Metallocene-produced very low density polyethylenes

ES 2 339 331 T3

DESCRIPTION

Low density polyethylene and very low density polyethylene blends produced with metallocene.

1. Field of the invention

The present invention relates generally to very low density polyolefins and to films produced from very low density polyolefins. More specifically, the present invention is directed to very low density polyethylenes produced using metallocene catalysts, and to extrusion cast films formed of very low density polyethylenes prepared by metallocene which have improved mechanical and sealing properties relative to metallocene films. conventional low-density polyethylene.

2. Background

Various polymeric materials have been used with success in thin cast films. A typical film casting process includes the steps of extruding the polymer, feeding the melt through a slot die, draw-down of the melt in the air gap, cold roll casting, cracking for trimming the edges, surface treatment if necessary, and winding. The polyolefin film can be extruded onto a paper, metal foil, or other flexible substrate material to form an extrusion coated substrate. Multilayer extrusion of polymeric materials, which include polyolefins as well as other materials, a process sometimes referred to as "coextrusion", is well known as well.

Various polymerization processes have been used to prepare polyolefins, including polyethylene and polypropylene, suitable for extrusion coating applications. Such processes include gas phase polymerization, solution polymerization, and bulk polymerization. More specifically, gas phase polymerization processes using Ziegler-Natta or vanadium-based catalyst systems have been used to prepare "low density polyethylenes" ("LDPEs"), that is, polyethylenes having densities of 0.916 to 0.928 g / cm³; "Medium density polyethylenes" ("MDPEs"), that is, polyethylenes having densities of 0.929 to 0.940 g / cm³; and "high density polyethylenes" ("HDPEs"), that is, polyethylenes having densities greater than 0.940.

The low density polyethylene extrusion coating market is dominated by conventional LDPE prepared in a high pressure process. LDPE is generally preferred because it is easy to extrude, has high melt strength, thereby minimizing neck-in, and has good sealing characteristics. Linear Low Density Polyethylene ("LLDPE") offers improved coating toughness, but its relatively narrow molecular weight distribution makes it more difficult to extrude, and it has relatively poor sealing properties; LLDPE constitutes approximately 5% of the low density polyethylene extrusion market.

Although LDPE and LLDPE are widely used, these materials suffer from several disadvantages in extrusion coating applications. In applications that require the adhesion of a coating to polypropylene, LDPE and LLDPE offer relatively poor adhesion, thus necessitating the extra expense and complexity of an adhesive or tie layer. It would therefore be desirable to have a polyethylene-based extrusion coating material capable of improving adhesion to polypropylene substrates. In addition, it would be desirable to have an extrusion coating material that offers improved mechanical properties and improved sealing performance. Furthermore, it would be desirable to have an extrusion coating material capable of being formed into a thinner layer than is conventionally possible with LDPE and LLDPE. Still further, it would be desirable to have an extrusion coating material that provides better organoleptic properties than LLDPE.

US Patent No. 5,382,631 describes linear interpolymer blends prepared from components that have a narrow molecular weight distribution (e.g., Mw / Mn <3) and a narrow composition distribution ( eg CDBI> 50%). The mixtures have either Mw / Mn> 3 and / or CDBI <50%, and combinations of each, and can be bimodal with respect to either or both of molecular weight and / or comonomer content. The blends are generally free of blend components having both a higher average molecular weight and a lower average comonomer content than other components of the blend.

3. Compendium of the invention

In one embodiment, the present invention is directed to a polymer blend, the blend including a very low density polyethylene (VLDPE) polymer having a density of 0.900 to 0.915 g / cm³, and a low-density polyethylene (LDPE) polymer, which has a density of 0.916 to 0.928 g / cm³. Preferably, the VLDPE and LDPE polymers are metallocene catalyzed polymers. In particular, the present invention provides a polymer blend composition comprising from 1 to 99% by weight of a VLDPE copolymer derived from ethylene and one or more alpha-olefin C comonomers.₃-C₂₀. The copolymer has a comonomer content of 5 to 15% by weight, a density of 0.900 to 0.915 g / cm³, a composition distribution width index in the range of 55% to 70%, a molecular weight distribution Mw / Mn of 2 to 3, a molecular weight distribution Mz / Mw less than 2, and a distribution of the bimodal composition. The blend further comprises 1 to 99% by weight of an LDPE having a density of 0.916 to 0.928 g / cm³.

ES 2 339 331 T3

In another embodiment, the present invention provides a polymer blend suitable for use as a film or coating, including the polymer blend of 1 to 99% by weight of a metallocene-produced VLDPE polymer having a density of 0.900 to 0.915 g / cm³, and 1 to 99% by weight of an LDPE polymer having a density of 0.916 to 0.928 g / cm³, where the sum of the VLDPE and the LDPE is 100%. Alternatively, the blend may have 5 to 95%, 10 to 90%, or 15 to 85% by weight of the LDPE polymer. The VLDPE polymer can have a melt index of 6 to 15 dg / min, or 9 to 12 dg / min. The VLDPE polymer can be a homopolymer of ethylene, or a copolymer of ethylene and an alpha-olefin C₃ to C₁₂. The LDPE polymer can have a melt index of 0.5 to 15 dg / min, or 1 to 10 dg / min. The LDPE polymer can be a homopolymer of ethylene, or a copolymer of ethylene and an alpha-olefin C₃ to C₁₂.

In another embodiment, the present invention is directed to a mixture of polymers, the mixture including a VLDPE polymer produced by metallocene in the gas phase, the VLDPE polymer being a copolymer of ethylene and at least one alpha-olefin C₃ to C₁₂ and having a density of 0.900 to 0.915 g / cm³ and a melt index of 5 to 20 g / 10 min; and an LDPE polymer produced by metallocene, the LDPE polymer being a copolymer of ethylene and at least one alpha-olefin C₃ to C₁₂ and having a density of 0.916 to 0.928 g / cm³ and a melt index of 0.5 to 15 g / 10 min. In this embodiment, the blend includes 5-95% by weight of the VLDPE polymer and 95-5% by weight of the LDPE polymer, based on the total weight of the VLDPE and LDPE polymers.

In another embodiment, the present invention is directed to a mixture of polymers, the mixture including a VLDPE polymer produced by gas phase metallocene, the VLDPE polymer being a copolymer of ethylene and 1-butene, 1-hexene or 1-octene, and having a density 0.910 to 0.915 g / cm³, a melt index of 5 to 20 g / 10 min, a composition distribution width index (CDBI) of 60 to 80% by weight and a molecular weight distribution (MWD) of 2.2 to 2.8 ; and an LDPE polymer produced by metallocene, the LDPE polymer being a copolymer of ethylene and 1-butene, 1-hexene or 1-octene and having a density of 0.916 to 0.928 g / cm³ and a melt index of 0.5 to 10 g / 10 min. In this embodiment, the blend preferably includes 10-90% by weight of the VLDPE polymer and 90-10% by weight of the LDPE polymer, based on the total weight of the VLDPE and LDPE polymers.

In one embodiment, the present invention is directed to a VLDPE / LDPE polymer blend, the blend including a metallocene-produced VLDPE polymer comprising an ethylene copolymer with a comonomer content of 25% by weight or less, preferably 20% by weight. weight or less, and more preferably 15% by weight or less.

In another embodiment, the present invention is directed to a blend of polymers, including blending from 1 to 99% by weight of a copolymer derived from ethylene and one or more alpha-olefin C comonomers.₃-C₂₀, and 1 to 99% by weight of a low density polyethylene polymer having a density of 0.916 to 0.928 g / cm³, where the sum of the weight of the copolymer and the low density polyethylene polymer is 100%. The copolymer is further characterized by properties that include one or more of the following: a comonomer content of 5 to 15% by weight, a density of 0.900 to 0.915 g / cm³, a composition distribution width index in the range of 55% to 70%, a molecular weight distribution Mw / Mn of 2 to 3, and a molecular weight distribution Mz / Mw less than 2.

In another embodiment, the present invention is directed to an article, the article including a substrate and a film disposed on the substrate. The film includes a polymer blend, including the polymer blend of 1 to 99% by weight of a copolymer derived from ethylene and one or more C3-C20 alpha-olefin comonomers, and 1 to 99% by weight of a polymer. low-density polyethylene having a density of 0.916 to 0.928 g / cm³, where the sum of the weight of the copolymer and the low density polyethylene polymer is 100%. The copolymer is further characterized by properties that include one or more of the following: a comonomer content of 5 to 15% by weight, a density of 0.900 to 0.915 g / cm³, a composition distribution width index in the range of 55% to 70%, a molecular weight distribution Mw / Mn of 2 to 3, and a molecular weight distribution Mz / Mw less than 2.

In another embodiment, the present invention is directed to a polymer blend composition, composition including (a) a copolymer derived from ethylene and one or more C3-C20 alpha-olefin comonomers, and (b) a polyethylene polymer of low density having a density of 0.916 to 0.928 g / cm³. The copolymer is further characterized by properties that include one or more of the following: a comonomer content of 5 to 15% by weight, a density of 0.900 to 0.915 g / cm³, a composition distribution width index in the range of 55% to 70%, a molecular weight distribution Mw / Mn of 2 to 3, a molecular weight distribution Mz / Mw less than 2, and a distribution of the bimodal composition.

In another embodiment, the present invention is directed to a monolayer film formed from a blend that includes (a) a copolymer derived from ethylene and one or more C3-C20 alpha-olefin comonomers, and (b) a polyethylene polymer. low density having a density of 0.916 to 0.928 g / cm³. The copolymer is further characterized by properties that include one or more of the following: a comonomer content of 5 to 15% by weight, a density of 0.900 to 0.915 g / cm³, a composition distribution width index in the range of 55% to 70%, a molecular weight distribution Mw / Mn of 2 to 3, a molecular weight distribution Mz / Mw less than 2, and a distribution of the bimodal composition.

