MXPA00003135A - Novel narrow molecular weight distribution copolymers containing long chain branches and process to form same - Google Patents

Abstract

The subject invention is directed to new and novel copolymers having long chain branches formed from ethylene and at least one vinyl alicyclic monomer, to solution polymerization using certain unstrained bridged metallocene catalysts which has been found capable of forming said copolymers and to packaging material formed therefrom.

Description

NOVEDOUS COPOLYMERS OF ANGOSTA DISTRIBUTION OF PESOS MOLECULARS CONTAINING LONG CHAIN BRANCHES AND PROCEDURE FOR PREPARATION FIELD OF THE INVENTION The present invention focuses on novel copolymers having a configuration of long chain branches and a novel process for their formation. Polyolefins have been formed by free radical polymerization that provides a polymer product having a broad molecular weight distribution and a structure that includes a significant amount of short and long chain branches. The good processability of these polyolefins has been attributed to a "combination of broad molecular weight distribution and long chain branches." It is known to produce polyolefins using conventional Ziegler catalysts The resulting polymers also have a broad molecular weight distribution but do not have a polymer structure with a significant amount of long chain branches and therefore have only a medium processing capacity to provide film products More recently, single site or metallocene polymerization catalysts have been employed to provide polyolefin products In general, the catalysts of Metalocene products provide polymer products with a narrower distribution of molecular weights without a significant amount of long chain branching and, therefore, also present processing problems in relation to melt fracture, low melt tension and the like. The metallocene complexes have been divided into several categories based on their chemical composition and molecular structure. For example, their organic portions can be based on cyclopentadienyl (Cp) or indenyl (Ind) or fluorenyl (Flu). The organic groups may not be bridged or they may be joined together in a bridged configuration. The bridged structure can form, with the metal atom of the complex, a restricted configuration (it is generally known as a constrained geometry catalyst technology or CGCT) or a substantially unrestricted configuration. The metallocene complexes of the various categories have activity in certain specific polymerization processes while being substantially inactive for other polymerization efforts. Attempts were made to improve the processing capacity of the polyolefins by expanding the molecular weight distribution of the polymer. One approach has included the generation of a polymer product that has a higher degree of branching than long chains as part of the polymer structure. U.S. Patents 5,380,810; 5,525,695; 5,272,236 and 5,278,272 describe polymerization processes that require the use of specific restricted geometry (CGCT) catalyst. It is believed that metallocene catalysts having a restricted geometry can be employed in solution polymerization to introduce long chain branches into polymer products formed from predominantly aliphatic alpha olefins. The resulting polymers have an improved processing capacity in narrow distributions of molecular weights. More recently, the application EP 0 676 421 presented the ability to carry out a gas phase polymerization of aliphatic alpha olefins by the use of certain metallocene compounds in order to produce products having long chain branches and, therefore, an improved processing capacity. The molecular weight distribution or polydispersity of the polymers is a well-known variable that can be defined as the ratio between the average weight of the molecular weight (Mw) and the average number of the molecular weight (Mn) and is commonly known as Mw / Mn. This can be measured by gel permeation chromatography techniques. It is often convenient to determine the polymer processing capacity by measuring the ratio of flow rate of polymer metal under different loads (10 Kg and 2 Kg), in accordance with that described in ASTM-D-1238. It is known that polyethylene-based resins having a narrow polydispersity (eg, 1.5 to 3) have a melt flow index ratio (I10 / I2), less than about 8 do not exhibit good processability while polymers that They have high melt flow index relationships that contain long chain branches and offer good processing power. Thus, from the melt flow ratio, a capacity of the thin shear polymer can be determined to provide a polymer with an improved processing capacity, for example, a low susceptibility to surface imperfections due to melt fracture, even under of high shear stress. Copolymers formed with units derived from certain monomers containing vinyl alicyclic are highly desired materials. For example, such materials are useful as film forming components such as, for example, the use of ethylene and 4-vinylcyclohexene copolymers as a crosslinking enhancing component of a multilayer film, of confo-anity with described in the co-pending North American application Serial No. 08 / 822,529, filed on the 24th March 1997, whose teachings are incorporated here by reference in its entirety. However, these polymers containing alicyclics are difficult to process in films due to their low polydispersity and due to the absence of significant long chain branches in their structure. It is an object of the present invention to provide ethylene-vinyl alicyclic monomer copolymers having low polydispersity while having long side chain branching and a high related value of their melt flow index ratio. Such copolymers have an increased processing capacity and are especially useful in film forming activities. Furthermore, it is an object of the present invention to provide a process for the catalytic polymerization of ethylene and at least one vinyl alicyclic comonomer by solution polymerization to provide a polymer product having good processing characteristics. Furthermore, it is an object of the present invention to provide a process for forming films and the resulting improved film product comprising at least one layer having the copolymer object of the present invention. COMPENDIUM OF THE INVENTION The present invention is directed to certain novel copolymers having long side chains formed from ethylene monomers and at least one monomer containing alicyclic groups, represented by the formula: í where C O represents a (i) saturated C5-C? 2 alicyclic group which may be unsubstituted or substituted or (ii) an alicyclic group Ce-C? which may be unsubstituted or substituted and which contains at least one carbon-carbon (non-aromatic) ethylenic double bond within the ring structure. The present invention is further directed to a solution polymerization process capable of forming the polymers of the present invention having long side chains employing certain non-restricted bridged metallocene catalysts. DETAILED DESCRIPTION The present invention focuses on novel long chain branched ethylene copolymers and an alicyclic vinyl group containing a comonomer represented by the formula: where C D represents an alicyclic group selected from a saturated Cs-C? 2 alicyclic group or a C6-C? ethylenically unsaturated alicyclic group. These groups may also have one or more of their hydrogen atoms substituted by a hydrocarbon Cj.-C? 2, in accordance with the writing below. The copolymer object of the present invention must have ethylene as one of its monomeric forming groups. In addition, the copolymer object of the present invention must have, as one of its monomeric groups of formation, at least one monomer of the formula I, above. This monomer must have (i) a vinyl group; (ii) a hydrogen atom pending from the beta carbon and the gamma carbon from the monomer I; and (iii) a group containing a pending alicyclic gamma carbon atom from the beta carbon. The alicyclic group can be a saturated Cs-C? 2 alicyclic group such as for example cyclopentyl; cyclohexyl; cyclooctyl; cyclononyl; cyclodecyl; cyclohendecyl; and cyclododecyl. These groups may be unsubstituted or may have one or more substitutions of Cj.-C2o hydrocarbon group in the alicyclic ring carbons provided that the carbon has a hydrogen atom pending. The substitution group may be an aliphatic hydrocarbon such as, for example, methyl, ethyl, isopropyl, pentyl and the like; an alkenyl group such as for example 3-butenyl, 4-hexenyl and the like, a saturated or unsaturated alicyclic group which may be fused or not fused on the alicyclic ring. The group containing a gamma, alicyclic carbon atom can alternatively be selected from an unsaturated (non-aromatic) alicyclic C6-C ?2 group such as, for example, cyclohexenyl, cyclohexadienyl, cycloheptenyl, 5-cyclooctenyl, 3-cyclooctenyl, 4-cyclooctenyl, cyclooctadienyl , cyclododecatrienyl and the like. The alicyclic groups may, in addition to having at least one ethylenic unsaturation within the alicyclic group, may have one or more substitutions per C? -C20 hydrocarbon group pending the alicyclic ring in the same manner as described above with reference to the saturated alicyclic group. The copolymer object of the present invention can, in addition to the monomers of ethylene and monomer I described above, contain at least one additional monomer other than those defined above. For example, the additional monomer may be a linear or branched C3-C2o alphaolefin such as propylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 1-octene, 4-methylpentene and the like; cycloolefins such as, for example, cyclopentene, norbornene, tetracyclododecene and the like; and non-conjugated dienes such as for example 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 2,5-norbornadiene, 1,3-divinylcyclohexene, 1,4-divinylcyclohexane, -alyl-5-vinylcyclooctane, dicyclopentadiene and the like. The ethylene must be a copolymer forming comonomer of the present invention. It may be present in an amount of from about 0.01 to about 99 mol% of the copolymer, preferably from 25 to 99 mol% and especially from 75 to 99 mol% of the copolymer formed. The monomer I must be a co-polymer forming comonomer of the present invention. It may be selected from one or more of a mixture (in any proportion) of more than one monomer I. It may be present in an amount of about 1 to about 25 mol% of the copolymer, preferably about 1 to 15 and especially about 1. to 10 mol% of the copolymer formed. The rest of the copolymer object of the present invention can be formed from other copolymerizable monomeric compounds, in accordance with that described above. The resulting copolymer has a narrow distribution of molecular weights and long chain branches in accordance with what is evidenced by its low polydispersity (Mw / Mn) (1.5-5) and for its high proportion of Melt Flow Index (I10 / I2) • In general, the presence of long chain branches is indicated by the fact that the ratio of flow index in fusion is greater than polydispersion in accordance with the following equation: The polymers of the present invention have polydispersity values of at least about 1.5 to 5 and preferably at least about 1.7 to about 4 and especially from 1.9 to 3. In combination, in low polydispersity polymers, the branched structure of long chains it is shown through the high values of melt flow index ratio of at least about 8 and preferably 8.5, and especially at least about 10, in accordance with that measured according to ASTM D-1238. The preferred copolymer of the present invention is formed from the comonomers of ethylene and vinylcyclohexene. This copolymer preferably has from about 1 to about 25 mol% vinylcyclohexene, preferably from about 1 to 10, and especially from about 2 to 8 mol% vinylcyclohexene. The copolymer of the present invention is generally a semi-crystalline copolymer although in some cases the polymer will be amorphous.

