixture of different α-olefin monomers may be used in whole or in part as the diluent. More preferably, the diluent comprises in at least a major part the α-olefin monomer or monomers to be polymerized. The polymers can be produced via a continuous controlled polymerization process (in a counter-batchwise manner) using at least one reactor, but can also be produced using multiple reactors (e.g., using a multiple reactors configuration as described in the US Pat. US No. 3,914,342 (Mitchel)), with the second ethylene polymer polymerized in at least one other reactor. The multiple reactors may be operated in series or in parallel, with at least one constrained geometry catalyst employed in at least one of the reactors at a polymerization temperature and sufficient pressure to produce the ethylene polymers having the desired properties. The melt index of the polymer compositions useful in the present invention will be chosen based on the application of white end use. For example, polymer compositions having a melt index of at least 2 grams / 10 minutes, preferably at least 3 grams / 10 minutes; and preferably not more than 8 grams / 10 minutes, preferably not more than 7 grams / 10 minutes, will be usefully employed in general purpose blowing film applications. Likewise, polymer compositions having a melt index of less than 1 gram / 10 minutes, preferably less than 0.75 grams / 10 minutes, will be usefully employed in heavy duty bags and other high strength film applications. Films of the invention which are characterized as high transparency films, will preferably be characterized by having a fogging of less than 12 percent, preferably less than 11 percent, more preferably less than 10 percent. For example, exemplary of the polymer compositions which lead to the production of such more preferred films, are the ethylene / α-olefin interpolymers of the invention having a melt index of less than 1 gram / 10 minutes, preferably less than 0.75 grams / 10 minutes, and having a 0 / l2 of at least 10, preferably at least 12.

The compositions of the invention optionally can be melt bonded with other thermoplastic polymers, such as, low density polyethylene, linear low density polyethylene, high density polyethylene, ethylene vinyl acetate, ethylene vinyl alcohol, polypropylene, polycarbonate, and ethylene / styrene interpolymers, which are provided with the formation of such a mixture do not interfere in a detrimental manner with the desired performance. Usually, such additional thermoplastic polymer will be provided to the mixture in an amount of 1 to 30 percent by weight, preferably from 1 to 15 percent by weight. Certain compositions of the invention will be prepared in a double reactor configuration in accordance with techniques known in the art. For example, dual reactor systems are described and claimed in US SN 08/858664 (EP 619,827) and EUA SN 08 / 747,419 (TCP Publication WO 94/14112). Examples of High Processing Polymers that Have an I? Greater than 2 g / 10 minutes The polymers of Comparative Examples A and B were commercially available low density polyethylenes. The polymers of Comparative Examples C, D, and E were substantially linear ethylene / α-olefin copolymers having one or 12 less than 9 and one Mp / Mn from 2,175 to 2,543. The polymers of Examples 1-3 were substantially linear ethylene / butene compositions prepared in a parallel double reactor polymerization process as described in US SN 08/858664 (EP 619, 827). In each example, a catalyst comprising (t-butylamido) dimethyl) -5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene catalyst, activated with trispentafluorophenylborane methylalumoxane and modified triisopropylaluminum (MMAO, available from Akzo Chemical) was used. In each example, reactor conditions were selected such as to produce a product having a uniform density (ie, each reactor was run in such a way as to give a product having the same density), but which is bimodal in molecular weight terms. In Table One, Parts I and II, the properties for the products of the first and second reactor are indicated by R1 and R2, respectively. For example, in the case of Example 3, the following reactor conditions may be employed. Table One: Part I The polymer of Example 4 was a substantially linear ethylene / 1-butene copolymer prepared in a single solution polymerization reactor. The polymer of Example 4 was prepared according to the procedures of the U.S. Patent.

No. 5,272,236 and Patent of E.U.A. No. 5,278,272, which uses a catalyst of (t-butylamido) dimethyl)? 5-tetramethylcyclopentadienyl) silanetitanium (11) 1,3-pentadiene activated with trispentafluorophenylborane and modified methylalumoxane. The properties of the polymers of Comparative Examples A-E and of Examples 1-4 are shown in the following Table One, Part II.

Table One, Part II n l2 measured in accordance with ASTM D1238, Condition 190 ° C / 2.16 Kg l10 measured in accordance with ASTM D-1238, Condition 190 ° C / 10 Kg Misting measured in accordance with ASTM D-1003 Evaluation of Films Fabricated from the Polymer of Comparative Example C v Example 1 The films were produced on an Egan blown film line extruder (5 cm), given 7.5 cm, die opening of 1 mm. Table two shows the manufacturing conditions used to produce the blowing films. The blowing films were manufactured at a melting temperature of 171 ° C. The back pressure and the motor amperages are similar for the polymers of Comparative Examples A and C and Example 1. The polymer of Comparative Example B processed with a lower back pressure and motor amperage.