ES 2 339 331 T3

In another embodiment, the present invention is directed to a multilayer film, the film including a first layer and a second layer, and at least one of the layers including a polymer blend composition. The polymer blend composition includes (a) a copolymer derived from ethylene and one or more alpha-olefin C comonomers₃-C₂₀, and (b) an LDPE polymer having a density of 0.916 to 0.928 g / cm³. The copolymer is further characterized by properties that include one or more of the following: a comonomer content of 5 to 15% by weight, a density of 0.900 to 0.915 g / cm³, a composition distribution width index in the range of 55% to 70%, a molecular weight distribution Mw / Mn of 2 to 3, a molecular weight distribution Mz / Mw less than 2, and a distribution of the bimodal composition.

In another embodiment, the present invention is directed to a polymer blend composition, the composition including a metallocene catalyzed very low density linear polyethylene polymer and a low density polyethylene polymer having a density of 0.916 to 0.928 g / cm³. The very low density polyethylene polymer is further characterized by properties that include one or more of the following: a comonomer content of 5 to 15% by weight, a density of 0.900 to 0.915 g / cm³, a composition distribution width index of 50% to 85%, a molecular weight distribution Mw / Mn of 2 to 3, and a molecular weight distribution Mz / Mw less than 2.

Polyethylene has two peaks in a TREF measurement.

In another embodiment, the present invention provides a polymeric film, the film being extrusion cast from a blend of a metallocene-produced VLDPE polymer and an LDPE, as described above.

In another embodiment, the present invention is directed to monolayer films formed from the polymer blends of the invention.

In another embodiment, the present invention is directed to multilayer films, wherein at least one layer of the multilayer film is formed from a mixture of polymers of the invention.

In other embodiments, the invention is directed to articles that include the films of the invention, articles wrapped with the films of the invention, and substrates coated with the films of the invention.

In another embodiment, the present invention provides an article of manufacture, the article including a flexible substrate and an extrusion coated polymeric film on the substrate, wherein the polymeric film is a blend of a metallocene-produced VLDPE polymer and an LDPE as described. described above. The substrate can be a flexible material, such as paper, a metal foil, a flexible polymeric material, or another flexible substrate capable of being coated.

The blends and films of the present invention show improved mechanical and / or sealing properties, relative to prior art LDPE and LLDPE materials.

Four. Detailed description

4.1. VLDPE polymers

The polymer and film blends of the present invention include a very low density polyethylene (VLDPE) polymer. As used herein, the terms "very low density polyethylene polymer" and "VLDPE polymer" refer to a homopolymer or preferably copolymer of polyethylene having a density of less than 0.916 g / cm³. Polymers that have more than two types of monomers, such as terpolymers, are also included within the term "copolymer" used herein. Comonomers that are generally useful for preparing VLDPE copolymers include α-olefins, such as α-olefins C₃-C₂₀ and preferably α-olefins C₃-C₁₂. The α-olefin comonomer can be linear or branched, and two or more comonomers can be used, if desired. Examples of suitable comonomers include α-olefins C₃ -C₁₂ linear, and α-olefins having one or more C alkyl branches₁-C₃, or an aryl group. Specific examples include propylene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted with ethyl, methyl or dimethyl; 1-dodecene; and styrene. It should be appreciated that the above list of comonomers is merely exemplary, and is not intended to be limiting. Preferred comonomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and styrene.

Other useful comonomers include conjugated and unconjugated dienes, acetylene, which can be included in minor amounts in terpolymer compositions. Unconjugated dienes useful as comonomers are preferably straight chain hydrocarbon diolefins or cycloalkenyl substituted alkenes having 6 to 15 carbon atoms. Suitable unconjugated dienes include, for example: (a) straight chain acyclic dienes, such as 1,4-hexadiene 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 1,4

ES 2 339 331 T3 cyclohexadiene; 1-5-cyclooctadiene and 1,7-cyclododecadiene; (d) multi-ring alicyclic bridged and fused ring dienes, such as tetrahydroindene; norbornadiene; methyl-tetrahydroindene; dicyclopentadiene (DCPD); bicyclo- (2.2.1) -hepta-2,5-diene; alkenyl-, alkylidene-, cycloalkenyl- and cycloalkylidene-norbornenes, such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) - 2-norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene (VNB); and (e) cycloalkenyl substituted alkenes, such as vinylcyclohexene, allylcyclohexene, vinylcyclooctene, 4-vinylcyclohexene, allylcyclodecene, and vinylcyclododecene. Of the unconjugated dienes typically used, the preferred dienes are dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, and tetracyclo- (A-11,12) -5-, 8- dodecene. Particularly preferred diolefins are 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, dicyclopentadiene (DCPD), norbornadiene, and 5-vinyl-2-norbornene (VNB). Note that throughout this description the terms "unconjugated diene" and "diene" are used interchangeably.

It should be appreciated that the amount of comonomer used will depend on the desired density of the VLDPE polymer and the specific comonomers selected. In general, the comonomer will be present in an amount of 0 to 15% by weight, typically 5 to 15% by weight for preferred comonomers such as butene, hexene, and octene. It is well understood in the art that, for a given comonomer, the density of the VLDPE polymer produced therefrom decreases as the comonomer content increases. One skilled in the art can easily determine the appropriate comonomer content to produce a VLDPE polymer having a desired density.

VLDPE polymer has a density less than 0.916 g / cm³, and preferably at least 0.890 g / cm³, more preferably at least 0.900 g / cm³. Thus, a preferred density range for the VLDPE polymer is 0.900 g / cm³ at 0.915 g / cm³. Alternative lower limits of VLDPE polymer density include 0.905 g / cm³ or 0.910 g / cm³.

The VLDPE polymer is further characterized by a melt index (IF) of 0.5 to 20 g / 10 min (dg / min), measured according to ASTM-1238, condition E. In one or more specific embodiments, alternative lower limits for melt index include 0.7 and 1.0 g / 10 min, and alternative upper limits for melt index include 5, 10 and 15 g / 10 min, the melt index ranges between any lower limit and any upper limit being within the scope of the invention. In a preferred embodiment, the melt index is 5 dg / min or less.

In one embodiment, the VLDPE polymer is prepared in a metallocene catalyzed polymerization process. As used herein, the terms "metallocene-catalyzed VLDPE," "metallocene-produced VLDPE," or "m-VLDPE" refer to a VLDPE polymer having the density and melt-index properties described herein. , and which are produced in the presence of a metallocene catalyst. One skilled in the art will recognize that a metallocene-catalyzed VLDPE polymer has measurable properties distinguishable from a VLDPE polymer having the same comonomers in the same weight percentages, but produced from a different process, such as a Ziegler-polymerization process. Conventional Natta.

The terms "metallocene" and "metallocene catalyst precursor", as used herein, mean compounds having a Group 4, 5, or 6 transition metal (M), with a cyclopentadienyl (Cp) ligand (s). which may be substituted, at least one ligand (X) not derived from a cyclopentadienyl, and zero or one ligand (Y) containing a heteroatom, the ligands being coordinated to M and corresponding in number to the valence of the same. Metallocene catalyst precursors generally require activation with a suitable cocatalyst (referred to as an "activator"), in order to provide an "active metallocene catalyst", that is, an organometallic complex with a site of coordination vacancy that can coordinate, insert, and polymerize olefins. The metallocene catalyst precursor is preferably one of, or a mixture of, the metallocene compounds of either or both of the following types:

(1) Cyclopentadienyl (Cp) complexes having two Cp ring systems per ligands. Cp ligands form a "sandwich" complex with the metal, and can be free to rotate (not bridged) or locked into a rigid configuration by a bridging group. The Cp ring ligands can be the same or different, unsubstituted, substituted, or a derivative thereof, such as a heterocyclic ring system that can be substituted, and the substitutions can be fused to form other saturated or unsaturated ring systems such as ring systems. tetrahydroindenyl, indenyl or fluorenyl. These cyclopentadienyl complexes have the general formula (Cp¹R¹m) R³n (Cp²R²p) MX_what in which: Cp¹ and Cp² they are the same or different cyclopentadienyl rings; R¹ and R² are each, independently, a halogen or a hydrocarbyl, halocarbyl, hydrocarbyl substituted organometalloid group or halocarbyl substituted organometalloid group containing up to about 20 carbon atoms; m is 0 to 5; p is 0 to 5; two R substituents¹ and / or R² at adjacent carbon atoms of the cyclopentadienyl ring associated therewith they can be joined together to form a ring containing from 4 to about 20 carbon atoms; R³ it is a bridging group; n is the number of atoms in the direct chain between the two ligands and is 0 to 8, preferably 0 to 3; M is a transition metal having a valence of 3 to 6, preferably group 4, 5

ES 2 339 331 T3 or 6 of the periodic table of elements, and is preferably in its highest oxidation state; each X is a non-cyclopentadienyl ligand, and is independently a halogen or a hydrocarbyl, oxyhydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid group, oxyhydrocarbyl-substituted organometalloid group, or halocarbyl-substituted organometalloid group containing up to about 20 carbon atoms, and q equals the valence of M minus 2.