The average weight of the molecular weight of the copolymers of the present invention will vary according to the particular monomer I present, the amount of said monomer I present in the copolymer, the specific conditions (e.g., temperature, pressure, etc.), polymerization as well as the particular catalyst used in its formation. Normally, the average weight of the molecular weight will be within a range of about 10,000 to 1,000,000, with about 25,000 to 125,000 being preferred. Altering the molecular weight can be achieved by the use of hydrogen in the polymerization reaction vessel, in accordance with what is fully described below. The presence of long chain branches, such as polymer structure that provides improved processing capacity, can be explained by the following theory, even though the theory is not intended to be a limitation to the present invention. Polymer chains that exceed a certain length or molecular weight, which is known as the critical entanglement molecular weight (Me), cause the polymer molecule to splice and have considerable entanglement when it is in a molten or melted state. Thus, a linear, monodispersed polymer of low molecular weight (< Mc) has a zero shear viscosity (n0) that is proportional to its molecular weight while higher molecular weight polymers have shear viscosities zero proportional to a factor of approximately the 3.4 power of its molecular weight. The relaxation time (? 0) of the polymer melt for such linear polymers follows a similar proportion. When the polymer has a branched structure, the zero shear viscosity and the relaxation time of the polymer melt is reduced when the branched chains are short and increases exponentially when a substantial number of chains are long. This increase is due, it is believed, to the entanglement of the branches of long chains with other polymer chain segments. Thus, the observation of a high average relaxation time (for example, greater than about 5 seconds at a temperature of 180 ° C) is an additional factor that supports the presence of long chain branches in the structure of a polymer. The presence of long chain branches (chains of 6 carbon atoms or more) in the copolymer structure of the present invention is evidenced by NMR analysis of copolymer films. For example, in addition to the NMR peaks that can normally be assigned to units of ethylene and vinylcyclohexene monomers, the NMR spectra exhibit peaks at about 38, 35 and 27 ppm. The peak of 38 ppm can be assigned to the branch connected to the carbon while the peaks 35 and 27 ppm can be assigned, respectively, to the carbons in the alpha and beta positions based on the allocations offered by the literature (see, for example, Randall, J.C.J. Mater, Sci., Rev. Macromol, Chem. Phys. 1989, C29, 201) of long chain branches in LDPE. It was unexpectedly found that the long chain branched copolymer object of the present invention can be formed through solution polymerization using certain bridged substantially unrestrained metallocene catalysts, in accordance with what is described below in combination with the specific monomers described above. The solvent forming the polymerization means may be an inert liquid hydrocarbon (relative to the present comonomers) which may be, for example, a C4-C aliphatic hydrocarbon or, for example, isobutane, pentane, isopentane or the like or mixtures thereof. the same; or an aromatic hydrocarbon, such as, for example, benzene, toluene, xylene or the like. Alternatively, the solvent may be selected from one or more of the monomers I (preferred) or the third monomer, if appropriate, present in excess either alone or together with an inert diluent solvent, such as the solvents described above. The polymerization is carried out in the presence of a bridged metallocene substantially restricted, represented by the formula: Cp '/ \ Z MY2 \ cPJ where Cp1, Cp2 each independently represent a cyclopentadienyl or substituted hydrogenated pentadienyl group, Y each represents, independently, a univalent anionic ligand, M represents zirconium, titanium or hafnium, and Z represents a group bridge comprising an alkylene group having from 1 to 20 carbon atoms either a silyl or germanyl group, or a phosphine or amine radical which may also be substituted. Preferred complexes are complexes in which M is zirconium and Z is a C2 alkylene group. Preferred univalent anionic ligands are hydrogen, halide, hydrocarbyl, alkoxide, amide or phosphide, and are preferably selected from halides. A particularly preferred metallocene complex is a complex substituted cyclopentadienyl bridged at C2, represented by the formula: p where Y and Y 'represent, each independently, an anionic group, preferably hydrogen, halide (Cl, Br, I), C1-C5 alkoxy, C1-C5 amide, or phosphide and where M and Z are respectively selected from metal atoms and groups defined above. R3 and R'3 each independently represent a linear or branched C1-C20 hydrocarbyl or hydrocarbyl substituted by halogen, a linear or branched C1-C20 alkoxy radical, a C3-C12 cyclohydrocarbyl radical or a cyclohydrocarbyl radical substituted by halogen, a radical aryl, an alkaryl radical, an arylalkyl radical, a linear or modified C1-C20 hydrocarbyl radical containing an atom of silicon, germanium, phosphorus, nitrogen, boron, aluminum, or a halogen atom. Preferred groups R 3 and R 3 are C 1 -C 2 alkyl and especially C 1 -C 5 alkyl groups and substituted groups of triarylsilyl, arylalkyl, and trialkylsilyl groups; R2, R'2, R5 and R'5 each independently represent hydrogen or a group R3, and the pair R2 and R3 as well as the pair R'2 and R'3 may each represent a substituted or unsubstituted cyclic group it may contain unsaturation to provide a fused aromatic or aromatic ring such as for example indenyl, tetrahydroindenyl, benzoindenyl, naphthyl, anthracenyl, phenanthracenyl and the like. The metallocene catalysts of the present invention useful for providing the branched polymer of Long chains according to the present invention are symmetrical metallocene compounds in C2, and especially those which are metallocene compounds based on indenyl or substituted tetrahydroindenyl. Zirconium is the preferred metal and Z is a C2 alkylene group. Co-catalysts, usually organoaluminoium compounds such as trialkylaluminum, trialkyloxyaluminum, dialkylaluminum halides or alkylaluminum dihalides may be employed in the present invention. Particularly useful alkyl alumins are trimethylaluminum and triethylaluminum with the latter, frequently known as TEAL, being the most preferred. Methylaluminoxane (MAO) can also be used to carry out the methods of the present invention, especially for precursors of netural metallocene catalysts. MAO can be used as co-catalyst with metallocene catalysts in amounts well above the stoichiometrically equivalent amount by providing molar ratios between aluminum and the coordination metal (Me) of about 100 to 10,000. Modified aluminoxanes that are formed by the reaction of a condensed isobutylaluminum compound with a methylaluminum compound are also useful co-catalysts for this invention. While the invention of the applicant should not be restricted by theory, it is believed that neutral metalocenes of certain metals are converted to active cationic complexes through reaction with MAO in the manner presented by Zambelli, A. et al., "Isotactic Polymerization of Propene: Homogeneous Catalysts Based on Group 4 Metallocenes Without Methylaluminoxane" (Isotactic Polymerization of Propene: Catalysts homogeneous based on group 4 metallocenes without methylaluminoxane), Macromolecules 1989, 22, pages 2186-2189. The catalyst precursors used in the present invention can be prepared by procedures similar to those presented in US Patent No. 4,892,851, while active cationic catalysts can be produced by simple conversion of the neutral methMiocene to the cationic state following such procedures such as those disclosed in European applications No. 277,003 and 277,004, or more preferably, by reaction with triphenylcarbenium bornanes. Similarly, B-alcohol complexes (PhF5) 3 can be used as anionic precursors for the formation of the active cationic metallocenes of the present invention where the alcoholic proton reacts with an alkyl group on the coordinating metal atoms to generate a cationic metallocene and an alkoxide-B (PhF5) anion 3. The co-catalyst in situ can be mixed directly with the metallocene object of the present invention or, optionally, it can be introduced in an inorganic support. Alternatively, the cocatalyst can be added to the polymerization medium together with the metallocene complex. The amount of co-catalyst mixed with the metallocene complex can be such that a metal-metal (M) atom ratio of the metallocene and the metal is provided in the co-catalyst of 1-10,000: 10,000-1 in the case of the aluminoxanes and 1-100: 100-1 in another way. - The catalyst supports may comprise a single oxide or a combination of oxides. They can also be physical mixtures of oxides. The supports can have a high surface area (250-1000 M2 / g) and a low pore volume (0-1 ml / g) or a low surface area (0-250 M2 / g) and a high pore volume (1-5 ml / g) or preferably a high surface area (250-1000 M2 / g) and a high pore volume (1-5 ml / g) (mesoporous). Preferred support materials are silica, alumina, titania, boria as well as anhydrous magnesium chloride or mixtures thereof, although any support used in heterogeneous catalysis / polymer catalysis can be employed. The support can be subjected to a pretreatment for the purpose of modifying its surface, for example, thermal or chemical dehydroxylation, or a combination thereof, using agents such as hexamethyldisilazane and trimethylaluminum. Other reagents that can be used are triethylaluminum, methylaluminoxane, and other aluminum-containing alkyls, magnesium alkyls, "especially dibutylmagnesium and alkylmagnesium halides, zinc alkyl, and lithium alkyls, as well as sources of halogenation." Several impregnating regimes may be employed for the purpose of adding surface treatment and subsequent impregnation of metallocene A metallocene or metallocene / co-catalyst can be added to the support or to another supported polymerization catalyst, during or after the surface treatment in order to modify the support surface / catalyst of any combination of these The impregnation can be carried out sequentially either in several separate steps or in a single step using any method known in the prior art including vapor phase / impregnation treatment techniques The chain branching copolymer long objects of the present invention are formed a by solution polymerization in the presence of the metallocene catalysts described above alone or in combination with another polymerization catalyst known, for example, Ziegler-type catalyst or the like. It is preferred that the metallocene catalyst is the only catalyst material used or the main catalyst material.

The polymerization catalyst employed in the process according to the present invention can be used to produce the copolymers of the present invention by solution polymerization techniques. Methods and apparatuses for effecting said polymerization reactions are well known and described for example, in Encyclopaedia of Polymer Science and Engineering, published by John Wiley and Sons, 1987, volume 7, pages 480 to 488 and 1988, volume 12, pages 504 a 541, whose teachings are incorporated here in their entirety with reference. The currently required catalyst can be used in similar amounts and under conditions similar to those presented in the aforementioned reference. It has been unexpectedly found that the above-described class of unrestrained metallocene catalysts bridged in solution polymerization can be employed to provide long branched chain copolymers having an increased processing capacity, particularly copolymers of monomers containing alicyclic groups of vinyl and ethylene. In addition, the process of the present invention offers improved long chain branched ethylene / vinylcyclohexene copolymers which are useful as components in film articles. The catalyst must be present in an amount of about 10"10 to 10" 4, preferably 10"8 to 10 ~ 4 mol per liter of solution. The polymerization can be carried out, optionally, in the presence of a chain transfer agent, such as, for example, hydrogen, in order to control the molecular weight of the copolymer object of the present invention. It has been found that when hydrogen is used, Mw and Mn of the copolymer are reduced. The amount of hydrogen can be such that the partial pressure of hydrogen compared to the partial pressure of the monomers in the reactor space is from about 0.01 to 200%, preferably from 0.01 to 10%.