Table Two Extruder temperature profiles: For samples of Comparative Examples A, B and C: 149/149/163/163/163/163/163/163/163 ° C For Example 1: 149/149/163/163/163/163/163/163/174 ° C Table Three shows the mechanical and optical properties of the resulting films. Table Three In order to improve the fogging of the blowing films, blends with various polymers were investigated. Mixtures of the polymer of Comparative Example C and Example 1 were made with 10% of PEBDAR 4012 (12 MI, 0.922 g / cm 3). Table Four shows the manufacturing conditions used to produce the blowing films. These films were produced in the Egan blown film line (5 cm extruder, 7.5 cm die, 1 mm die opening). The blowing films were manufactured at a melting temperature of 157 ° C. Table Four Extrusion Temperature Profiles: 149/149/149/149/149/149/149/149/149 ° C Table four also shows the optical properties of the resulting films. The films produced with the blends described above exhibited improved optical properties. In the case of the 10 percent mixture of PEBDAR 4012 in the polymer of Example 1, this specific mixture exhibited a similar fogging value as Comparative Example A. It was shown that a polymer of Example 1 does not detrimentally affect the mechanical properties of the films prepared with heterogeneously branched linear low density polyethylene. The films were made with 12.5 weight percent blends of the polymers of Comparative Examples A-C and Example 1, with 78.5 weight percent DOWLEX 2045. Table five shows the manufacturing conditions used to produce the blowing films. These films were produced on the Gloucester film line (6 cm extruder, 15 cm die, 1.8 mm die opening). The processability of the mixture of Example One with the LDPE showed some improvement in the subsequent pressure of the extruder over the mixtures of Comparative Examples A and B with the PEBDL.

Temperature profiles of the extruder: 135/143/146/146/191/191/191/191 ° C.

Table Six shows the mechanical and optical properties of the resulting blow film. The optical properties of the mixture using the polymer of Example One were slightly lower than those of the blends using the polymer of Comparative Examples A and B. The properties were affordable with the cited exceptions: the films prepared from the mixtures they use the polymer of Example One exhibited greater dart impact and greater Elmendorf MD breakage than the films prepared from the blends using the polymers of Comparative Examples A and B. Table Six The films were prepared using the polymer of Example 2. The films were produced on a line of Egan blowing film (5 cm extruder, given 7.5 cm, die opening of 1 mm). The blowing films were manufactured at a melting temperature of 157 ° C. Table Seven shows the manufacturing conditions used to produce the blow films, as well as physical properties representative of the films. Table Seven Temperature profiles of the extruder: 149/149/149/149/149/149/149/149/149 ° C The polymers of Comparative Examples D and F were made into blowing films on an Egan blowing film line (5 cm extruder, given of 7.5 cm, opening of the die of 1 mm). The blowing films were manufactured at a melting temperature of 157 ° C. Table Eight shows the manufacturing conditions used to produce the blowing films, and representative properties of the blowing films. Table Eight Temperature profiles of the extruder: 149/149/149/149/149/149/149/149/149 ° C Subsequent pressures for the polymers of Comparative Examples C and D are similar to those of the polymer of Comparative Example A. Engine loads for polymers of Comparative Examples C and D are greater than those of Comparative Example A (although the exit rate was lower for the polymer of Comparative Example A, which will influence the load of the motor). The fogging values for the films prepared with the polymers of Comparative Examples C and D are significantly greater than the films prepared with Comparative Example A. A concentrate of Irgafos 168 and Irganox 1010 was dry blended with a polymer of Example 3, such as giving 1200 ppm Irgafos 168 and 300 ppm Irganox 1010 in the polymer. The blowing films were also prepared with strip concentrate and antiblock, such as to give 500 ppm of erucamide strip agent and 2000 ppm of White Mist anti-block in the polymer. The films were produced on an Egan blowing film line (5 cm extruder, given 7.5 cm, 1.0 mm die opening): the blowing films were manufactured at a melting temperature at 157 ° C. Table Nine shows the manufacturing conditions used to produce the blowing films.