(2) Monocyclopentadienyl complexes having only one Cp ring system as a ligand. The Cp ligand forms a "half-sandwich" complex with the metal, and can be free to rotate (not bridged) or blocked in a rigid configuration by a bridging group to a ligand containing a heteroatom. The bridging structures can be meso configurations or racemic stereoisomers, or a mixture thereof. The ring ligand Cp can be unsubstituted, substituted, or a derivative thereof such as a heterocyclic ring system that can be substituted, and the substitutions can be fused to form other saturated or unsaturated ring systems, such as tetrahydroindenyl, indenyl or ring systems fluorenyl. The heteroatom-containing ligand is attached both to the metal and optionally to the Cp ligand via the bridging group. The heteroatom itself is an atom with a coordination number of three, from group 15 or 16 of the periodic table of the elements. These mono-cyclopentadienyl complexes have the general formula (Cp¹R¹m) R³n (Y_rR²) MX_s where: each R¹ is, independently, a halogen or a hydrocarbyl, halocarbyl, hydrocarbyl substituted organometalloid group or halocarbyl substituted organometalloid group containing up to about 20 carbon atoms, "m" is 0 to 5, and two R substituents¹ on adjacent carbon atoms of the cyclopentadienyl ring associated therewith may be linked together to form a ring containing from 4 to about 20 carbon atoms; R³ it is a bridging group; "N" is 0 to 3; M is a transition metal that has a valence of 3 to 6, preferably group 4, 5 or 6 of the periodic table of elements, and is preferably in its highest oxidation state; Y is a group containing a hetero atom, wherein the hetero atom is an element with a coordination number of three from the group VA or a coordination number of two from the group VIA, preferably nitrogen, phosphorus, oxygen or sulfur; R² is a radical selected from a group consisting of C hydrocarbon radicals₁ to C₂₀, hydrocarbon radicals C₁ to C₂₀ substituted, in which one or more hydrogen atoms are replaced by a halogen atom, and when Y is coordinated three and has no bridge, there may be two R groups² at Y, each being independently a radical selected from the group consisting of C1 to C20 hydrocarbon radicals, C1 to C20 substituted hydrocarbon radicals, in which one or more hydrogen atoms are replaced by a halogen atom, and each X is a non-cyclopentadienyl ligand and is independently a halogen or a hydrocarbyl, oxyhydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid group, oxyhydrocarbyl substituted organometalloid group or halocarbyl substituted organometalloid group containing up to about 20 carbon atoms, "s" equals the valence of M minus 2.

Examples of biscyclopentadienyl metallocenes of the type described in group (1) above for producing the m-VLDPE polymers of the invention are described in US Patent Nos. 5,324,800; 5,198,401; 5,278,119; 5,387,568; 5,120,867; 5,017,714; 4,871,705; 4,542,199; 4,752,597; 5,132,262; 5,391,629; 5,243,001; 5,278,264; 5,296,434; and 5,304,614.

Illustrative, but not limiting, examples of suitable bridged biscyclo-pentadienyl metallocenes of the type described in group (1) above are the racemic isomers of:

j «- (CH3) 2 Si (indenyl) 2M (Cl) 2;

j «- (CH₃)₂ Yes (indenyl)₂M (CH₃ )₂;

j «- (CH₃)₂ Yes (tetrahydroindenyl)₂M (Cl)₂;

j «- (CH₃)₂ Yes (tetrahydroindenyl)₂M (CH₃)₂;

//-(CII,).· Si (indenyl) 2M (CH2 CH3) 2; and jn- (C6H₅) 2C (indenyl) 2M (CH3) 2;

where M is Zr or Hf.

Examples of suitable non-symmetric cyclopentadienyl metallocenes of the type described in group (1) above are described in US Patent Nos. 4,892,851; 5,334,677; 5,416,228; and 5,449,651; and in the publication J. AM. Chem. Soc. 1988,110, 6255.

Illustrative, but not limiting, examples of non-symmetric cyclopentadienyl metallocenes of the type described in group (1) are:

jU- (C₆H₅)₂C (cyclopentadienyl) (fluorenyl) M (R)₂;

ES 2 339 331 T3 jU- (C₆H₅)₂C (3-methylcyclopentadienyl) (fluorenyl) M (R)₂;

j «- (CH₃)₂ C (cyclopentadienyl) (fluorenyl) M (R)₂;

jU- (C₆H₅)₂C (cyclopentadienyl) (2-methylindenyl) M (CH₃)₂;

jU- (C₆H₅)₂C (3-methylcyclopentadienyl) (2-methylindenyl) M (Cl)₂;

jU- (C₆H₅)₂C (cyclopentadienyl) (2,7-dimethylfluorenyl) M (R)₂; yj «- (CH₃)₂ C (cyclopentadienyl) (2,7-dimethylfluorenyl) M (R)₂;

where M is Zr or Hf, and R is Cl or CH₃.

Examples of suitable monocyclopentadienyl metallocenes of the type described in group (2) above are described in US Patent Nos. 5,026,798; 5,057,475; 5,350,723; 5,264,405; 5,055,438; and in international patent application WO 96/002244.

Illustrative, but not limiting, examples of preferred monocyclopentadienyl metallocenes of the type described in group (2) are:

j «- (CH₃)₂ Si (cyclopentadienyl) (1-adamantylamido) M (R)₂;

j «- (CH₃)₂ Si (3-eerc-butylcyclopentadienyl) (1-adamantylamido) M (R)₂;

j «- (CH₃)₂ Si (tetramethylcyclopentadienyl) (1-adamantylamido) M (R)₂;

j «- (CH₃)₂ Si (tetramethylcyclopentadienyl) (1-adamantylamido) M (R)₂;

j «- (CH₃)₂ C (cyclopentadienyl) (1-adamantylamido) M (R)₂;

j «- (CH₃)₂ Si (cyclopentadienyl) (1-eerc-butylamido) M (R)₂;

j «- (CH₃)₂ Si (fluorenyl) (1-ether-butylamido) M (R)₂;

j «- (CH₃)₂ Si (tetramethylcyclopentadienyl) (1-cyclododecylamido) M (R)₂; and jU- (C₆H₅)₂Si (tetramethylcyclopentadienyl) (1-cyclododecylamido) M (R)₂;

where M is Ti, Zr or Hf, and R is Cl or CH₃.

Another class of organometallic complexes that are useful catalysts for the VLDPE polymers described herein are those with diimido ligand systems, such as those described in international patent application WO 96/23010.

The metallocene compounds are contacted with an activator to produce an active catalyst. One class of activators is that of non-coordinating anions, where the term "non-coordinating anion" (NCA) means an anion that either does not coordinate with the transition metal cation or that coordinates only weakly with the transition metal cation. , thus remaining labile enough to be displaced by a neutral Lewis base. "Compatible" non-coordinating anions are those that do not degrade to neutrality when the initially formed complex decomposes. Furthermore, the anion will not transfer an anionic substituent or fragment to the cation to cause it to form a neutral four-coordinated metallocene compound and a neutral by-product of the anion. The noncoordinating anions useful in accordance with this invention are those that are compatible, stabilize the metallocene cation in the sense of balancing its ionic charge in a +1 state, and yet retain sufficient lability to allow its displacement by an ethylenic or monomer. acetylenically unsaturated during polymerization. Additionally, the anions useful in this invention will be large or bulky, in the sense of having sufficient molecular size to greatly inhibit or prevent neutralization of the metallocene cation by Lewis bases other than the polymerizable monomers that may be present in the process. polymerization. Typically, the anion will have a molecular size greater than or equal to about 4 angstroms.

A further method of preparing metallocene catalysts uses ionization of anionic precursors that are initially neutral Lewis acids but form the cation and anion after an ionization reaction with the metallocene compounds. For example, tris (pentafluorophenyl) boron acts to abstract an alkyl, hydride, or silyl ligand from the metallocene compound to give a metallocene cation and a stabilizing non-coordinating anion; see, eg, European patents EP-A-0 427 697 and EP-A-0 520 732. Metallocene catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds with anionic precursors containing metal oxidizing groups along with the anionic groups; see European patent EP-A-0 495 375.

ES 2 339 331 T3

Examples of suitable activators capable of producing ionic cationization of the metallocene compounds of the invention, and the consequent stabilization with a resulting non-coordinating anion, include:

trialkyl-substituted ammonium salts, such as:

triethylammonium tetraphenylborate;

tripropylammonium tetraphenylborate;

tri (n-butyl) ammonium tetraphenylborate;

trimethylammonium tetrakis (p-tolyl) borate;

trimethylammonium tetrakis (o-tolyl) borate;

tributylammonium tetrakis (pentafluorophenyl) borate;

N, N-dialkylanilinium salts, such as:

N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate;

N, N-dimethylanilinium tetrakis (heptafluoronaphthyl) borate;

N, N-dimethylanilinium tetrakis (perfluoro-4-biphenyl) borate;

N, N-dimethylanilinium tetraphenylborate;

N, N-diethylanilinium tetraphenylborate; and N, N-2,4,6-pentamethylanilinium tetraphenylborate;

dialkylammonium salts, such as:

di- (isopropyl) ammonium tetrakis (pentafluorophenyl) borate; and dicyclohexylammonium tetraphenylborate; and triarylphosphonium salts, such as:

triphenylphosphonium tetraphenylborate;

tri (methylphenyl) phosphonium tetraphenylborate; and tri (dimethylphenyl) phosphonium tetraphenylborate.

Additional examples of suitable anionic precursors include those that include a stable carbonium ion, and a compatible non-coordinating anion. These include:

tropilium tetrakis (pentafluorophenyl) borate;

triphenylmethylium tetrakis (pentafluorophenyl) borate;

benzene (diazonium) tetrakis (pentafluorophenyl) borate;

tropilium phenyltris (pentafluorophenyl) borate;

triphenylmethylium phenyl- (trispentafluorophenyl) borate;

benzene (diazonium) phenyl-tris (pentafluorophenyl) borate;

tropilium tetrakis (2,3,5,6-tetrafluorophenyl) borate;

triphenylmethylium tetrakis (2,3,5,6-tetrafluorophenyl) borate;

benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate;

tropilium tetrakis (3,4,5-trifluorophenyl) borate;

benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate;

ES 2 339 331 T3 tropilium tetrakis (3,4,5-trifluorophenyl) aluminate;

triphenylmethylium tetrakis (3,4,5-trifluorophenyl) aluminate;

benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) aluminate; tropilium tetrakis (1,2,2-trifluoroethenyl) borate;

triphenylmethylium tetrakis (1,2,2-trifluoroethenyl) borate;

benzene (diazonium) tetrakis (1,2,2-trifluoroethenyl) borate; tropilium tetrakis (2,3,4,5-tetrafluorophenyl) borate;

triphenylmethylium tetrakis (2,3,4,5-tetrafluorophenyl) borate; and benzene (diazonium) tetrakis (2,3,4,5-tetrafluorophenyl) borate.