The present solution polymerization can be carried out at a temperature from about 0 ° C to 250 ° C, preferably from about 25 ° C to 150 ° C and especially from 50 ° to 100 ° C. The ability to employ elevated temperatures by solution polymerization offers a means to increase the reaction rate and the ability to form the polymer of the present invention in commercially feasible form. The present solution polymerization can be carried out under a pressure of about 1 atmosphere to about 20 atmospheres. A low pressure of about 1 to 20 atmospheres, preferably of 1 to 10 atmospheres, offers the copolymer of desired long branched chains. The initial pressure is provided through the partial pressures of ethylene, comonomers, solvent and optionally inert gas, such as nitrogen, argon or helium. The long chain branched copolymers of the present invention are useful for forming films or packaging materials, especially in the case of food packaging applications. The copolymer of the present invention has a high degree of processability, has a high zero-viscosity, a low propensity to melt fracture, a high melt tension as well as a long relaxation time under melting conditions. Thus, the present copolymer can be easily processed (eg, extruded) at high speeds in films having highly desired characteristics (e.g., high clarity, reduced surface imperfections at high extrusion rates), alone or as a layer in the case of a multi-layer film. The copolymer of the present invention offers a film that is suitable as a packaging material. The copolymer of the present invention can be used as the sole polymeric material for the formation of at least one layer of a film (the film can be a multilayer film having, for example, a gas barrier layer, a layer of adhesion, etc.). Alternatively, the copolymer of the present invention can be further mixed with one or more other useful polymers such as Film forming materials for packaging. Such polymers are thermoplastic and make the film more adaptable for use as packaging layers. Suitable polymers include, but are not limited to, polyethylene, low density polyethylene, very low density polyethylene, linear low density polyethylene, ultra low density polyethylene, high density polyethylene, polyethylene terephthalate (PET), polyvinyl chloride, polyvinylidene dichloride and copolymers thereof and ethylene copolymers such as ethylene-vinyl acetate, ethylene- (meth) acrylates of alkyl, ethylene-acid (meth) acrylic, and ethylene-ionomers of (meth) acrylic acid. In rigid articles such as beverage containers, PET is often used. Mixtures of different polymers can also be used. In general, these polymers are semi-crystalline materials useful for the formation of packaging materials and films. The selection of the polymeric diluent depends to a great extent on the article to be manufactured and on the final use of said article. Said selection factors are well known in the art. For example, certain polymers are known to provide adhesion, cleaning, barrier, mechanical properties and / or texture properties to the resulting article. Other conventional additives which may also be incorporated in the copolymer or mixture of copolymers include, without necessarily limited to them, fillers, pigments, dyes, stabilizers, processing aids, plasticizers, flame retardants, anti-fog agents, antioxidants, etc., and will be used in conventional quantities. The copolymer of the present invention provides improved packaging articles used in various fields. Packaging items are obtained in various forms including rigid containers, flexible bags, and combinations of the two, etc. Typical rigid or semi-rigid articles include cartons, bottles, containers, trays, cups, and the like having wall thicknesses within a range of about 100 to 1000 microns. The copolymer object of the present invention can be used as a coating that forms part of said articles. Flexible packings such as films, bags and the like typically have thicknesses of about 5 to 250 microns and may comprise a single-ply or multi-ply material. A single layer article can be prepared by solvent casting or by extrusion (preferred method). The multi-layer articles are typically prepared using co-extrusion, coating, lamination or extrusion lamination. Additional layers of a multi-layer article may include "oxygen barrier" layers, ie, layers of material that has an oxygen transmission rate equal to or less than 500 cubic centimeters per square meter per day per atmosphere (cc / (m2DdDatm)) at room temperature, that is, at a temperature of approximately 25 ° C. Typical oxygen barrier layers comprise poly (alkoxyethylene vinyl), poly (vinyl alcohol), polyacrylonitrile, polyvinyl chloride, poly (vinylidene dichloride), polyethylene terephthalate, silica, and polyamides such as Nylon 6 and Nylon 6,6. Copolymers of certain materials described above as well as sheet metal layers can also be used. Other additional layers may include one or more oxygen permeable layers. In a preferred packaging construction, especially for flexible food packaging, the layers include, in order starting from the outside of the packaging towards the innermost layer (the layer exposed to the cavity within a packaging formed suitable for containing a material packaging) of the packaging, (i) an oxygen barrier layer, (ii) a removal layer, and optionally, (iii) an oxygen permeable layer. The control of an oxygen barrier property of (i) allows a device to regulate the life of the packing removal by limiting the oxygen penetration rate to the removal component (ii), and thus limiting the speed of Consumption of the removal capacity. He control of the oxygen permeability of the layer (iii) allows a means to establish an upper limit in terms of the rate of removal of oxygen for the overall structure regardless of the composition of the removal component (ii). This can serve the purpose of extending the life of the films in the presence of air before sealing the package. In addition, the layer (iii) may offer a barrier against migration of the individual components in the removal films or removal by-products in the inner part of the package. In addition, the layer (iii) also improves the ability of thermal seal, clarity and / or blocking resistance (the tendency of the film to adhere on itself, especially during storage and handling) of the multilayer film. Thus, the layer (ii) can be exposed directly or indirectly to the cavity of the formed package. Additional layers such as adhesive layers can also be used. The compositions typically employed for the adhesive layers include polyolefins functionalized with anhydride and other well known adhesive layers. It has also been unexpectedly found that the copolymers of the present invention, more particularly the copolymers having units derived from at least one unsaturated vinyl alicyclic monomer, and preferably ethylene vinylcyclohexene copolymers, offer a coating improved adhesive inside a multi-layer film. For example, film layers composed of polyvinylidene chloride offer a barrier property to the resulting film. However, detachment is a concern and special efforts must be made to produce acceptable films. This concern is overcome by using the polymer of the present invention as an adjacent layer, or by mixing the copolymer with this difficulty to adhere the polymer layer material. The films formed from the copolymers of the present invention unexpectedly have higher densities than the ethylene / alpha-olefin copolymers that form conventional films (EAOC), and, therefore, can be used to provide barrier properties to a film in terms of the molecules that cross it. For example, copolymer films of the present invention offer reduced oxygen and moisture transmission rates compared to EAOC films having similar melting temperatures. The copolymers of the present invention offer films that have very good optical characteristics, high clarity and low cloudy. In addition, such copolymers have a thermal seal capability and offer films that can be oriented and shrunk and are therefore suitable for application in shrink films and vacuum packaging.

The polymer of the present invention is easily oxidized resulting in films that have high levels of oxygen on the surface. It is anticipated that these oxidized or surface treated films will have substantially superior surface properties such as, for example, fog properties, printability and adhesion to polar substrates. It is interesting to note that partially oxidized EVCH copolymers exhibit exceptionally good adhesion to metals and glass, especially in the hot state. Such properties are useful as hot melt adhesives. In addition, the partially oxidized, low molecular weight EVCH copolymers can serve as outstanding processing aids for the extrusion of thermoplastics by virtue of an increased sliding in the wall of an extruder. This could be effectively employed to retard the onset of melt fracture thus allowing film processing at a higher extrusion rate with reduced pressure and lower energy requirements. Like other semicrystalline polyolefin resins, EVCH can be thermally sealed, can be crosslinked and can be oriented and broken. The copolymers are therefore very suitable for applications in shrink films as well as vacuum packed.

The following examples are provided for illustrative purposes only and are not intended to limit the invention, as defined in the appended claims. All parts and percentages are by weight unless otherwise indicated. EXPERIMENTAL PROCEDURES: __ Ethylene (Air Products, Grade CP) and argon were purified by passage through columns containing molecular sieves (Davison, 3A, 4-8 mesh) and an activated copper catalyst (BASF-R3-11). 4-vinyl-l-cyclohexene was sprayed (Aldrich, 99% estimated and well DuPont, purity 97%) with argon, dried on molecular sieves (Davison 4A, 8-12 mesh) and passed through a short column containing neutral alumina immediately before use. Ethylenebis (indenyl) zirconium dichloride was purchased from Boulder Scientific (IV) racemic (catalyst A, rac-En (Ind) 2ZrCl2), racemic dimethylsilylbis (indenyl) zirconium (IV) dichloride (catalyst B, rac-Me2Si (Ind) 2ZrCl2), racemic dimethylsilylbis (2-methylindenyl) zirconium (IV) dichloride (catalyst C rac-Me2Si (2-Me-Ind) 2ZrCl2), and ethylene bis (2,4,6,6-dichloride) , 7-tetrahydroindenyl) zirconium (IV) racemic (catalyst D, rac-En (Thind) 2ZrCl2) and said catalysts were purified by recrystallization. The 1H-NMR spectra of several purified metallocene catalyst precursors were consistent with the literature assignments for these compounds Poly (methylaluminoxane) (MAO, Akzo, 7.8% Al by weight in toluene) was used as received. All the manipulations were carried out using syringes, inoculation tanks or cannula techniques to exclude air and moisture. The catalysts and MAO were stored and transferred in an oxygen-free and moisture-free glove box. The reactor used for the polymerizations was an autoclave with 2 L stainless steel jackets (Zipperclave by Autoclave Engineers) equipped with a Magnedrive from above and a helical impeller at 400 revolutions per minute. The control of the temperature was maintained using an external recirculation bath (NesLab RTE-100). The pressure and ethylene flow rate were measured and controlled using a calibrated mass flow controller. The stirring speed was typically within 25 revolutions per minute of the set value while the temperature and pressure were maintained within 1 ° C and 1 psig, respectively. The density (± 0.005 g / cm3) was estimated either from the melting strand coming from the melt flow indexer (MFI, thread density) or by melt pressure of a thick film (10-30 mils). Density measurements were carried out on an analytical balance using a density adapter with ethanol absolute as a liquid phase. Differential scanning calorimetry was performed on TA Instruments DSC 2920 or a Perkin-Elmer DSC-7 at a heating / cooling rate of 10 ° C / min and the instruments were calibrated with an Indian NIST standard. 13C NMR analysis was measured using a Bruker DMX-400 MHz NMR spectrometer, with proton decoupling with benzene-de as an internal block at 120 ° C in 1,2,4-trichlorobenzene. Molecular weight and molecular weight distributions were measured using a Waters 150 CV gel permeation chromatograph at a temperature of 150 ° C in trichlorobenzene that was calibrated using polystyrene standards of narrow molecular weight distribution. The molecular weight distribution, and the statistical moments (Mn, Mw, M2, etc.) of these were determined using the universal calibration method. The melt flow index was measured using a CSI MFI-2 at a temperature of 190 ° C and weights of 2.16 kg (I2) or 10 kg (l) according to ASTM D 1238. The responses of the material to the temperature and effort The cutting was carried out in the following manner: Resin discs, 50 mm in diameter and approximately 3 mm thick, were prepared by compression molding the resin pellets of each sample at a temperature of 160 ° C and 550 psig for five minutes. The discs could then be cooled to room temperature. Discs free from air bubbles were easily produced with the resins in question and in the aforementioned molding conditions. Each disk was placed between the plates of a 50 mm diameter parallel plate device of the Rheometrics RMS-800 Mechanical Spectrometer and the spacing of the plates was adjusted to 1,500 mm. Any rejected fusion squeezed beyond the edge of the plate during space adjustment was removed with a spatula. A dynamic tension of 5% was imposed on the sample since the oscillation frequency ranged from 10 ~ 2 rad / sec to 102 rad / sec at logarithmically spaced intervals of two points per decade. Frequency scans were performed at each of three temperatures at 20 ° C intervals of 180 ° C to 140 ° C, to minimize thermal degradation of sample, and to facilitate the construction of a shear viscosity master curve. The parallel plate device was initially set to zero at a temperature of 180 ° C, and a coefficient of thermal expansion of 2.5 mm / ° C was specified to take into account the change in plate space of the parallel plate device with temperature, in accordance with that recommended by Rheometrics Scientific, Inc. This procedure complies with ASTM D 4440.