Table nine Temperature profiles of the extruder: 149/149/149/149/149/149/149/149/149 ° C. Table Ten shows the optical and mechanical properties of the films prepared with the polymer of Example 3, with various combinations of additives as described above. Table Ten illustrates the improvement over optics which results from the incorporation of PEBDAR in the polymer, and the negative affects optics which result from the addition of strip additives and antiblocking. Table Ten 1-AO package containing 1200 ppm Irgafos 168 and 300 ppm Irganox 1010 2-Strip package containing 500 ppm of Euracamide 3-Package of antiblock containing 2000 ppm White Mist As illustrated above, the polymers of Examples 1- 3 they exhibit mechanical properties which are better than those of Comparative Examples A and B, while not degrading optical performance to an unacceptable level. Figures 2 and 3 provide plots of l2 against Mp and h0 / l2 against Mp / Mn for the polymers of Examples 1-3, as well as polymers of the other examples and comparative examples. As shown in Figure 2, the polymers of Examples 1-3 will be characterized to satisfy the following inequality: | 2 < 1 n [-3.5_5-Log (M)] + ^^ In addition, as shown in Figure 3, the polymers of Examples 1-3 will be characterized to satisfy the following inequality: ho / l2 > [1.5 * Mp / Mn] +2.59 High processing polymers having a Fractional Fusion Index The polymers of Examples 1-5 were prepared with a constrained geometry catalyst according to the procedures of the U.S. Patent. No. 5,272,236 and the U.S. Patent. No. 5,278,272. In each case, the catalyst employed t-butylamido) dimethyl) 5-tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene catalyst, activated with trispentafluorophenylborane and modified triisopropylaluminum methylalumoxane (MMAO, available from Akzo Chemical). For example, the polymer of Example 8 can be prepared using the following process conditions: The polymers of Comparative Examples A and B were commercially available low density polyethylene. A description of the properties of the polymers of Examples 1-5, as well as the polymers of Comparative Examples A and B, as described above, are shown in the following Table Eleven. cn ro or cn cn Table Eleven Note: Density measured according to ASTM D-792, l2 measured in accordance with ASTM D-1238, Condition 190 ° C / 2.16 Kg ho measured in accordance with ASTM D-1238, Condition 190 ° C / 10 Kg Measuring fogged according to with ASTM D- 1003 The polymers of Example 5 and Comparative Examples A and B were manufactured in the blowing films. The blowing films were manufactured at a melting temperature of 160 ° C. Table Twelve shows the manufacturing conditions used to produce the blowing films, as well as the mechanical and optical properties of the resulting films. Table Twelve Extruder temperature profile: 149/149/149/149/149/149/149/149/149 ° C ** The CD and MD contractions were measured at 125 ° C, 20 seconds, 10 cm x 10 cm) film sample. The optical properties of the films prepared with the polymers of Comparative Examples A and B differ. The film prepared with the polymer of Comparative Example A exhibits much better optical properties than the film prepared with the polymer of Comparative Example B. The film prepared with the polymer 5 exhibited better optical properties, stress (ultimate strength and tensile stiffness), and Elmendorf breaking values than the films of any of the films of Comparative Examples A or B. The bubble stability during the process was similar for each of the films prepared. The optical properties are also improved by manufacturing the films at a higher temperature. The blowing films were manufactured at a melting temperature of 190.55 ° C of the polymers of Comparative Examples A and B, and of the polymer of Examples 5 and 6. Table 13 shows the manufacturing conditions used to produce the films of blown, as well as the mechanical and optical properties of the resulting films. Table Thirteen Temperature profiles of the extruder: 149/163/177/182/182/182/182/182/188/188 ° C ** Contraction CD and MD were measured at 125 ° C, 20 seconds, sample 10 x 10 cm A comparison of Tables Twelve and Thirteen illustrates that, in the case of the films prepared with the polymers of Comparative Examples A and B with the polymer of Example 5, the films manufactured at higher melting temperature exhibited better optical properties (fogging and luster) than the films manufactured at lower melting temperature. In addition, films prepared with the polymers of Examples 5 and 6 exhibited Elmendorf optical, tensile, and breaking properties than films made with the polymers of Comparative Examples A and B. The bubble stability during the process was similar for the manufacture of each of the films. High Processing Polymers having a Melt Index of 1 to 2 g / 10 minutes The polymer of Example 9 is a substantially linear ethylene / 1-octene interpolymer prepared in a single solution polymerization reactor, according to the procedures of US Patents Nos. 5,272,236 and 5,278,272.