Where the metal ligands include halide moieties, for example (methyl-phenyl) silylene (tetra-methylcyclopentadienyl) (eerc-butylamido) zirconium dichloride, which are not capable of producing ionizing abstraction under standard conditions, they can be converted by alkylation reactions known with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes or Grignard reagents. See European patents EPA-0 500 944, EP-A1-0 570 982 and EP-A1-0 612 768 for procedures describing the reaction of alkylaluminum compounds with dihalide substituted metallocene compounds before or with the addition of compounds. anionic activators. For example, an alkylaluminum compound can be mixed with the metallocene prior to its introduction into the reaction vessel. Since alkylaluminum is also suitable as a scavenger (as described below), its use in excess of that normally required stoichiometrically for alkylation of the metallocene will allow its addition to the reaction solvent with the metallocene compound. Normally, alumoxane would not be added with the metallocene, to avoid premature activation, but it can be added directly to the reaction vessel in the presence of the polymerizable monomers when it serves as both a scavenger and an alkylation activator.

Alkylalumoxanes are additionally suitable as catalyst activators, particularly for those metallocenes having halide ligands. An alumoxane useful as a catalyst activator is typically an oligomeric aluminum compound represented by the general formula (R-Al-O)_n, which is a cyclic compound, or R (RAl-O)_nAlR₂, which is a linear compound. In these formulas, each R or R₂ is a C alkyl radical₁ to C₅, for example, methyl, ethyl, propyl, butyl, or pentyl, and "n" is an integer from 1 to about 50. Most preferably, R is methyl and "n" is at least 4, that is, methylalumoxane (MAO ). Alumoxanes can be prepared by various procedures known in the art. For example, an aluminum alkyl can be treated with water dissolved in an inert organic solvent, or it can be contacted with a hydrated salt, such as hydrated copper sulfate suspended in an inert organic solvent, to give an alumoxane. Generally, however prepared, the reaction of an aluminum alkyl with a limited amount of water gives a mixture of the linear and cyclic species of alumoxane.

Preferably, a scrubbing compound is also used. The term "scavenger compound", as used herein, refers to those compounds effective to remove polar impurities from the reaction solvent. Such impurities can be inadvertently introduced with any of the components of the polymerization reaction, particularly with the solvent, the monomer and comonomer feed, and adversely affect the activity and stability of the catalyst, decreasing or even eliminating the activity. catalytic, particularly when a non-coordinating metallocene cation-anion pair is the catalyst system. Polar impurities, or catalyst poisons, include water, oxygen, oxygenated hydrocarbons, and metallic impurities. Preferably, steps are performed prior to provision of such in the reaction vessel, for example, by chemical treatment or careful separation techniques after or during the synthesis or preparation of the various components, but usually still minor amounts of scavenger compound will be required. in the polymerization process itself. Typically, the scavenger compound will be an organometallic compound such as Group 13 organometallic compounds of US Patent Nos. 5,153,157 and 5,241,025; European patent EP-A-0 426 638; International patent application WO-A-91/09882; International patent application WO-A-94/03506; and international patent application WO-A-93/14132. Exemplary compounds include triethylaluminum, triethylborane, tri-isobutylaluminum, isobutyl-aluminumxane, those having bulky substituents covalently attached to the metal or metalloid center, it being preferred to minimize adverse interaction with the active catalyst.

The catalyst system is preferably supported on a support, typically an inorganic oxide or chloride or a resinous material such as polyethylene. Preferably, the catalyst system includes a metallocene component with single or multiple cyclopentadienyl components reacted with either a metal alkyl or alkoxy component or an ionic compound component. These catalysts can include partially and / or fully activated precursor compositions. Catalysts can be modified by prepolymerization or encapsulation. Specific metallocenes and catalyst systems useful in the practice of the invention are described in international patent applications WO 96/11961 and WO 96/11960. Other non-limiting examples of metallocene catalysts and catalyst systems are discussed in US Patent Nos. 4,808,561, 5,017,714, 5,055,438, 5,064,802, 5,124,418, 5,153,157, and 5,324,800. .

ES 2 339 331 T3

The VLDPEs of the invention can be prepared using a gas phase polymerization process. As used herein, the term "gas phase polymerization" refers to the polymerization of polymers from monomers in a gas fluidized bed. Generally, the VLDPEs of the present invention can be prepared by polymerizing alpha-olefins in the presence of a metallocene catalyst under reactive conditions in a gas phase reactor having a fluidized bed and a fluidizing medium. In a specific embodiment, the VLDPE polymer can be prepared by polymerization in a single reactor (rather than multiple reactors). As discussed in more detail below, various gas phase polymerization procedures can be used. For example, the polymerization can be carried out in non-condensed or "dry" mode, condensed mode, or "super-condensed mode". In a specific embodiment, the liquid in the fluidizing medium can be maintained at a level greater than 2 percent by weight based on the total weight of the fluidizing medium.

The material leaving the reactor includes a very low density polyethylene (VLDPE), which has a density of 0.890 to 0.915 g / cm³, more preferably a density of 0.910 to 0.915 g / cm³, and a stream containing unreacted monomer gases. After polymerization, the polymer is recovered. In certain embodiments, the stream can be compressed and cooled, and mixed with the feed components, whereby a gas phase and a liquid phase are then returned to the reactor.

In a preferred aspect, the VLDPEs of the invention are copolymers, prepared from ethylene monomers together with at least one comonomer, eg, hexene or octene. Polymers that have more than two types of monomers, such as terpolymers, are also included within the term "copolymer" as used herein. For example, VLDPE terpolymers can be prepared using ethylene monomer in conjunction with any two of butene, hexene, and octene. For one embodiment of the VLDPE polymer comprising an ethylene / butene copolymer, the molar ratio of butene to ethylene should be from about 0.015 to 0.035, preferably from 0.020 to 0.030. For one embodiment of the VLDPE polymer comprising an ethylene / hexene copolymer, the molar ratio of hexene to ethylene should be from about 0.015 to 0.035, preferably from 0.020 to 0.030. For one embodiment of the VLDPE polymer comprising an ethylene / octene copolymer, the molar ratio of octene to ethylene should be from about 0.015 to 0.035, preferably from 0.020 to 0.030.

Comonomers that are generally useful for preparing VLDPE copolymers include α-olefins, such as α-olefins C₃-C₂₀ and preferably α-olefins C₃-C₁₂. The α-olefin comonomer can be linear or branched, and two or more comonomers can be used, if desired. Examples of suitable comonomers include α-olefins C₃-Ci₂ linear, and α-olefins having one or more Ci-C alkyl branches₃, or an aryl group. Specific examples include propylene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted with ethyl, methyl or dimethyl; 1-dodecene; and styrene. It should be appreciated that the above list of comonomers is merely exemplary, and is not intended to be limiting. Preferred comonomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and styrene, more preferably

1- butene, 1-hexene and 1-octene.

Although not generally preferred, other useful comonomers include polar vinyl, conjugated and unconjugated dienes, acetylene, and aldehyde monomers, which can be included in minor amounts in terpolymer compositions. Unconjugated dienes useful as comonomers are preferably straight chain hydrocarbon diolefins or cycloalkenyl substituted alkenes having 6 to 15 carbon atoms. Suitable unconjugated dienes include, for example: (a) straight chain acyclic dienes, such as 1,4-hexadiene 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 1,4-cyclohexadiene; 1-5-cyclooctadiene and 1,7-cyclododecadiene; (d) multi-ring alicyclic bridged and fused ring dienes, such as tetrahydroindene; norbornadiene; methyl-tetrahydroindene; dicyclopentadiene (DCPD); bicyclo- (2.2.1) -hepta-2,5-diene; alkenyl-, alkylidene-, cycloalkenyl- and cycloalkylidene-norbornenes, such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2- norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene (VNB); and (e) cycloalkenyl substituted alkenes, such as vinylcyclohexene, allylcyclohexene, vinylcyclooctene, 4-vinylcyclohexene, allylcyclodecene, and vinylcyclododecene. Of the unconjugated dienes typically used, the preferred dienes are dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-

2- norbornene, and tetracyclo- (A-11,12) -5-, 8-dodecene. Particularly preferred diolefins are 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, dicyclopentadiene (DCPD), norbornadiene, and 5-vinyl-2-norbornene (VNB). Note that throughout this description the terms "unconjugated diene" and "diene" are used interchangeably.

It should be appreciated that the amount of comonomer used will depend on the desired density of the VLDPE polymer and the specific comonomers selected. In general, the comonomer may be present in an amount of 25% by weight or less, preferably 20% by weight or less, and more preferably 15% by weight or less. In one embodiment, the comonomer can be present in an amount of 5% by weight or more. For a given comonomer, the density of the VLDPE polymer produced therefrom decreases as the comonomer content increases. One skilled in the art can easily determine the appropriate comonomer content to produce a VLDPE polymer having a desired density.