The data for the shear viscosity of complex shear (? *) And loss (G ") and storage modules (G") in shear stress obtained from frequency scans at the three melting temperatures were collapsed in a master curve by the reference of each frequency sweep through a time-temperature superposition to the data obtained at 180 ° C. The time-temperature superposition was achieved using a Rhios Version 4.2.2 rheological analysis program that operates in the horizontal displacement mode. An Arrhenius adjustment of the resulting displacement factors for each melting temperature provided an estimate of the flow activation energy. A discrete relaxation spectrum for the master curve was determined from the nonlinear least squares adjustment of the data G ', G "considering approximately two relaxation times and modules for each tenth angular frequency,?. G ° N, was estimated from the intersection of a nonlinear least-squares adjustment of the master curve G 'for frequencies greater than or equal to 1 rad / sec, in accordance with the following model equation: G '(?) = C í +? where c and d are constants obtained from non-linear regression analysis.

The complex shear viscosity master curves were modeled by a nonlinear least squares regression fit to the Cross Model equation: where? 0 is the zero shear viscosity,? 0 is the average relaxation time of the melt, and b is the Cross Model exponent, related to the degree of shear thinning in the melt. Example 1 Copolymerization of ethylene-4-vinylcyclohexene (E-VCH) in solution A solution of 4-vinyl-l-cyclohexene (3 M in toluene) was transferred to a 2 L Zipperclave reactor and 3.8 mL of MAO (7.8) was injected. % by weight of Al in toluene) using a syringe. The solution was allowed to equilibrate at 50 ° C under a pressure of 5 psig of ethylene and 2 mg of rac-En (Ind) 2ZrCl2 (catalyst A, dissolved in 20 L of degassed dried toluene) was injected into the reactor. The polymerization was allowed to take place with ethylene fed on request to maintain the pressure in the reactor. After 2.8 h, the contents of the reactor were discharged in methanol, stirred, filtered, and dried in vacuo. The amorphous polymer (155 g) had a melt flow index (2.16 kg, 190 ° C) of 1.7 dg / min and an I10 / I2 of 13.3 with a molecular weight (according to GPC): Mw = 90,700 g / mol and a polydispersity index PDI-2.7. This example demonstrates that substantially amorphous ethylene copolymers can be prepared which contain long chain branches. EXAMPLE II Copolymerization of ethylene-4-vinylcyclohexene To a dry, deoxygenated 2 L Zipperclave autoclave, 900 g of a 3.0 M solution of VCH in toluene was added. MAO (1.8 mL of a 7.8% by weight solution of Al in toluene) was injected into the reactor using a syringe and the reactor was heated to 75 ° C. The solution was saturated at 15 psig of ethylene and the polymerization initiated by the injection of 1 mg of a catalyst A dissolved in 5 mL of toluene. The polymerization was monitored and the polymer solution was periodically removed from the reactor through a ball valve connected to the bottom of the reactor. Aliquots were removed from the reactor after 15, 40, 60 and 65 minutes. The aliquots of the polymer solution were precipitated in methanol, filtered, and dried in a vacuum oven. A total of 120 g of polymer was collected. The melting temperature (° C) and the melting index of the aliquots appear-in Table 1. This indicates a characteristic of the invention in which the magnitude of the long chain branches as evidenced by the increase of I10 / I2 rises as the polymerization progresses. The increase in I10 / I2 is accompanied by a decrease in the Melt Flow Index (I2). Table 1. Effect of polymerization time on the melt flow properties of E-VCH. - Time Temperature IIO / IJ (min) of fusion 15 99.0 3. 52 8. 2 40 96.6 0. 49 13. 6 60 95.4 0. 15 16. 7 65 93.3 0. 08 19. Example II Copolymerization of ethylene-4-vinylcyclohexene A polymerization was carried out according to Example I except that 866 g of VCH / (3M in toluene) were used and the samples were taken from the reactor after 15, 32 and 52 minutes whose results appear in table 2. Aliquots (approximately 50 L) of the polymer were discharged in these cases in a bottle containing hindered phenolic stabilization (Irganox 1076 and Irgafos 168) dissolved in toluene. The volatile parts were removed using a vacuum oven. To the remaining polymer solution in the reactor, 4 fractions (based on polymer weight) were collected with increasing levels of Irganox 1076 aggregates (406, 875, 1360 and 2000 ppm). A total was isolated of 123 g of polymer. The results are summarized in table 3. Table 2. Effect of polymerization time on the melt flow properties of E-VCH Time Temperature I2 I10 / I2 (min) of melting 15 91.9 2.65 9.67 32 89.3 0.59 13.37 52 87.7 0.12 18.4 Table 3. Effect of the antioxidant level on the melt flow properties of E-VCH Irganox level I2 I10 / I2 1076 406 0. 028 22. 8 875 0. 055 21. 6 1360 0. 056 21. 7 2000 0. 058 21. 3 These examples show that the increase in I10 / I2 occurs in the reactor and that the polymer can be stabilized by the addition of a conventional stabilizer, such as Irganox 1076. This shows that hydrogen can be used as a molecular weight modifier of polymers while continuing to obtain higher I10 / I2 ratios than expected. Example IV Copolymerization of ethylene-4-vinylcyclohexene A polymerization was carried out according to Example 1 except that 862 g of VCH / (3 M in toluene) were used, 0.0123 mol of hydrogen was added and the samples were taken from the reactor after 17, 32 and 60 minutes. The polymer was unloaded in these cases in flasks containing a small amount of Irganox 1076 and Irgafos 168. The volatile parts were removed using a rotary evaporator with subsequent drying in a vacuum oven. The results are summarized in Table 4. The final polymer 130 g, stabilized with 770 ppm Irganox 1076 and 380 ppm Irgafos 168. Table 4. Effect of polymerization time on the melt flow properties of E-VCH. Time temperature of l -1? 0o / l. (min) merger 17 94.5 75.0 nd 32 93.3 19.4 nd 60 89.7 2.2 11.7 These examples show that the increase in terms of is occurring in the reactor and not due to some subsequent cross-linking. This example further demonstrates that hydrogen can be used as a modifier of molecular weights of polymers while still obtaining I10 / I2 ratios greater than expected. EXAMPLE V Copolymerization of ethylene-4-vinylcyclohexene A polymerization was carried out in accordance with Example I. To a 2L Zipperclave reactor were added 798 g of a VCH solution (3 M in toluene) and 1.2 mL of MAO solution. (10.3% by weight of Al in toluene). The solution was heated to a temperature of 75 ° C and saturated to 15 psig of ethylene. The racemic dimethylsilylbis (indenyl) zirconium (IV) dichloride (catalyst B, 1 mg) was dissolved in 5 mL of toluene and injected into the reactor using a syringe. The polymerization was allowed to continue for 60 minutes and samples were removed from the reactor after 15 minutes and 40 minutes. The polymer (a total of 106 g) was precipitated in methanol, filtered and dried according to that described above. The resulting polymer exhibited a broad melting endotherm of 40 to 120 ° C, and exhibited the following melt flow properties (Table 5). Table 5. Effect of polymerization time on melt flow properties Time temperature of I2 I10 / I2 (min) melting (° C) 15 82.7 75.0 14.1 40 80.0 19.4 19.2 60 76.9 2.2 33.1 This example demonstrates that the formation of LCB is not unique to catalyst A but is a general characteristic of solution polymerization employing bridged indenyl-based C2 symmetrical metallocenes. Example VI Copolymerization of ethylene-4-vinylcyclohexene A polymerization was carried out according to Example I. To a 2L Zipperclave reactor was added 858 g of a VCH solution (3 M in toluene) and 2.5 mL of an MAO solution (10.3% by weight of Al in toluene). The solution was heated to a temperature of 50 ° C and saturated to 15 psig of ethylene. Racemic dimethylsilylbis (2-Me-1-indenyl) zirconium (IV) dichloride (catalyst C, 1 mg) was dissolved in 5 mL of toluene and injected into a reactor using a syringe. The polymerization was allowed to proceed for 60 minutes and samples were taken from the reactor after 21 minutes and 40 minutes. The polymer (approximately 60 g) was precipitated in methanol, filtered and dried according to that described above. The resulting polymer had a melting temperature of 80.8 ° C and had the following melt flow properties (Table 6). Table 6. Effect of polymerization time on melt flow properties Time temperature of I2 I? O / I2 (min) melting (° C) 21 nd 0 05 9. 6 40 nd 0. 021 11. 9 60 80.8 0. 007 18. 2 This example further demonstrates that the formation of LCB is not unique to catalyst A but is a general characteristic of solution polymerization employing substituted indenyl-based C2 symmetrical metalócenos. Example VII Copolymerization of ethylene-4-vinylcyclohexene A polymerization was carried out according to Example I except that the polymerization was carried out at a temperature of 50 ° C, 7 psig of ethylene in 824 g of 3M VCH in toluene using 2 mL of an MAO solution (9.6% by weight of Al in toluene) and 1.5 mg of racemic ethylenebis (tetrahydroindenyl) zirconium (IV) dichloride (catalyst D). The polymerization was allowed to proceed for 3 hours and 68 g of polymer was isolated.