The polymer product 9 can be produced in a solution polymerization process using a well-mixed recirculating cycle reactor. Ethylene and hydrogen (as well as any ethylene and hydrogen) which are recycled from the separator, are combined in a stream before being introduced into the diluent mixture, a mixture of saturated C8-C10 hydrocarbons, such as ISOPAR ™ -E (available from Exxon Chemical Company) and the comonomer, 1-octene. The metal complex and the cocatalysts are combined in a single stream and are also injected continuously into the reactor. The catalyst used is (t-butylamido) dimethyl (? 5-tetramethylcyclopentadienyl) silanetitanium (IV) dimethyl, activated with trispentafluorophenylborane (available after Boulder Scientific as a 3% solution in mixed ISOPAR-E hydrocarbon) and modified triisopropylaluminum methylalumoxane (MMAO Type 3A, available from Akzo Nobel Chemical Inc. as a solution in heptane having 2% by weight of aluminum). Sufficient residence time is allowed for the metal complex and cocatalyst to react before being introduced into the polymerization reactor. The reactor pressure remains constant at around 33.39 kg / cm2. After the polymerization, the reactor outlet stream is introduced into a separator where the fused polymer is separated from the unreacted comonomer, unreacted ethylene, unreacted hydrogen, stream of diluent mixture, which in turn is recycled by combination with fresh comonomer, ethylene, hydrogen, and diluent, for introduction into the reactor. The fused polymer is subsequently cut into strips or formed into pellets, and, after cooling in a water bath or forming into pellets, the solid pellets are collected. Table 14 describes the polymerization conditions and the resultant polymer properties. Table Two Polymers such as those of Example 9 are bleached to replace HP-PEBDAR in optical grade film markets, such as transparent liners and bake films. Performance requirements include: (1) extruder processing capacity and bubble stability similar to highly branched low density polyethylene; (2) optics similar to high density branched low density polyethylene; and (3) better mechanical properties than highly branched low density polyethylene. Table Fifteen shows the properties of the Polymer of the Example 9, as well as the polymers of Comparative Examples F (PEBDAR 503, a highly branched low density polyethylene, available from The Dow Chemical Company)) and G (DOWLEX ™ linear low density polyethylene (available from The Dow Chemical Company Table 15 also reports the performance attributes of these polymers and of blowing films prepared from these polymers.

As shown in Table Fifteen, the polymer of Example 9 exhibits optical properties which exceed those of Comparative Example F, exhibit a processing capacity and mechanical properties which are generally intermediate to those of Comparative Examples F and G.

Claims (20)