Generally, when carrying out the gas phase polymerization processes described herein, the reactor temperature may be in the range of 50 ° C to 110 ° C, sometimes higher. However, the

ES 2 339 331 T3 reactor temperature must not exceed the melting point of the VLDPE being formed. A typical reactor temperature is 80 ° C. The reactor pressure should be 689 kPa to 6895 kPa, preferably 1034 to 4137 kPa, more preferably 1379 to 3448 kPa, and most preferably 1723 to 2758 kPa.

Preferably, the process is carried out in a continuous cycle. A specific, non-limiting embodiment of the gas phase polymerization process that is carried out in a continuous cycle will now be described, it being understood that other forms of gas phase polymerization may also be used.

A gaseous stream containing one or more monomers is passed continuously through a fluidized bed under reactive conditions in the presence of a metallocene catalyst. This gaseous stream is withdrawn from the fluidized bed and recycled back to the reactor. Simultaneously, the product polymer can be removed from the reactor, and new monomer or monomers are added to replace the reacted monomer (s). In one part of the cycle, in a reactor, a circulating gas stream is heated by the heat of polymerization. This heat is removed in another part of the cycle by a cooling system external to the reactor. The heat generated by the reaction can be removed in order to maintain the temperature of the gas stream within the reactor at a temperature below the degradation temperatures of the polymer and catalyst. Furthermore, it is often desirable to prevent agglomeration or formation of polymer chunks that cannot be removed as a product. This can be achieved in various ways known in the art, such as, for example, by controlling the temperature of the gas stream in the reaction bed to a temperature below the melting or adhesion temperature of the polymer particles. produced during the polymerization reaction.

Heat must be removed, since the amount of polymer produced in the fluidized bed polymerization process is generally related to the amount of heat that can be removed from a reaction zone in a fluidized bed within the reactor. During the gas phase polymerization process, heat can be removed from the gas recycle stream by cooling the stream outside the reactor. The velocity of the gaseous recycle stream in a fluidized bed process must be sufficient to maintain the fluidized bed in a fluidized state. In certain conventional fluidized bed reactors, the amount of fluid circulated to remove the heat of polymerization is often greater than the amount of fluid required to support the fluidized bed and for adequate mixing of the solids in the fluidized bed. However, to prevent excessive incorporation of solids into a gaseous stream drawn from the fluidized bed, the velocity of the gaseous stream must be regulated.

The recycle stream can be cooled to a temperature below the dew point, resulting in condensation of a portion of the recycle stream, as described in US Patent Nos. 4,543,399 and 4,588. 790. As disclosed in those patents, the resulting stream, containing incorporated liquid, must be returned to the reactor without the agglomeration and / or clogging mentioned above, which can occur when a liquid is introduced during the fluidized bed polymerization process. For the purposes of this patent, this intentional introduction of a liquid into a recycle stream or reactor during the process is generally referred to as a "condensed mode" operation of the gas phase polymerization process. As the above-mentioned patents teach, when the temperature of a recycle stream is lowered to a point below its dew point in condensed mode operation, an increase in polymer production is possible, compared to production in a condensed mode. "Not condensed" or "dry", due to increased cooling capacity. Also, a substantial increase in space-time yield, the amount of polymer production in a given reactor volume, can be achieved by operating in condensed mode, with little or no change in product properties. Also, in certain condensed mode operations, the liquid phase of the two phase recycle stream mixture, gas / liquid, remains incorporated or suspended in the gas phase of the mixture. Cooling the recycle stream to produce this two phase mixture results in a liquid / vapor equilibrium. Vaporization of the liquid occurs when heat is added or pressure is reduced. The increase in space-time efficiencies are the result of this increase in the cooling capacity of the recycle stream, which, in turn, is due to both the greater temperature differential between the incoming recycle stream and the fluidized bed temperature and vaporization of condensed liquid incorporated in the recycle stream. In a specific non-limiting embodiment of the process described herein, a condensed mode of operation is utilized.

When operating the gas phase polymerization process to obtain the VLDPEs of this invention, the amount of polymer and catalyst, the reactor operating temperature, the comonomer (s) to monomer ratio, and the hydrogen to monomer ratio must be determined in advance, so that the desired density and melt index can be achieved.

Although various gaseous polymerization procedures can be used to prepare the polyolefins of the present invention, including the non-condensed or dry mode, it is preferred to use one of four uncondensed of several condensed mode processes, including the condensed mode processes described in the above patents. , as well as improved condensed mode gaseous polymerization processes, such as those described in US Patent Nos. 5,462,999 and 5,405,922. Other types of condensed mode procedures are also applicable, including so-called "super condensed mode" procedures, as discussed in US Patent Nos. 5,352,749 and 5,436,304.

The condensable fluids that can be used in one of the condensed mode gas phase polymerization operations can include saturated or unsaturated hydrocarbons. Examples of inert condensable fluids ade

ES 2 339 331 T3 which are easily volatile liquid hydrocarbons, which can be selected from saturated hydrocarbons containing from 2 to 8 carbon atoms. Some suitable saturated hydrocarbons are propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, and other C hydrocarbons.₆ saturated, n-heptane, n-octane and other C hydrocarbons₇ and C₈ saturated, or mixtures thereof. The preferred inert condensable hydrocarbons are C saturated hydrocarbons.₄ and C₆. The condensable fluids can also include polymerizable condensable comonomers such as olefins, alpha-olefins, diolefins, diolefins containing at least one alpha-olefin, or mixtures thereof, including some of the monomers mentioned above, which can be partially or entirely incorporated into the polymeric product.

The density of the polyethylene having the improved properties of this invention ranges from 0.890 to 0.915 g / cm³, preferably 0.910 g / cm³ at 0.915 g / cm³, more preferably 0.911 to 0.913 g / cm³. Preferably, the polymers have a melt index (IF) ranging from 0.01 to 20.0, preferably 0.5 to 15.0. Melt index is measured according to ASTM-1238, condition E.

Preferred gas phase produced metallocene VLDPE polymers can be further characterized by a narrow composition distribution. As those skilled in the art well know, the compositional distribution of a copolymer refers to the uniformity of the comonomer distribution among the polymer molecules. Metallocene catalysts are known to incorporate the comonomer very uniformly between the polymer molecules they produce. Thus, copolymers produced from a catalyst system having a single metallocene component have a very narrow composition distribution, because most of the polymer molecules will have approximately the same comonomer content, and within each molecule the comonomer will be randomly distributed. In contrast, conventional Ziegler-Natta catalysts generally yield copolymers having a considerably wider composition distribution, with comonomer inclusion that varies widely among polymer molecules.

One measure of composition distribution is the "Composition Distribution Breadth Index" ("CDBI"). The definition of Composition Distribution Breadth Index (CDBI) and the method for determining CDBI can be found in US Patent No. 5,206,075 and PCT Publication WO 93/03093. From the weight fraction vs. composition distribution curve, the CDBI is determined by establishing the percent by weight of a sample that has a comonomer content within 50% of the median comonomer content on each side of the median. The CDBI of a copolymer is readily determined using well known techniques to isolate individual fractions from a sample of the copolymer. One such technique is Temperature Increasing Elution Fractionation (TREF) as described in Wild, et al., J. Poly. Sci., Phys. Ed., Vol. 20, p. 441 (1982).

To determine the CDBI, a solubility distribution curve for the copolymer is first generated. This can be done using data acquired from the TREF technique described above. This solubility distribution curve is a graphical representation of the weight fraction of the copolymer that is solubilized as a function of temperature. This becomes a curve of weight fraction versus composition distribution. For the purpose of simplifying the correlation of composition with elution temperature, all fractions are assumed to have Mn> 15,000, where Mn is the number average molecular weight of the fraction. Any low weight fraction present generally represents a negligible part of the VLDPE polymers. The remainder of this description and the appended claims maintain this convention of assuming that all fractions have Mn> 15,000 as far as the CDBI.

VLDPE polymers can also be characterized by molecular weight distribution (MWD). Molecular Weight Distribution (MWD) is a measure of the molecular weight range within a given polymer sample. It is well known that the amplitude of MWD can be characterized by the ratios of various average molecular weights, such as the ratio of weight average molecular weight to number average molecular weight, Mw / Mn, or the ratio of Z average molecular weight to weight. weight average molecular, Mz / Mw.

Mz, Mw and Mn can be measured using gel permeation chromatography (GPC), also known as size exclusion chromatography (SEC). This technique uses an instrument containing columns packed with porous beads, an elution solvent, and a detector, in order to separate polymer molecules of different sizes. In a typical measurement, the GPC instrument used is a Waters chromatograph equipped with ultrastyro gel columns operating at 145 ° C. The elution solvent used is trichlorobenzene. The columns are calibrated using sixteen polystyrene standards of precisely known molecular weights. A correlation of the retention volume of the polystyrene obtained from the standards to the retention volume of the tested polymer gives the molecular weight of the polymer.

The mean molecular weights M can be computed from the expression:

i

ES 2 339 331 T3 where N, is the number of molecules that have a molecular weight M ,. When n = 0, M is the number average molecular weight, Mn. When n = 1, M is the weight average molecular weight, Mw. When n = 2, M is the average molecular weight Z, Mz. The desired MWD function (eg, Mw / Mn or Mz / Mw) is the ratio of the corresponding M values. The measurement of M and MWD is well known in the art, and is discussed in more detail in, for example, Slade, PE Ed., Polymer Molecular Weights Part II, Marcel Dekker, Inc., NY, (1975) 287-368; Rodríguez, F., Principles of Polymer Systems 3rd ed., Hemisphere Pub. Corp., NY, (1989) 155-160; US Patent No. 4,540,753; Verstrate et al., Macromolecules, vol. 21, (1988) 3360; and the references cited therein.