The resulting E-VCH copolymer had a melting temperature of 107 ° C and an I2 of 1.8 dg / min with a melt flow ratio (I? O / I2) of 8.5. This example demonstrates that other isospecific catalysts described in the present application can be employed to prepare branched long chain copolymers of the present invention. Example VII Copolymerization of ethylene-4-vinylcyclohexene A polymerization was carried out according to Example I, except that the polymerization was carried out at a temperature of 50 ° C, 4 psig of ethylene in 850 g of VCH 3 M in toluene using 4.7 mL of a solution MAO (9.6% by weight of Al in toluene), and 3 mg of racemic ethylenebis (tetrahydroindenyl) zirconium (IV) dichloride. The polymerization was continued for 90 minutes and "117 g of the polymer was isolated.The resulting E-VCH copolymer had a melting temperature of 99 ° C and an I2 of 0.40 dg / min with a melt flow ratio (I? I2) of 20.5 The average weight of the molecular weight was 80,300 g / mol with a PDI of 1.9 (both measurements according to GPC). This example further demonstrates that other isospecific catalysts can be used to prepare branched long chain copolymers and that high I? / I2 ratios are obtained with low polydispersity values. EXAMPLE IX Preparation of high-melting ethylene-4-vinylcyclohexene copolymer Polymerization was carried out according to Example 1, except that the polymerization was carried out at a temperature of 50 ° C, 50 psig of ethylene in 868 g of 2.2 M VCH in toluene using 2.8 mL of an MAO solution (7.8% by weight of Al in toluene) and 0.5 mg of racemic ethylenebis (indenyl) zirconium (IV) dichloride. The polymerization it was continued for 54 minutes and 58 g of polymer was isolated. The resulting E-VCH copolymer had a melting temperature of 121 ° C and an I2 of 0.03 dg / min with a melt flow ratio (I10 / I2) of 31.5. The copolymer contained 1 mol% VCH (according to 13C NMR), the average weight of the molecular weight of 107,000 g / mol with a PDI of 2.3 (both measurements by GPC). This example demonstrates that copolymers with higher melting points can be prepared which contain long chain branches. EXAMPLE X Preparation of high melting point ethylene-4-vinylcyclohexene copolymer Polymerization was carried out according to Example I, except that the polymerization was carried out at a temperature of 50 ° C, 50 psig of ethylene in 870 g of VCH 2.2 M in toluene using 2.8 mL of an MAO solution (7.8% by weight of Al in toluene) and 0.5 mg of racemic ethylenebis (indenyl) zirconium (IV) dichloride (catalyst A). The polymerization was continued for 17 minutes and 37 g of polymer were isolated. The resulting E-VCH copolymer had a melting temperature of 119 ° C and an I2 of 0.09 dg / min with a melt flow ratio (I? O / I2) of 17.9. The copolymer contained 1.1 mol% VCH (according to 13C NMR), the average weight of the molecular weight was 105,000 g / mol with a PDI of 2.2 (both determinations by GPC). This example demonstrates additionally that higher melting point copolymers can be prepared which contain long chain branches. Example XI Preparation of high melting ethylene-4-vinylcyclohexene copolymer Polymerization was carried out according to Example I, except that the polymerization was carried out at a temperature of 50 ° C, 50 psig of ethylene in 880 g of VCH 2.2 M in toluene using 2.8 mL of an MAO solution (7.8% by weight of Al in toluene) and 0.5 mg of racemic ethylenebis (indenyl) zirconium (IV) dichloride (catalyst A). Hydrogen (0.01106 mol) was added. The polymerization was allowed to proceed for 33 minutes and 56 g of polymer was isolated. The resulting E-VCH copolymer had a melting temperature of 120 ° C and an I2 of 0.22 dg / min with a melt flow ratio (I10 / I2) of 15.5. The copolymer contained 1 mol% VCH (according to 13C NMR), the average weight of the molecular weight was 88,000 g / mol with a PDI of 2.1 (both determinations by GPC). This example demonstrates that higher melting point copolymers can be prepared which contain long chain branches, and hydrogen can be added to modify the molecular weight of the polymer. Example XII Preparation of amorphous copolymer of ethylene-4-vinylcyclohexene A polymerization was carried out according to Example I, except that the polymerization was carried out at a temperature of 50 ° C, 50 psig of ethylene in 834 g of HCV using 3.8 mL of an MAO solution (7.8% by weight of Al in toluene) and 2 mg of racemic ethylenebis (indenyl) zirconium (IV) dichloride. Polymerization proceeded for 125 minutes and 63 g of amorphous polymer was isolated. The resulting E-VCH copolymer exhibited an I2 of 6.5 dg / min with a melt flow ratio (I10 / I2) of 8.9. The copolymer was found to contain 15.7 mol% VCH (according to 13C NMR), the average weight of the molecular weight was 62,000 g / mol with a PDI of 2.0 (both determinations by GPC). This example demonstrates that substantially amorphous copolymers containing long chain branches can also be prepared through this process. Example XIII Preparation of amorphous copolymer of ethylene-4-vinylcyclohexene A polymerization was carried out according to example I, except that the polymerization was carried out at a temperature of 50 ° C, 5 psig of ethylene in 846 g of HCV using 3.8 L of an MAO solution (7.8% by weight of Al in toluene) and 2 mg of racemic ethylene bis (indenyl) zirconium (IV) dichloride (catalyst A). The polymerization was continued for 165 minutes and 174 g of amorphous polymer was isolated.

The resulting E-VCH copolymer presented an I2 of 1.71 dg / min with a melting-finite ratio (I10 / I2) of 11.3. It was found that the copolymer contained 18.1 mol% VCH (according to 13C NMR), the average weight of the molecular weight was 91,000 g / mol with a PDI of 2.6 (both determinations by GPC). This example demonstrates that substantially amorphous copolymers containing higher levels of branched long chain branches can be prepared. Example XIV Copolymerization of ethylene-4-vinicyclohexene A polymerization was carried out according to Example I, except that the polymerization was carried out at a temperature of 50 ° C, 5 psig of ethylene in 830 g of HCV using 3.8 L of an MAO solution (7.8% by weight of Al in toluene) and 2 mg of ethylenebis (indenyl) zirconium dichloride (IV) racemic. The polymerization was sampled after 33, 67 and 133 minutes and the molecular weight of the fractions was measured. The polymerization was allowed to continue for 200 minutes and 125 g of amorphous polymer were isolated. The resulting E-VCH copolymer exhibited an I2 of 1.22 dg / min with a melt flow ratio (I? O / I2) of 11.2. The final copolymer contained 15.5 mol% VCH (according to 13C NMR), the average weight of the molecular weight was 86,000 g / mol with a PDI of 2.6 (both determinations by GPC). The results of the sampling are shown below in table 7. This example demonstrates that substantially amorphous ethylene copolymers can be prepared with very high levels of long chain branches and that the molecular weight of the polymer increases during polymerization. Table 7. Effect of polymerization time on the melt flow properties in example 14. Polymer time% Mw (g / mol) PDI merization (min) VCH in copolymer 33 14.9 56,500 1.9 67 15.1 62, 600 2.1 133 16.6 72,500 2.3 200 15.9 86,300 2.6 Example XV Copolymerization of ethylene-4-vinylcyclohexene A polymerization was carried out according to Example I, except that the polymerization was carried out at 50 ° C, 5 psig of ethylene using 53.1 g of VCH, 512 g of toluene containing 0.1% by weight of Al (MAO), a small amount of hydrogen (a 40 mL sample cylinder containing 50 psig) and 2.2 mg of ethylenebis (indenyl) zirconium dichloride (IV) racemic (catalyst A). The polymerization was allowed to continue for 70 minutes and isolated 110 g of semicrystalline polymer. The resulting E-VCH copolymer presented an I2 of 1.18 dg / min with a ratio of flow in fusion (I10 / I2) of 15.4. The copolymer had a melting temperature of 103.5 ° C, and the VCH content was estimated (based on the melting temperature) at 4.3 mol% VCH and the average weight of the molecular weight was 60.100 g / mol with a PDI of 2.4 (both determinations according to GPC). Example XVI Copolymerization of ethylene-4-vinylcyclohexene A polymerization was carried out according to Example I, except that the polymerization was carried out at a higher polymerization temperature of 75 ° C, 10 psig of ethylene using 211 g of VCH, 876 g of toluene containing 0.075% by weight of Al (MAO) and 1 mg of racemic ethylenebis (indenyl) zirconium (IV) dichloride (catalyst A). The polymerization was allowed to proceed for 70 minutes and 158 g of semicrostatin polymer was isolated. The resulting E-VCH copolymer exhibited an I2 of 1.13 dg / min with a melt flow ratio (I10 / I2) of 12.9. The copolymer had a melting temperature of 94.1 ° C and the VCH content was estimated (based on its melting temperature) at 5.9 mol% VCH. Example XVII Copolymerization of ethylene-4-vinylcyclohexene A polymerization was carried out according to Example I, except that the polymerization was carried out at a temperature of 75 ° C, 10 psig of ethylene using 409 g of VCH, 670 g of toluene containing 0.075% by weight of Al (MAO) and 3 mg of racemic ethylenebis (indenyl) zirconium (IV) dichloride (catalyst A). The polymerization was continued for 110 minutes and 184 g of a semicrystalline polymer was isolated. The resulting E-VCH copolymer exhibited an I2 of 4.53 dg / min with a melt flow ratio (I10 / I2) of 10.7. The copolymer had a melting temperature of 81.6 ° C, and the VCH content was estimated (based on its melting temperature) at 7.8 mol% VCH. Example XVIII Copolymerization of ethylene-4-vinylcyclohexene Polymerization was carried out in a Meyers Mixer with a 30 L jacket equipped with a wall cleaner (70 revolutions per minute) and a high speed mixer (3000 revolutions per minute). ). The polymerization was carried out at a temperature of 70 ° C (± 3 ° C) and 25 psig of ethylene using 17.1 kg of VCH and about 46 g of an MAO solution (10% by weight of Al in toluene). Polymerization initiated by injection of catalyst D (10 mg). The polymerization was continued for 30 minutes with an average ethylene absorption of 40 standard liters per minute. The total ethylene absorption was 1217 standard liters and the total polymer yield was estimated at approximately 1500 g. Polymerization was completed by rapid reactor venting, injection of 3 mL of a methanol / water mixture (approximately 4: 1) and stabilized with 2.5 g of Irganox 1076. An aliquot of polymer solution was evaporated to dryness and the resulting polymer was found to have a melting temperature of 87.5 ° C., an I2 of 2.46 and an I10 / I2 ratio of approximately 8. The average weight of the molecular weight was 69,500 and the PDI of 1.9 according to GPC. Example XIX A comparison copolymerization of two alpha olefins was carried out in accordance with Example I. The resulting copolymer did not exhibit the desired properties. To a 2 L Zipperclave reactor were charged 48 g of distilled, dry 1-hexene and 750 g of a toluene solution containing 0.075% by weight of Al. The solution was heated to a temperature of 75 ° C and saturated to 50 psig. and ethylene was fed according to the demand. Ethylenebis (racemic indenyl2ZrCl2 (0.03 mg) was injected into the reactor and the polymerization proceeded for 75 minutes, aliquots were removed from the reactor after 12 minutes, 43 minutes and 65 minutes respectively, after 75 minutes, the reactor contents were discharged into the reactor. Methanol was stirred, filtered and dried The final EH copolymer (84.5 g) had a melting temperature of 107.7 ° C and an I2 of 2.9 g / min and an I? 0 / I2 ratio of 7.3 which is consistent with a linear polymer substantially free of long chain branches.