1. CLAIMS 1. A film having at least one layer comprising a homogeneous interpolymer of ethylene and at least one comonomer selected from the group consisting of C3-C20 α-olefins, dienes, and cycloalkanes, wherein the interpolymer is characterized for having: a. a density of 0.910 to 0.930 g / cm3, b. a melt index (12) of 0.2 to 10 g / 10 minutes, c. a h0 / l2 from 9 to 20, and d. a molecular weight distribution, Mp / Mn from 2.1 to 5. The film of claim 1, wherein the ether polymer is a substantially linear polymer characterized by having: a. a molecular weight distribution, Mp / Mn, as determined by gel permeation chromatography and defined by the equation: (Mp / Mn) < (ho / l2) -4.63, b. a rheology of gas extrusion in such a way that the rate of critical shear stress at the beginning of the surface melt fracture for the interpolymer is at least 50 percent greater than the rate of critical shear stress at the beginning of the fracture surface melt for a linear ethylene polymer, wherein the ether and the linear ethylene polymer comprise the same monomers or comonomers, wherein the linear ethylene polymer has a l2, Mp / Mn and density within ten percent of the interpolymer , and wherein the respective critical shear rates of the interpolymer and the linear ethylene polymer are measured at the same melt temperature using a gas extrusion rheometer. 3. The film of claim 1, wherein the interpolymer has 0.01 to 3 long chain branches / 1000 carbons. The film of claim 1, wherein the polymer is characterized as having one to two crystallization peaks at 45 ° C and 98 ° C, each of which has an IATC less than 18 ° C, as determined by FEET. 5. The film of claim 1, wherein the polymer is characterized by producing a gel permeation chromatogram which exhibits two peaks. The film of claim 5, wherein the interpolymer is prepared in two polymerization reactors, each of which contains a restricted geometry of a single site or metallocene catalyst. 7. The film of claim 6, wherein the ether polymer, when fractionated by gel permeation chromatography, is characterized by comprising: a. from 25 to 90 percent of a first polymer fraction having a melt index (12) of 0.05 to 1.0 g / 10 minutes; and b. from 10 to 75 percent of a second polymer fraction having a melt index (12) of at least 30 g / 10 minutes. 8. the film of claim 1, wherein the ether polymer is characterized as having a total melt index (12) of 1.0 to 7.0 g / 10 minutes. 9. The film of claim 6, wherein the interpolymer is characterized by satisfying the following inequalities: a. | 2 < 10 [-3-525 * Log (Mp) + 17-84], and b. ho / l2 > [1-5 * Mp Mn] + 2.59. 10. The film of claim 6, wherein the ether polymer, when fractionated by gel permeation chromatography, is characterized by comprising: a. from 30 to 85 percent of a first polymer fraction having a melt index (12) of 0.05 to g / 10 minutes; and b. from 15 to 70 percent of a second polymer fraction having a melt index (12) of at least 30 g / 10 minutes. The film of any of claims 5-10, wherein the interpolymer is characterized as having two crystallization peaks between 45 ° C and 98 ° C, each having an IATC less than 18 ° C, as determined by FEET . 12. The film of claim 2, wherein the ether polymer is further characterized by having: a. one l2 from 0.05 to less than 2.5 g / 10 minutes, b. a h0 / l2 of at least 12.5, and c. an Mp / Mn of 2.1 to 3.0. 13. The film of claim 12, wherein the interpolymer is further characterized by having a single crystallization peak between 45 ° C and 98 ° C having an IATC of less than 18 ° C., as determined by FEET. 14. A process for preparing a blow film comprising: a. melt an interpolymer at a temperature of 149 to 177 ° C, b. Extrude the polymer in the rate of 6.8 to 45 h / hr through a die having a die opening of 0.76 to 2.5 mm, c. blowing the film in a bubble, in a blow up ratio of 1.3: 1 to 2.5: 1, to form a gauge film of 0.01 to 0.1 mm, and d. cooling the film by means external to the bubble, wherein the interpolymer is a polymer of ethylene and at least one comonomer selected from the group consisting of C3-C20 α-olefins, dienes, and cycloalkenes are characterized by having: . a density of 0.910 to 0.930 g / cm3, ii. a melt index (12) of 0.2 to 10 g / 10 minutes, ii. a h0 / l2 from 9 to 20, and iv. a molecular weight distribution, Mp / Mn of 2.1 to 5. 15. A process for preparing a blowing film comprising: a. melt an interpolymer at a temperature of 149 to 204 ° C, b. Extrude the polymer in the 6.8 to 45 kg / hr regime through a die having a die opening of 0.76 to 2.5 mm, c. blow the film in a bubble, in a blow ratio of 2: 1 to 4: 1, to form a preli- cal with a gauge of 0.05 to 0.1 mm, and d. cooling the film by means external to the bubble, wherein the interpolymer is an ethylene ether polymer and at least one comonomer selected from the group consisting of α-olefins, dienes, and cycloalkenes are characterized by having: i. a density of 0.910 to 0.930 g / cm3, ii. a melt index (12) of 0.5 to 2.5 g / 10 minutes, iii. one l10 / l2 from 12.5 to 20, and iv. a molecular weight distribution, Mp / M "of 2.1 to 3. 16. The process of any of claims 14 or 15, wherein the interpolymer is characterized as having one to two crystallization peaks between 45 ° C and 98 ° C, each having an IATC less than 18 ° C, as determined by FEET. 17. A polymer composition consisting essentially of an interpolymer of ethylene and at least one comonomer selected from the group consisting of C3-C20 α-olefins, dienes, and cycloalkenes, wherein the interpolymer is characterized as having: a. a density of 0.910 to 0.930 g / cm3, b. a melt index (12) of 0.2 to 10 g / 10 minutes, c. a h0 / l2 from 9 to 20, d. a molecular weight distribution, Mp / Mn from 2.1 to 5, e. a molecular weight distribution, Mp / Mn, as determined by gel permeation chromatography and is defined by the equation: (Mp / M ") <; (ho / l2) -4.63, and f. a rheology of gas extrusion in such a way that the rate of critical shear stress at the beginning of the surface melt fracture for the interpolymer is at least 50 percent greater than the rate of critical shear stress at the beginning of the fracture surface melt for a linear ethylene polymer, wherein the interpolymer and the linear ethylene polymer comprises the same comonomer or comonomers, wherein the linear ethylene polymer has a l2, Mp / Mn and density within ten percent of the etherpolymer , and wherein the respective critical shear rates of the interpolymer and the linear ethylene polymer are measured at the same melt temperature using a gas extrusion rheometer. The composition of claim 17, wherein the interpolymer is characterized as having one to two crystallization peaks between 45 ° C and 98 ° C, each having an IATC less than 18 ° C, as determined by FEET . The composition of claim 17, in the form of a blend with a thermoplastic polymer selected from the group consisting of low density polyethylene, linear low density polyethylene, high density polyethylene, ethylene vinyl acetate, ethylene vinyl alcohol , polypropylene, polycarbonate, ethylene / styrene interpolymers, and mixtures thereof. The composition of claim 19, wherein the thermoplastic polymer is provided to the composition in an amount of 1 to 30 weight percent.