The VLDPE polymers cited in the claims below are preferably linear polymers, ie without long chain branching. As used herein, the term "linear" applies to a polymer that has a linear backbone and does not have long-chain branching; that is, a "linear" polymer is one that does not have the characteristic long chain branches of a SLEP polymer as defined in US Patent Nos. 5,272,236 and 5,278,272. Thus, a "substantially linear" polymer as described in those patents is not a "linear" polymer due to the presence of long chain branching.

Preferred VLDPE polymers have one or more of the following characteristics, in addition to density, melt index, and other parameters described herein:

a) a composition distribution breadth index, CDBI, of 50 to 85%, alternatively 60 to 80%, or 55 to 75%, or 55% or more to 70% or less;

b) a molecular weight distribution, MWD, of 2 to 3, alternatively 2.2 to 2.8;

c) a molecular weight distribution Mz / Mw less than 2; Y

d) the presence of two peaks in a TREF measurement.

Particularly preferred VLDPEs having all or some of these characteristics are the gas phase metallocene produced VLDPEs described above.

Two peaks in the TREF measurement, as used in this specification and in the appended claims, means the presence of two distinct normalized ELS (evaporative light scattering) response peaks on a graph of the normalized ELS response (vertical axis oy) versus elution temperature (horizontal x or x axis, with increasing temperature from left to right) using the TREF method described in the EXAMPLES section below. A "peak", in this context, means the place where the overall slope of the graph changes from positive to negative with increasing temperature. Between the two peaks there is a local minimum at which the overall slope of the graph changes from negative to positive with increasing temperature. The “general trend” in the graph is intended to exclude multiple local lows and highs that can occur at intervals of 2 ° C or less. Preferably, the two distinct peaks are at least 3 ° C apart, more preferably at least 4 ° C apart, even more preferably at least 5 ° C apart. Additionally, both different peaks occur at a temperature on the graph above 20 ° C and below 120 ° C, where the elution temperature is run at 0 ° C or lower. This limitation avoids confusion with the apparent peak on the low temperature graph caused by material remaining soluble at the lower elution temperature. Two peaks on such a graph indicate a bimodal composition distribution (DC). Bimodal DC can also be determined by other methods known to those of skill in the art. One such alternative method for the TREF measurement that can be used if the above method does not show two peaks is described in B. Monrabal, "Crystallization Analysis Fractionation: A New Technique for the Analysis of Branching Distribution in Polyolefins", Journal of Applied Polymer Science, Vol. 52,491-499 (1994).

A preferred balance of properties, particularly in film applications, according to the invention is achieved when the long chain branching of the VLDPE is low. Therefore, with respect to the catalyst structures described above, bis-Cp structures are preferred over mono-Cp structures, non-bridged structures are preferred over bridged structures, and non-bridged bis-Cp structures are the most preferred. Preferred catalyst systems that will minimize or eliminate long chain branching to produce polymers substantially free of or free of long chain branching are based on bridged bis-Cp zirconocenes, such as, but not limited to, bis (1- methyl-3-n-butyl-cyclopentadiene) zirconium.

Symmetric metallocenes can be used to produce a VLDPE polymer of the present invention. Symmetric metallocenes include, but are not limited to, bis (methylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,2-dimethylcyclopentadienyl) zirconium dichloride, bis (1,2 , 4-trimethylcyclopentadienyl) zirconium, bis (1,2,3-trimethylcyclopentadienyl) zirconium dichloride,

ES 2 339 331 T3 bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bispentadienyl cyclopentadienyl dichloride (bispentadienyl dichloride ) zirconium, bis (pentylcyclopentadienyl) zirconium dichloride, bis (isopentylcyclopentadienyl) zirconium dichloride, bis (cyclopentylcyclopentadienyl) zirconium dichloride, bis (phenylcyclopentadienyl) zirconium dichloride, bis (benzylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylmethylcyclopentadienyl) zirconium dichloride, bis (cyclopropylmethylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) cyclopentyl cyclopentyl zirconium dichloride (cyclopentadienyl) dichloride (cyclopentadienyl) zirconium dichloride bis (propenylcyclopentadienyl) zirconium, bis (butenylcyclopentadienyl) zirconium dichloride, bis (1,3-ethylmethylcyclopentadienyl) zirconium dichloride, bis (1,3-propylmethylcyclopentadienyl) zirconium dichloride, bis (1,3-butylmethylcyclopentadienyl) zirconium dichloride, bis (1,3-isopropylmethylcyclopentadienyl) zirconium dichloride, bis (1,3-isobutylmethylcyclopentadienyl) zirconium dichloride bis (1,3-methylcyclopentylcyclopentadienyl) zirconium, and bis (1,2,4-dimethylpropylcyclopentadienyl) zirconium dichloride.

Non-symmetric metallocenes can be used to produce a VLDPE polymer of the present invention. Non-symmetric metallocenes include, but are not limited to, cyclopentadienyl (1,3-dimethylcyclopentadienyl) zirconium dichloride, cyclopentadienyl (1,2,4-trimethylcyclopentadienyl) zirconium dichloride, cyclopentadienyl (tetramethylcyclopentadienyl) zirconium dichloride (tetramethylcyclopentadienyl) zirconium pentamethylcyclopentadienyl) zirconium, cyclopentadienyl (propylcyclopentadienyl) zirconium dichloride, cyclopentadienyl (butylcyclopentadienyl) zirconium dichloride, cyclopentadienyl (pentylcyclopentadienyl) zirconium dichloride, cyclopentadienyl (isobutylcyclopentadienyl) zirconium dichloride,

ES 2 339 331 T3 cyclopentadienyl (cyclopentylcyclopentadienyl) zirconium dichloride, cyclopentadienyl (isopentylcyclopentadienyl) zirconium dichloride, cyclopentadienyl (benzylcyclopentadienyl) zirconium, cyclopentadienylcyclopentadienyl (cyclopentadienyl) cyclopentadienyl cyclopentadienyl dichloride, cyclopentadienyl cycloconium (dichloride) cyclopentadienyl (1,3-butylmethylcyclopentadienyl) zirconium, cyclopentadienyl (1,3-isobutylmethylcyclopentadienyl) zirconium dichloride, Cyclopentadienyl (1,2,4-dimethylpropylcyclopentadienyl) zirconium dichloride, (tetramethylcyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (tetramethylcyclopentadienyl) (1,3-dimethylcyclopentadienyl) zirconium dichloride, 1,2-dimethylcyclopentadienyl (1,2-dimethylcyclopentadienyl) zirconium dichloride trimethylcyclopentadienyl) zirconium, (tetramethylcyclopentadienyl) (propylcyclopentadienyl) zirconium dichloride, (tetramethylcyclopentadienyl) (cyclopentylcyclopentadienyl) zirconium dichloride, (pentamethylcyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (pentamethylcyclopentadienyl) (1,3-dimethylcyclopentadienyl) zirconium dichloride, (pentamethylcyclopentadienyl) (1,2,4-trimethylcyclopentadienyl) (pentamethylcyclopentadienyl) (1,3-dimethylcyclopentadienyl) zirconium dichloride, (pentamethylcyclopentadienyl) (1,2,4-trimethylcyclopentadienyl) (pentamethyl) cyclopentadienyl dichloride (pentamethylcyclopentadienyl) (cyclopentylcyclopentadienyl) zirconium dichloride, cyclopentadienyl (ethyltetramentylcyclopentadienyl) zirconium dichloride, cyclopentadienyl (propyltetramentylcyclopentadienyl) zirconium dichloride, (methylcyclopentadienyl) (propyltetramentylcyclopentadienyl) zirconium dichloride, (1,3-dimethylcyclopentadienyl) (propyltetramentylcyclopentadienyl) dichloride (propyltetramentylcyclopentadienyl) zirconium dichloride, (propyltetramentylcyclopentadienyl) zirconium (1,2-pentadienyl) zirconium-dimethylcyclopentadienyl-cyclo- propylcyclopentadienyl) (propyltetramentylcyclopentadienyl) zirconium, cyclopentadienyl (indenyl) zirconium dichloride, (Methylcyclopentadienyl) (indenyl) zirconium dichloride, (1,3-dimethylcyclopentadienyl) (indenyl) zirconium dichloride, (1,2,4-trimethylcyclopentadienyl) (indenyl) zirconium dichloride, (tetramethylcyclopentadienyl) (indenium) dichloride, (Pentamethylcyclopentadienyl) (indenyl) zirconium dichloride, cyclopentadienyl (1-methylindenyl) zirconium dichloride, cyclopentadienyl (1,3-dimethylindenyl) zirconium dichloride, cyclopentadienyl (1,2,3-trimethylindenyl) zirconium dichloride, cyclopentadienyl (4,7-dimethylindenyl) zirconium dichloride,

ES 2 339 331 T3 (tetramethylcyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, (pentamethylcyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, cyclopentadienyl (5,6-dimethylindenyl) zirconium dichloride, pentamethyl dichloride (5,6-dimethylindenyl) zirconium, and (tetramethylcyclopentadienyl) (5,6-dimethylindenyl) zirconium dichloride.

The preferred method of producing the catalyst of the invention is described below, and can be found in U.S. Patent Application Serial Numbers 265,533, filed June 24, 1994, now abandoned, and 265,532, filed on June 24, 1994. In a preferred embodiment, the metallocene catalyst component is typically suspended in a liquid to form a metallocene solution, and a separate solution is formed containing an activator and a liquid. The liquid can be any compatible solvent or other liquid capable of forming a solution or the like with at least one metallocene catalyst component and / or at least one activator. In the preferred embodiment, the liquid is a cyclic or aromatic aliphatic hydrocarbon, most preferably toluene. The metallocene and activator solutions are preferably mixed with each other and added to a porous support, such that the total volume of the metallocene solution and the activator solution or the metallocene and activator solution is less than four times the volume. pore of the porous support, more preferably less than three times, still more preferably less than two times, and more preferably in the range of 1-1.5 times to 2.5-4 times, and most preferably in the range of 1.5 to 3 times. Also, in the preferred embodiment, an antistatic agent is added to the catalyst preparation.