In addition, I2 and the I10 / I2 ratio did not change substantially during the course of the polymerization in accordance with that evidenced by similar I2 and I? / I2 values, this example clearly shows that certain monomers such as (I) in combination with certain catalysts have an improved capacity in accordance with the process of the present invention to form long chain branches as compared to α-olefins. EXAMPLE XX Mixtures 60/40 of ethylene vinylcyclohexene copolymers with thermoplastic resins In a series of experiments, E-VCH copolymer (24 g, 60% of Example XVIII) was added to the Brabender mixing chamber at a temperature of 130 ° C. under nitrogen purge. A second resin of the mixture (16g, 40%) was added to the chamber in accordance with the following table. In some cases, which are indicated below, the temperature was slightly elevated to allow the melting temperature of the particular polymer. All samples were mixed for 30 minutes with a constant nitrogen purge. The samples were removed from the mixer, hot, and pressed into sheets. A small sample was then cut from the sheet and pressed at 140 ° C for about 1 minute to provide a "thin" film (5-11 mils) for optical measurements. The measures Optics were performed on a Haze-Gard Plus and brightness was measured at 45 ° using a Micro brightness meter (both from MYK Gardner). Five different mixtures were prepared in a 60/40 ratio: low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer (E-VA), ethylene-propylene copolymer (EPC) and ethylene-butyl acrylate copolymer (E-BA). The preferred mixtures are mixtures with good optical characteristics that can be defined as autotransmittance, clarity and brightness and with low cloud values. The copolymer of the present invention produces good blends of optical qualities with LDPE, LLDPE, and EPC, the various resins employed herein which are typically those employed in film forming activities. Resin Name Supplier Density commercial MFI E-VCH - - 0.93 2.5 A LDPE POLY-ETH Chevron 0.918 7.0 1017 B LLDPE Dowlex Dow 0.935 2.5 2037 C E-VA LD-318.92 Exxon 0.930 2.0 D EPC PD 9302 Exxon 4.0 E E-BA Lotryl Elf EBA-18 Atochem Table 8 Temp. Thickness% of trans-% of% of% of (° C) (thousand) mitancy cloudy brightness brightness E-VCH / A 140 11 92.8 9.7 83.9 64 E-VCH / B 140 5 93.3 7.34 95.7 63 E-VCH / C 130 8 94.5 14.2 79.8 57 E-VCH / D 150 10 93.2 67.2 78.3 43 E-VCH / E 130 12 93.9 47.7 90.6 49 Example XXI A series of semi-crystalline copolymers of ethylene and vinylcyclohexene was prepared in accordance with what is described below. Each of the copolymer products was analyzed to determine its melting temperature (Tm) and melt flow index (I2), and pressed into films in order to determine their physical properties. The results appear in the following table. These results are compared with linear low density polyethylene which has a higher melting temperature of about 122 ° C. Preparation of E-VCH copolymer 1 A polymerization was carried out according to Example I, except that the polymerization was carried out at a temperature of 50 ° C, 5 psig of ethylene using 88 g of VCH, 510 g of toluene which contained 0.1% by weight of Al (of MAO). Polymerization started by the injection of 2 mg of racemic ethylenebis (indenyl) zirconium (IV) dichloride (catalyst A) dissolved in 10mL of toluene. The polymerization was allowed to proceed for 150 minutes and 115 g of a semi-crystalline polymer was isolated. The resulting E-VCH copolymer had a melting temperature of 69 ° C, an I2 of 4.6 dg / min. It was found that the copolymer had a density of 0.936 g / cm 3 and contained 10 mol% of VCH in accordance with that determined by 13 C NMR. Preparation of E-VCH 2 copolymer A polymerization was carried out according to Example I, except that the polymerization was carried out at a temperature of 50 ° C, 5 psig of ethylene using 119 g of VCH, 510 g of toluene containing 0.1% by weight of Al (of MAO). Polymerization started by injection of 2 mg of racemic ethylenebis (indenyl) zirconium (IV) dichloride (catalyst A) dissolved in 5 mL of toluene. The polymerization was allowed to proceed for 110 minutes and 78 g of a semi-crystalline polymer was isolated. The -copolimer The resulting E-VCH had a melting temperature of 78 ° C, an I2 of 0.029 dg / min. and an I? 0 / I2 ratio of 17.8. The copolymer was found to have a density of 0.930 g / cm 3 and contain 9 mol% VCH in accordance with that determined by 13 C NMR. Preparation of E-VCH copolymer 3 A polymerization was carried out in accordance with Example I, except that the polymerization was carried out at 50 ° C, 5 psig of ethylene using 77 g of HCV, 530 g of toluene containing 0.1% by weight of Al (of MAO). The polymerization was started by the injection of 2 mg of racemic ethylene bis (indenyl) zirconium (IV) dichloride (catalyst A) dissolved in 5 L of toluene. The polymerization was allowed to proceed for 112 minutes and 76 g of a semi-crystalline polymer was isolated. The resulting E-VCH copolymer had a melting temperature of 83 ° C, an I2 of 0.176 dg / min and an I10 / I2 ratio of 21.7. The copolymer had a density of 0.929 g / cm 3 and contained 8 mol% of VCH in accordance with that determined by 13 C NMR. Preparation of E-VCH copolymer 4 The polymerization was carried out according to Example I, except that the polymerization was carried out at 50 ° C, 5 psig of ethylene using 102 g of HCV, 260 g of toluene containing 0.1% by weight of To (from MAO). The polymerization was started by the injection of 1 mg of racemic ethylenebis (indenyl) zirconium (IV) dichloride (catalyst A) dissolved in 20mL of toluene. The polymerization was allowed to proceed for 43 minutes and 25 g of a semi-crystalline polymer was isolated. The resulting E-VCH copolymer had a melting temperature of 90 ° C, an I2 of 0.85 dg / min and an I? 0 / I2 ratio of 12.1. It was found that the copolymer had a density of 0.943 g / cm3.

Preparation of E-VCH copolymer 5 A polymerization was carried out according to Example I, except that the polymerization was carried out at a temperature of 50 ° C, 5 psig of ethylene using 36 g of HCV, 530 g of toluene containing 0.1% by weight of Al (of MAO). Polymerization initiated by the injection of 2 mg of racemic ethylenebis (indenyl) zirconium (IV) dichloride (catalyst A) dissolved in 5 L of toluene. The polymerization was allowed to proceed for 90 minutes and 81 g of a semi-crystalline polymer was isolated. The resulting E-VCH-copolymer had a melting temperature of 103 ° C, an I2 of 0.013 dg / min and an I? O / I2 ratio of 18.7. It was found that the copolymer had a density of 0.930 g / cm 3 and contained 4 mol% of VCH in accordance with that determined by 13 C NMR. Example XXII Tension and elongation results Samples of E-VCH showing variations in VCH content were tested to determine their tensile strength, ultimate elongation and Young's modulus and compared with an LLDPE (table 9). As expected, Young's modulus increased as the degree of crystallinity increased. The lower tensile strength and the elongation at the lower break resulted in an overall reduction in hardness (area under the curve of strain / strain T & E) of the resin. It should be emphasized, however, that LLDPE had a higher melting temperature and therefore is expected to be hard. The results of tension and elongation of E-VCH are good and suggest that they are useful as material for film layers. The physical resistance combined with its inherent crosslinking capacity (potentially at low doses of electron beams) can nevertheless be used profitably in structures exposed to low doses of radiation, especially to obtain resistance to fats, for example. Table 9. Summary of tensile strength properties of ethylene-vinyl-cyclohexene copolymers Poly-% molar Resistance- strength modulus (° C) (dg / VCH Young a tion (in # / of min) (per voltage last inch3) refeNMR) (psi) (psi) rencia 69 4.6 10 5631 3050g 750g 8451g +321 +460 +100 ± 989 78 0.03 3700 4200 - 58-5 7800 +110 +330 +10 _ +360 83 0.18 5800 4472 636 9700 +114 +285 +12 +505 90 0.85 nd 8600 5300 583 11100 +236 +924 +45 +1232 103 0.01 4 18900 3500 470 9200 - +814 +806 +51 +1770 LLDPEe nd 1.0 1.7 (0) 51600 5175 735 17160 (12 milé + 4434 +353 +22 +1194 gaps) LLDPEe nd 1.0 1.7 (0) 48110 5060 748 1712Q (20 milé- +1215 +222 +16 +749 chasms inch) LLDPEe nd 1.0 1.7 (0) 47390 4954 747 16830 (30 mil- _ + 787 _ + 278 _ + 23 _ + 1021 das of an inch) a) Melting temperature from DSC at 10 ° C / min; b) melt flow index at 190 ° C and 2.16 kg; c) Young's modulus measured with a crosshead speed of 0.5 inch / min; d) stress properties measured with a crosshead speed of 10 inches / min with hardness considered as the area under the stress / strain curve using test specimens with a thickness of 15 to 30 mils; e) linear low density polyethylene, 0.920 g / cc, Dowlex 2045.03 (Dow); f) Young's modulus measured by a crosshead speed of 1.0 inch / min; g) measured tension properties with a crosshead speed of 5 inches / min with a hardness considered as the area under the stress / strain curve. EXAMPLE XXIII (Single Layer Film of an Ethylene Copolymer LCB-inylcyclohexene) Films hot pressed from an EVCH copolymer having approximately 2 mol% VCH, of approximate dimensions of 0.020 inch x 2.5 inch x 2.5 inch, prepared and stretched in a laboratory biaxial orientation device (TM Long Company). Using an analogous procedure, hot pressed films of 0.918 g / cm3 of linear heterogeneous low density polyethylene (Dow, Dowlex 2045.03), of approximate dimensions of 0.014 inch x 2.5 inch x 2.5 inches were prepared and stretched. The selection of (LLDPE) as a reference sample is based on its similarity in terms of its Vicat softening temperature relative to the EVCH copolymer. Stretching conditions for each of the pressed films were as follows: Stretching mode: simultaneously biaxial at 3x3_ During stretch: 185 ° -F (85 ° C) __ stretch speed: 2 and 20 inches per second After stretching , all the films were cooled with ambient air, removed from the apparatus and maintained at a temperature of approximately 73 ° C for at least two days before the test. The voltage module (ASTM D882-91, Method A) and the free shrink properties were tested along each of the two orthogonal directions of stretching in the film samples, and the values were averaged. The impact resistance is determined in accordance with ASTM D3763-86. The EVCH film presents superior properties of tensile strength, free shrinkage and impact resistance. Example XXIV (Single-Layer Film Oriented and an Ethylene Copolymer) LCB / vinylcyclohexene) i Films hot pressed from an ethylene-vinylcyclohexene copolymer with approximately 3 mol% VCH, approximately 0.020 inch x 2.5 inch x 2.5 inch, were prepared and stretched in a laboratory biaxial orientation apparatus (TM Long Company). By an analogous procedure, hot pressed films of a very low density polyethylene (0.905 g / cm3; Dow Attane4203) VLDPE of approximately 0.014 inch x 2.5 inch x 2.5 inches were prepared and stretched. The reference sample was chosen based on its similar Vicat softening temperature relative to the ethylene-vinylcyclohexene copolymer sample. The Stretching conditions for each of the pressed films were as follows: Stretch mode: simultaneously biaxial at 3x3 During stretch: 185 ° F (85 ° C) Stretch speed: 2 and 20 inches per second After stretching, all Films are cooled with ambient air, removed from the apparatus and maintained at a temperature of approximately 73 ° C for at least two days before the test. The tension module (ASTM D882-91, Method A) and free shrink properties were tested along each of the two orthogonal directions of stretch in the film samples, and the values were averaged. Impact resistance was determined in accordance with ASTM D3763-86. The EVCH film presents superior drops of tensile strength, free shrinkage and impact resistance. EXAMPLE XXV (Single Layer Film of an Ethylene LCB / Vinylcyclohexene Copolymer) Films hot pressed from an ethylene-vinylcyclohexene copolymer with 5 mol% VCH, of approximate dimensions 0.020 inch x 2.5 inch x 2.5 inch, were prepared and stretched in a laboratory biaxial orientation apparatus (TM Long Company). By an analogous procedure, films were prepared and stretched pressed in the hot state of a homogeneous ethylene-octene copolymer (sample EAO, 0.901 g / cm3 by ASTM_D 1505), approximate dimensions of 0.014 inch x 2.5 inch x 2.5 inches. The selection of the EAO as a reference sample is based on its high level of hardness in relation to other ethylene-1-olefin copolymers together with its similar Vicat softening temperature (approximately 90 ° C) in relation to the ethylene copolymer sample -vinylcyclohexene EVCH (approximately 91 ° C). Stretching conditions for each of the pressed films were as follows: Stretch mode: simultaneously biaxial to 3x3 During stretch: 185 ° F (85 ° C) stretch speed: 2 and 20 inches per second After stretching, all the films were cooled with ambient air, removed from the apparatus and maintained at a temperature of approximately 73 ° C for at least two days before the test. The voltage module (ASTM D882-91, Method A) and the free shrink properties were tested along the two orthogonal directions of stretching of the film samples, and the values were averaged. Impact resistance was determined in accordance with ASTM D3763-86. The EVCH film presented superior properties of tensile strength, free shrinkage and impact resistance.