In one embodiment, the metallocene catalyst is prepared from silica dehydrated at 600 ° C. The catalyst is a commercial scale catalyst prepared in a mixing vessel with a stirrer. An initial load of 462 kg is added to the mixer. This was followed by mixing 421 kg of 30 weight percent methylalumoxane in toluene. This is followed by 46 kg of 20 weight percent bis (1,3-methyl-n-butylcyclopentadienyl) zirconium dichloride in toluene (9.3 kg of contained metallocene). An additional 66 kg of toluene is added to the mixer to clear the metallocene feed cylinder and allowed to mix for 30 minutes under ambient conditions. This is followed by 25 kg of AS-990 in toluene, a surface modifying solution, containing 2.4 kg of contained AS990. 46 Additional kg of toluene rinsed the surface modifier container and was added to the mixer. The resulting suspension is dried under vacuum at 70.6 kPa at 79 ° C to a free-flowing powder. The final weight of the catalyst was 497 kg. The catalyst can have a final zirconium loading of 0.40% and an aluminum loading of 12.0%.

In a preferred embodiment, a substantially homogeneous catalyst system is preferred. For the purposes of this patent specification and its appended claims, a "substantially homogeneous catalyst" is one in which the molar ratio of the transition metal of the catalyst component, preferably with an activator, is uniformly distributed throughout a support. porous.

The procedure for measuring the total pore volume of a porous support is well known in the art. Details of one of these procedures are discussed in Volume 1, Experimental Methods in Catalytic Research (Academic Press, 1968) (see specifically pages 67-96). This preferred procedure involves the use of a classical BET apparatus for nitrogen absorption. Another method well known in the art is described in Innes, Total Porosity and Particle Density of Fluid Catalysts By Liquid Titration, Vol. 28, No. 3, Analytical Chemistry 332334 (March, 1956).

The molar ratio of the metal of the activator component to the transition metal of the metallocene component is in the range of ratios between 0.3: 1 to 1000: 1, preferably 20: 1 to 800: 1, and most preferably 50: 1 to 500: 1. Where the activator is an ionizing activator as described above, the molar ratio of the metal of the activator component to the transition metal of the metallocene component is preferably in the ratio range of 0.3: 1 to 3: 1.

Typically, in a gas phase polymerization process a continuous cycle is employed, where in part of a reactor cycle, a circulating gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization. This heat is removed in another part of the cycle by a cooling system external to the reactor. (See, for example, US Patent Nos. 4,543,399, 4,588,790, 5,028,670, 5,352,749, 5,405,922, 5,436,304, 5,453,471 and 5,462,999).

Generally, in a fluidized bed process for producing a polymer from monomers, a gaseous stream containing one or more monomers is continuously circulated through a fluidized bed in the presence of a catalyst under reactive conditions. The gas stream is removed from the fluidized bed and recycled back to the reactor. Simultaneously, the product polymer is removed from the reactor and new or fresh monomer is added to replace the polymerized monomer.

In one embodiment of the process of the invention, the process is essentially free of a scrubber. For the purposes of this patent specification and its appended claims, the term "essentially exempt"

ES 2 339 331 T3 means that during the process of the invention no more than 10 ppm of a scrubber is present based on the total weight of the recycle stream at any given time point during the process of the invention.

In another embodiment of the process of the invention, the process is substantially free of a scrubber. For the purposes of this patent specification and its appended claims, the term "substantially exempt" is defined as that during the process of the invention no more than 50 ppm of a scrubber is present based on the total weight of a fluidized bed in any given point of time during the process of the invention.

In one embodiment, during reactor startup, to remove impurities and ensure that polymerization begins, a scavenger is present in an amount less than 300 ppm, preferably less than 250 ppm, more preferably less than 200 ppm, even more. preferably less than 150 ppm, still more preferably less than 100 ppm, and most preferably less than 50 ppm, based on the total bed weight of a fluidized bed during the first 12 hours from the time the catalyst is put into the reactor, preferably up to 6 hours, more preferably less than 3 hours, still more preferably less than 2 hours, and most preferably less than 1 hour, and then the introduction of the scrubber is stopped.

In another embodiment of the process of the invention, the scrubber is present in a sufficient amount until the catalyst of the invention has achieved a catalytic productivity on a weight ratio basis greater than 1000 grams of polymer per gram of catalyst, preferably greater than about 1500, more preferably greater than 2000, even more preferably greater than 2500, and most preferably greater than 3000.

In another embodiment of the process of the invention, during start-up the scrubber is present in a sufficient amount until the catalyst of the invention has achieved a catalytic productivity of 40 percent of steady state, preferably less than 30 percent. , even more preferably less than 20 percent and most preferably less than 10 percent. For the purposes of this patent specification and its appended claims, "steady state" is the rate of production, weight of polymer that is produced per hour.

The productivity of the catalyst or catalyst system is influenced by the partial pressure of the main monomer (ie, ethylene or propylene). The preferred mole percent of the monomer, ethylene or propylene, is from about 25 to 90 mole percent, and the partial pressure of the monomer ranges from about 517 kPa (75 psia) to about 2069 kPa (300 psia). ), which are typical conditions in a gas phase polymerization process.

When a scrubber is used in the process of the invention, the scrubber can typically be introduced into the reactor directly or indirectly in the recycle stream or in any external means capable of introducing the scrubber into the reactor. Preferably, the scrubber enters the reactor directly, and most preferably, directly into the reactor bed or below the manifold plate of a typical gas phase process, preferably after the bed is in a fluidized state. In one embodiment, the scrubber can be introduced at once, intermittently, or continuously to the reactor system.

The scrubber used in the process of the invention is introduced into the reactor at a rate equivalent to 10 ppm to 100 ppm, based on steady state, production rate, and then the introduction of the scrubber is stopped.

In yet another embodiment, particularly during start-up, the scrubber, when in use, is introduced at a rate sufficient to provide an increase in catalyst productivity, on a weight ratio basis, at a rate of 200 grams of polymer per gram of catalyst per minute, preferably at a rate of 300, even more preferably at a rate of 400, and most preferably at a rate of 500.

In another embodiment, the molar ratio of the metal of the scrubber to the transition metal of the metallocene catalyst component is equal to about 0.2 times the ppm of a scrubber, based on the production rate times the productivity of the catalyst in kilograms. of polymer per gram of catalyst. The range of the molar ratio is approximately 300 to 10. In a preferred embodiment, where an aluminum alkyl is used as a scavenger, the molar ratio is represented as aluminum (Al) to transition metal, eg, zirconium, where the moles of Al are based on the total amount of scavenger used.

It is also preferred that hydrogen is not added to the system simultaneously with the scrubber. It is also within the scope of this invention that the scrubber can be introduced into a support separate from that used when a supported metallocene catalyst system is employed in the process of the invention.

Fines, for the purposes of this patent specification and its appended claims, are polymer particles less than 125 mesh units in size. Fines of this size can be measured using a standard 120 mesh unit sieve. In a preferred embodiment, with the amount of scrubber present in the reactor at any given point of time during the process of the invention, the level of fines less than 125 mesh units is less than 10%, preferably less than 1%, more preferably from less than 0.85% to less than 0.05%.

ES 2 339 331 T3

It is within the scope of the invention that a system external to the reactor can be used to remove the scrubbers introduced in the process of the invention from the recycle stream. This would then prevent recycling of the scrubber back to the reactor, and would prevent buildup of the scrubber in the reactor system. It is preferred that such a system is placed before the heat exchanger or compressor in the recycle stream line. It is contemplated that such a system would condense the scrubber out of the fluidizing medium in the recycle stream line. It would be preferred that the fluidizing medium be treated to remove the scrubber, see for example US Patent No. 4,460,755.

It is also contemplated by the process of the invention that the scrubber may be introduced intermittently during the process, where more than 90%, preferably more than 95% of all introduced scrubber is removed from the recycle stream.

It is also contemplated by this invention that the catalyst or catalyst system or components thereof of the invention could be used after start-up as a scrubber, however this would be an expensive process.

In the most preferred embodiment of the invention, the process is a gas phase polymerization process operating in a condensed mode. For the purposes of this patent specification and its appended claims, the method of intentionally introducing a recycle stream having a liquid phase and a gas phase into a reactor such that the weight percent of liquid based on the total weight of the recycle stream is greater than about 2.0 weight percent is defined to be operating as a gas phase polymerization process in a "condensed mode".

In one embodiment of the process of the invention, the weight percent liquid in the recycle stream based on the total weight of the recycle stream is in the range of about 2 to about 50 percent by weight, preferably greater than 10 weight percent and more preferably greater than 15 weight percent and even more preferably greater than 20 weight percent, and most preferably in the range between about 20 and about 40 percent. However, any level of condensate can be used, depending on the desired production rate.

In another embodiment of the process of the invention, the amount of scrubber used, if any, should be in a molar ratio of less than 100, preferably less than 50, more preferably less than about 25, based on the molar ratio of the metal. from the transition metal scrubber to the metallocene transition metal, where the scrubber is an aluminum-containing organometallic compound and the metallocene transition metal is a Group 4 metal, then the above molar ratio is based on the moles of aluminum to the moles of the Group 4 metal of the catalyst.