EXAMPLE XXVI (Hot air orientation of a multilayer film containing propylene / ethylene copolymer and ethylene copolymer LCB / vinylcyclohexene) A palindromic three-layer coextruded film with an A / B / A structure is oriented with hot air to a temperature of 115 ° C. The outer layers "A" are polymers of propylene / ethylene with 3% by weight of ethylene. The inner layer "B" is EVCH in accordance with that described in example XI above. The relative thicknesses of layers A / B / A are in a ratio of 1/2/1, respectively. The film exhibits a good processing capacity - by extrusion and has a good peel strength. Example XXVII (hot air orientation of a multilayer film containing propylene homopolymers and ethylene / vinylcyclohexene copolymers) A palindromic coextruded three-layer film having an A / B / A structure is oriented with hot air at a temperature of 115 ° C. The outer layers "A" are made of propylene homopolymer. The inner layer "B" is an EVCH copolymer having 19 mol% VCH and a branched structure of long chains. The relative thicknesses of these layers A / B / A are in the ratio of 1/2/1, respectively. The movie presents a good processing capacity by extrusion and good resistance to the release of the resulting film. Examples 27-33 Seven films were made, in each case by coextruding a multi-layer substrate, then exposing the substrate to an electron beam at an absorbed dosage of 4.5 megarads to induce crosslinking of the film, and then coating by extrusion of two or more additional layers in the substrate, by extrusion coating either simultaneously or sequentially. Each film is then oriented by hot water, through the trapped bubble method, with preheat and hot bath temperatures within the range of 185 ° F to 205 ° F. The composition and structure of each film is given in Table 11, where all the layers to the left of the double diagonals (//) are electronically crosslinked. Table 10 Polymer Identification Resin Description Name of commercial supplier name EVA # 1 Poly (ethylene-co-acetate from Dupont ELVAX vinyl) 8.9% by weight of VA 2128 EVA # 2 Poly (ethylene-co-Exxon Escorene vinyl acetate) 9% by weight of VA LD "318.92 EVA # 3 poly (ethylene-co-Exxon Escorene vinyl acetate) 19% by weight VA LD-720.92 EVA # 4 poly (ethylene-co-acetate) of Rexene PE 1335 vinyl) 3.3% by weight of VA EVA # 5 poly (ethylene-co-vinyl acetate) 3.5% by weight of VA EVCH # 1 poly (ethylene-co-vinylcyclohexene) 2% molar of VCH EVCH # 2 poly (ethylene-co-vinylcyclohexene) 3 mol% VCH EVCH # 3 poly (ethylene-co-vinylcyclohexene) 4 mol% VCH EVCH # 4 poly (ethylene-co-vinylcyclohexene) 5% VCH molar EVCH # 5 poly (ethylene-co-vinylcyclohexene) 6% molar of VCH EVCH # 6 poly (ethylene-co-vinylcyclohexene) 7% molar of VCH EVCH # 7 poly (ethylene-co-vinylcyclo- hexene) 9 mol% VCH EVCH # 8 poly (ethylene-co-vinylcyclohexene) 19 mol% VCH EVCH # 9 poly (ethylene-co-vinylcyclohexene) 25 mol% VCH EVCH # 10 poly (ethylene- co-vinylcyclo- hexene) 30% molar of VCH EVCH # 11 poly (ethylene-co-vinylcyclohexene) 35% molar of VCH EAOC # 1 0.901 g / cm3 of homogeneous poly (ethylene-Dow DPF co-1-octene) 1150.01 EAOC # 2 0.905 g / cm3 of poly (ethylene- Dow Atañe® co-1-octene) (VLDPE) hetero4203 généne EAOC # 3 0.918 g / cm3 of poly (ethylene- Dow DOWLEX® co-1-octene) (LLDPE) heterogeneous 2045.03 VDCMA- poly (vinylidene chloride- Dow SARAN co-methyl acrylate) MA134 I SEE ethylene vinyl alcohol Evalca Eval PEC propylene / ethylene copolymer (3% by weight of ethylene) PP propylene homopolymer VDCMA vinylidene chloride copolymer / methyl acrylate ah-PO polyolefin modified by N6 anhydride nylon 6 (polycaprolactam) I CP copolyester ionomer Table - 11 Example Movie structure 27 EVA # 1 / EVCH # 3 // VDCMA / EVA # 2 28 EVA # 1 / EVCH # 3 // VDCMA / EVA # 3 29 EVA # 1 / EVCH # 3 // VDCMA / EVA # 3 / EVA # 2 30 EVA # 1 / EVCH # 3 / EVA # 3 // VDCMA / EVCH # 3 / EVA # 2 31 EVA # 1 / EVCH # 3 / EVA # 3 // EVA # 3 / VDCMA / EVCH # 3 / EVA # 2 32 EVA # 1 / EVCH # 3 / EVA # 3 // EVCH # 8 / VDCMA / EVCH # 3 / EVA # 2 33 EVCH # 7 / EVA # 3 // VDCMA / EVA # 2 Examples 34 to 41 Eight films were made in each case by coextrusion of multiple layers and then by biaxial orientation of the film coextruded with hot air at a temperature comprised within a range of 113 ° C to 115 ° C. The composition and structure of each film is given in table 12. Example Film structure 34 EVCH # 5 / EVA # 4 / EVCH # 5 35 50% EVCH # 5 + 50% EVA # 3 / VEO / 50% EVCH # 5 + 50% EVCH # 3 36 EVA # 27EVCH # 8 * / EVOH / EVCH # 8 * / EVA # 2 37 EVCH # l / EVA # 3 / EVOH / EVA # 3 / EVCH # l 38 EVCH # l / EVA # 3 / N6 / EVOH / N6 / EVA # 3 / EVCH # l 39 EVCH # l / EVCH # 8 * / N6 / EVOH / N6 / EVCH # 8 * / EVCH # l 40 EAOC # 2 / EVA # 5 / ah- PO / EVOH / ah-PO / EVA # 5 / EVCH # 4 41 EAOC # 2 / EVA # 5 / EVCH # 7 * / EVOH / EVCH # 7 * / EVA # 5 / EVCH # 4 * = includes 2%, in weight of resin, of chemically grafted maleic anhydride.

Example 42 The multilayer film of examples 26 to 30 is adhered in each case to a foamy polystyrene fabric, using heat and pressure. The outer layer # 2 (the polymer indicated for the layer at the right end of the structures of examples 26 to 30 of table 8) is bonded directly onto the foamy polystyrene fabric. The foamed polystyrene with the multilayer film laminated there is then thermoformed into a tray. Example 43 A five layer multilayer film is coextruded and rapidly cooled. The multilayer film has a first layer of an ethylene / vinyl acetate copolymer, a second layer of a metal neutralized salt of an ethylene / acrylic acid copolymer (ie, ionomer); a third layer of an ethylene / vinyl acetate copolymer; a fourth layer of EVCH # 10; and a fifth layer of polystyrene. Example 44 The five layer multilayer film of example 43 is adhered on a metallized polyester fabric with an adhesive. The resulting sheet-like structure is thermoformed in a tray. Example 45 An eight layer film is co-extruded in the form of a multilayer film, and then by rapid cooling. The eight layer film has the structure: EVA # l / I / EVA # l / adhesive / VE0 / adhesive / EVCH # 9 / polystyrene The film is thermoformed in a tray. Example 46 A two-layer film is co-extruded, in the form of a tube. The two-layer film has a first layer (the inner layer of the tube) of an ethylene / vinyl acetate copolymer having 25% vinyl acetate by weight of the polymer, and a second layer (the outer layer of the tube) of a mixture of 50% by weight of EVCH # 6 and 50% by weight of an ethylene / vinyl acetate copolymer having 8% vinyl acetate. The tube is irradiated and then oriented with hot air. After orientation, the tube is collapsed and flattened in such a way that the first layer adheres to itself thereby forming the tube in a four-layer film. Examples 47 to 49 Three films were each made by coextrusion of cast down. The structures of the films are shown in Table 12. After co-extrusion, each film is converted into a bag suitable for use in medical applications. During the conversion to the bag structure, the film of examples 36 to 38 is sealed by radiofrequency (RF), with the fourth layer (towards the far right in the table) is a seal layer, and the third layer is a layer of susceptibility agent. Table 13 Example film structure 47 PEC / adhesive / EVCH # 9 ** / PEC 48 CP / adhesive / EAOC # 2 / adhesive / EVCH # 10 49 CP / adhesive / 50% EVCH # ll + 50% EVA # 3 / PEC ** = partially oxidized. Example 50 A seven layer barrier film comprising any of the films of Examples 38 to 4 1 is laminated with an adhesive isocyanate to form an 8 mil sheet of an ethylene / vinylcyclohexene copolymer incorporating at least 35% molar of vinylcyclohexene. The resulting laminate is thermoformed to provide a thermoformed fabric suitable for vacuum packaging applications. The adhesive of examples 44, 45 and 46 to 48 may be of any suitable composition and type, and may be, for example, a polyurethane adhesive, an isocyanate adhesive, or an anhydride-grafted polyolefin such as, for example, those sold by DuPont under, the trademark Byner®, by Mitsui under the trademark Admer®, by Millenium under the trademark Plexaar®, etc. These are typically characterized by the presence of anhydride maleic or another anhydride functionality. Example 51 The interfacial bond resistances were determined for a series of films formed from copolymers of examples XV, XVI and XVII above and polyvinylidene dichloride copolymers (PVDC). In addition, for comparison purposes, the interfacial bond strength between a linear low density polyethylene (LLDPE) film (Dowlex 2045 from Dow Chemical Co.) and polyvinylidene dichloride was carried out. All tests were performed in accordance with the procedure of ASTM F-904.91. Films were laminated at 35.4 psi at a temperature of 300 ° F for 1 minute and then stored in accordance with ASTM D-1928A procedure. The results appear in Table 13 below and show that the copolymers of the present invention offer a stronger interfacial bond strength than the conventional packaging polymer, LLDPE. In addition, the results show that even smaller amounts of vinylcyclohexene provide improved resistances. Table 13 Sample% molar strength of shedding force 4-VCH shedding strength 16 folds - (pound / inch) das x 102 PVDC / LLDPE - 0.12 5.3 PVDC / Ex. 4.3 0.17 5.3 PVDC / Ex. 5.9 0.46 15.3 PVDC / Ex. 7.8 0.69 21.2

Claims (3)

1. CLAIMS A polymer product composed of a copolymer having long chain branches comprising units derived from monomers of (i) ethylene and (ii) at least one vinyl alicyclic monomer represented by the formula: I where CO represents an alicyclic group selected from a saturated Cs-C? 2 alicyclic group unsubstituted or substituted by C? -C? 2 hydrocarbyl or an unsubstituted C6-C12 alicyclic group or substituted by hydrocarbyl C? -C? 2 containing at least one ethylenic, non-aromatic unsaturation; said copolymer has a polydispersity (Mw / Mn) of at least about 1.5 and a melt index ratio (I10 / I2) of at least about 8. The polymer according to claim 1 wherein the copolymer units derived from the at least a vinyl alicyclic are present in at least 1 mol% of the copolymer. The polymer according to claim 1 wherein the copolymer units derived from ethylene are present from 0.1 to 99 mole%. 4. The polymer according to claim 2 wherein the copolymer units derived from ethylene are present from 0.1 to 99 mole%. 5. The polymer according to claim 1 wherein R represents a C5-C2 saturated alicyclic group. 6. The polymer of claim 4 wherein R represents a saturated Cs-C? 2 alicyclic group. The polymer according to claim 1 wherein R represents a C 1 -C 2 alicyclic group having at least one ethylenic, non-aromatic unsaturation. 8. The polymer according to claim 4 wherein R represents a C6 ~ C2 alicyclic group having at least one ethylenic, non-aromatic unsaturation. 9. The polymer according to claim 2 wherein the vinyl alicyclic monomer is vinylcyclone. 10. The polymer according to claim 4 wherein the vinyl alicyclic monomer is vinylcyclone. 11. The polymer according to claim 9 wherein the melt index ratio is at least 8. The polymer according to claims 1, 2, 3, 4, 5, 6, 7, 8, 9 , 10, or 11 wherein the copolymer further comprises units derived from at least one third monomer having at least one ethylenically unsaturated group capable of forming copolymers with the monomers (i) and (ii). . The polymer according to claim 12 wherein the third monomer is selected from alpha olefins C3-C2o •. A process for the formation of a copolymer product having long chain branches as part of its polymer structure and units derived from monomers comprising ethylene and at least one vinyl alicyclic monomer, comprising the introduction, in an inert liquid, of monomers comprising ethylene and at least one vinyl alicyclic compound represented by the formula: where CO represents a selected alicyclic group within a C5-C12 saturated alicyclic group unsubstituted or substituted by hydrocarbyl C? -Cj.2 or a C-C? 2 alicyclic group unsubstituted or substituted by C1-C12 hydrocarbyl having less an ethylenic, non-aromatic unsaturation; polymerizing said monomers in the presence of an inert liquid and a catalyst composed of a bridged methanocene complex represented by the formula: CP '/ \ Z. Y2 \ / C2 where Cp1, Cp2 each independently represent a substituted or unsubstituted indenyl group or a hydrogenated indenyl group, where each Y independently represents a univalent anionic ligand, M represents zirconium, titanium or hafnium, and Z represents a bridging group comprising an alkylene group having from 1 to 20 carbon atoms either a dialkylsilyl or dialkylgermanyl group, or an alkylphosphine or amine radical; recovering a branched long chain copolymer product having a molecular weight distribution (Mw / Mn) of at least about 2.5 and a melt flow index (I? o / I2) of at least about 6.5. 15. A process according to claim 14, wherein M is zirconium. 16. A process according to claim 14 wherein the metallocene complex has the formula: where Y and Y ', each independently represent, an anionic group; M represents a metal atom selected from zirconium, titanium or hafnium; Z represents a bridging group selected from C 1 -C 20 alkylene, dialkylsilyl, germanyl, alkylamine or alkylphosphine; R3 and R'3 each independently represent a C1-C20 hydrocarbyl. C3-C2o cyclohydrocarbyl, C1-C20 alkoxy, C6-C12 aryl, alkarylarylalkyl or C1-C20 hydrocarbyl having an atom of silicon, germanium, phosphorus, nitrogen, boron, aluminum, or a halogen atom; R2, R'2, R5 and R'5 each independently represent hydrogen or a group R3; or R2 and R3 together and R'2 and R'3 together represent each a substituted or unsubstituted cyclohydrocarbyl group. 17. A process according to claim 15 wherein the metallocene complex has the formula: 18. A process according to claim 14, 15, 16 or 17 wherein the metallocene complex is employed in the presence of a co-catalyst. 19. A process according to claim 18 wherein the co-catalyst is an organoaluminum compound. 20. A process according to claim 18 wherein the metallocene complex is supported. A packaging material in the form of a rigid article, semi-rigid article, or film comprising at least one layer, wherein at least one of said layers comprises the long chain branched copolymer of claim 1.
2. 2. A material packaging in the form of a rigid article, semi-rigid article, or film comprising at least one layer, wherein at least one of said layers comprises the long chain branched copolymer of claims 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.
3. 3. A packaging material in the form of a rigid article, semi-rigid article, or film comprising at least a layer, wherein at least one of said layers comprises the long chain branched copolymer of claim 12. 24. A packaging material in the form of a rigid, semi-rigid article, or of a film comprising at least one layer, wherein at least one of said layers comprises the long chain branched copolymer of claim 13. 25. The packaging material according to claim 21 wherein said at least one layer containing the long chain branched copolymer consists of a mixture of said copolymer and at least one additional polymer selected from the group consisting essentially of polyolefins, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polyethylene copolymer and mixtures thereof. 26. The packaging material according to claim 25 wherein said additional polymer comprises at least one polyolefin. 27. The packaging material according to claim 21 wherein the packaging material is a flexible film having a thickness of 5 to 250 micrometers. 28. The packing material in accordance with the claim 23 wherein the packaging material is a flexible film having a thickness of 5 to 250 micrometers. 29. The packaging material according to claim 25 wherein the packaging material is a flexible film having a thickness of 5 to 250 micrometers. 30. The packaging material according to claim 21 in the form of a film. 31. The packaging material according to claim 30 wherein the film further comprises an additional polymeric layer. 32. The packaging material according to claim 30 wherein at least one layer of the film is crosslinked. 33. The packaging material according to claim 32 wherein the layer comprising the long chain branched copolymer of claim 1 is between a thermal seal layer and another polymeric layer. 34. The packaging material according to claim 30 wherein the film further comprises an oxygen barrier layer. 35. The packaging material according to claim 30 wherein the film further comprises an adhesive layer. . The packaging material according to claim 30 wherein at least one layer comprises a mixture of the branched long chain copolymer and a second polymer. . The packaging material according to claim 36 wherein the second polymer is selected from the group consisting of polyethylene, ethylene / olefin copolymer, - propylene / olefin copolymer, polypropylene, ethylene / vinyl chloride and ethylene / copolymer of vinyl ester. . The packaging material according to claim 30 wherein the film is oriented. . The packaging material according to claim 30 wherein the film is heat shrinkable. . A package comprising an article, and a film wrapped around the article, the film comprises the film of claim 30.