Fouling is a term used to describe the accumulation of polymer deposits on reactor surfaces. Fouling is detrimental to all parts of a polymerization process, including the reactor and its associated systems, and the hardware. Fouling is especially damaging in areas that restrict gas flow or liquid flow. The two main areas of concern are fouling of the heat exchanger and the manifold plate. The heat exchanger consists of a series of small diameter tubes arranged in a bundle of tubes. The distributor plate is a solid plate that contains numerous small diameter holes, through which the gas contained in a recycle stream is passed before entering the reaction zone or is distributed in a solid polymer bed of a fluidized bed reactor, as described in US Patent No. 4,933,149.

Fouling manifests itself as an increase in pressure drop across either the plate, the cooler, or both. Once the pressure drop becomes too high, the gas or liquid can no longer be efficiently circulated through the compressor, and it is often necessary to shut down the reactor. Cleaning the reactor can take several days, and is time consuming and expensive. Fouling can also occur in the recycle gas lines and the compressor, but it usually accompanies the hob and cooler.

To quantify the fouling rate, it is useful to define a fouling factor, F. F is the fraction of the area of ​​a hole that is fouled. If F = 0 (0%) then there is no fouling. Conversely, if F = 1 (100%) the hole is completely plugged. It is possible to relate fouling to the pressure drop, DELTA P, at a given time, in terms of the pressure drop of a clean system, DELTA P0. As fouling increases, DELTA P increases and is greater than the initial pressure drop, DELTA P0. F is given by the following expressions: [See equation in original] (I) Cooler fouling [See Original Patent for Chemical Structure Diagram] (II) In general, when F is greater than about 0.3 to about 0 , 4 (30-40%), a reactor shutdown is unavoidable. Preferably F is less than 40%, preferably less than 30%, still more preferably less than 20%, still more preferably less than 15% and most preferably less than 10% to 0%. The fouling rate, the change in F as a function of time, is used to quantify fouling. If no fouling occurs, the fouling rate is zero. A minimum acceptable fouling rate for a commercial operation is about 12 percent / month or 0.4 percent / day, preferably less than 0.3 percent / day, even more preferably less than 0.2 percent / day, and most preferably less than 0.1 percent / day.

The particle size is determined as follows; Particle size is measured by determining the weight of material collected on a series of US standard sieves and determining the weight average particle size.

ES 2 339 331 T3

Fines are defined as the percentage of the total distribution that passes through a standard 120 mesh screen.

In one embodiment, the process is operated using a metallocene catalyst based on bis (1,3-methyl-n-butylcyclopentadienyl) zirconium dichloride that is described in this example. It shows the fouling effect of running a commercial reactor using TEAL. This example includes information, from a commercial reactor startup, on a metallocene catalyst.

Possible gas phase polymerization process optimizations and additional catalyst preparations are described in US Patent Nos. 5,763,543, 6,087,291 and 5,712,352, and published PCT applications WO 00/02930 and WO 00 / 02931.

Although the VLPDE polymer component of the VLDPE / LDPE blends of the invention has been discussed as a single polymer, blends of two or more VLDPE polymers such, preferably two or more m-VLDPE polymers, having the properties described herein are also contemplated. memory.

In any of the gas phase polymerization processes described herein, including those of the patents referenced herein, unreacted monomers in the product stream can be recycled. Preferably, to prepare the VLDPEs of the invention to the desired density, the composition of the recycle stream must be carefully controlled so that the proper ratio of comonomers is maintained, as discussed above.

Another aspect of the invention relates to a polymeric product containing any one of the very low density polyethylenes (VLDPEs) prepared using a gas phase polymerization process carried out in the presence of metallocene. Such polymeric products preferably contain a sufficient amount of the VLDPE to provide them with improved properties, such as the toughness properties described earlier in the Digest, eg, the Dart Drop and / or Puncture values ​​mentioned above. Such products include various film-based products, such as films made from VLDPEs, cast films, melt blown films, coextruded films, films made from blends of VLDPE together with other polymers, laminated films, extrusion coatings, films. with high oxygen transmission rates, multilayer films containing the VLDPEs, sealant layers and adherent layers containing the VLDPEs and products that include such sealant layers and adherent layers. The blends of the invention have VLDPE together with other polymers, such as LDPE, MDPE, HDPE, polypropylene, and copolymers such as ethylene / propylene copolymers. This invention also includes products that have specific end uses, particularly film-based products for which toughness properties are desirable, such as stretch films, ocean freight bags, flexible and food packaging (eg, product packaging. fresh cut food), film sachets for personal care, medical film products (such as IV bags (for intravenous products)), diaper backsheets, and household plastic wrap. Another product of this invention includes a VLDPE that has been made breathable and used either alone (as a single layer film) or in combination with one or more other layers or films or fabrics, including woven or non-woven films or fabrics. The products also include extrusion coating compositions containing the VLDPE. Various applications of specific films and coatings are described below.

4.2 The LDPE component

The polymer blend also includes a low density polyethylene (LDPE) polymer. As used herein, the terms "low density polyethylene polymer" and "LDPE polymer" refer to a homopolymer or preferably copolymer of ethylene having a density of 0.916 to 0.928 g / cm³. Polymers that have more than two types of monomers, such as terpolymers, are also included within the term "copolymer" used herein. Comonomers that are generally useful for preparing LDPE copolymers include α-olefins, such as α-olefins C₃-C₂₀ and preferably α-olefins C₃-C₁₂. The α-olefin comonomer can be linear or branched, and two or more comonomers can be used, if desired. Examples of suitable comonomers include α-olefins C₃-C₁₂ linear, and α-olefins having one or more C alkyl branches₁C₃, or an aryl group. Specific examples include propylene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene one or more methyl, ethyl or propyl substituents; 1-nonene one or more methyl, ethyl or propyl substituents; 1-decene substituted with ethyl, methyl or dimethyl; and styrene. It should be appreciated that the above list of comonomers is merely exemplary, and is not intended to be limiting. Preferred comonomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and styrene.

Other useful comonomers include polar vinyl, conjugated and unconjugated dienes, acetylene, and aldehyde monomers, which can be included in minor amounts in terpolymer compositions. Unconjugated dienes useful as comonomers are preferably straight chain hydrocarbon diolefins or cycloalkenyl substituted alkenes having 6 to 15 carbon atoms. Suitable unconjugated dienes include, for example: (a) straight chain acyclic dienes, such as 1,4-hexadiene 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 1,4-cyclohexadiene; 1-5-cyclooctadiene and 1,7-cyclododecadiene; (d) dienes of

ES 2 339 331 T3 multi-ring fused and alicyclic bridged rings, such as tetrahydroindene; norbornadiene; methyltetrahydroindene; dicyclopentadiene (DCPD); bicyclo- (2.2.1) -hepta-2,5-diene; alkenyl-, alkylidene-, cycloalkenyl- and cycloalkylidene-norbornenes, such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2- norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene (VNB); and (e) cycloalkenyl substituted alkenes, such as vinylcyclohexene, allylcyclohexene, vinylcyclooctene, 4-vinylcyclohexene, allylcyclodecene, and vinylcyclododecene. Of the unconjugated dienes typically used, the preferred dienes are dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, and tetracyclo- (A-11,12) -5,8dodecene. . Particularly preferred diolefins are 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, dicyclopentadiene (DCPD), norbornadiene, and 5-vinyl-2-norbornene (VNB).

The amount of comonomer used will depend on the desired density of the LDPE polymer and the specific comonomers selected. One skilled in the art can easily determine the appropriate comonomer content to produce an LDPE polymer having a desired density.

LDPE polymer has a density of 0.916 g / cm³ at 0.928 g / cm³, and preferably 0.916 g / cm³ at 0.925 g / cm³. The LDPE polymer can have a melt index of 0.5 to 20 g / 10 min (dg / min), measured in accordance with ASTM-1238, condition E. Alternative lower limits for melt index include 0.7 and 1.0 g / 10 min, and alternative upper limits for melt index include 5, 10 and 15 g / 10 min, with the melt index ranges between any lower limit and any upper limit within the scope of the invention. .

The LDPE polymer can be produced using any conventional polymerization procedure and suitable catalyst, such as a Ziegler-Natta catalyst or a metallocene catalyst. Metallocene catalyzed LDPEs (m-LDPE) are preferred. Particularly preferred m-LDPEs are gas phase metallocene catalyzed LLPDEs described in international patent application WO 94/26816, the disclosure of which is incorporated herein by reference for the purposes of patent practice by USA Examples of suitable LDPEs include the metallocene LDPEs available commercially under the trade name EXCEED ™ from ExxonMobil Chemical Co., Houston, Texas, the Ziegler-Natta LDPEs available as ExxonMobil LL series LDPEs from ExxonMobil Chemical Co. , Houston, Texas, and DOWLEX ™ LDPE resins available from Dow Chemical Co.

Although the LLPDE polymer component of the VLDPE / LDPE blends of the invention has been discussed as a single polymer, blends of two or more such LDPE polymers, preferably two or more metallocene catalyzed LDPE polymers, having the properties described in the present memory.

4.3 VLDPE-LDPE blends

In one embodiment, the present invention provides a polymer blend, the blend including a VLDPE polymer and an LDPE polymer. The blend may include any of the VLDPE polymers described herein, preferably a metallocene catalyzed VLDPE polymer, and more preferably a gas phase produced metallocene catalyzed VLDPE polymer. The blend may include any of the LDPE polymers described herein, preferably a metallocene catalyzed LDPE polymer, and more preferably a gas phase produced metallocene catalyzed LDPE polymer.

Mixtures can be formed using conventional equipment and methods, such as dry mixing of the individual components and subsequently melt blending in a mixer, or by mixing the components together directly in a mixer, such as a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin screw extruder including a composer extruder and a side arm extruder used directly downstream of a polymerization process. Additionally, additives may be included in the blend, in one or more components of the blend, and / or in a product formed from the blend, such as a film, if desired. Such additives are well known in the art, and can include, for example, fillers; antioxidants (eg, hindered phenolic compounds such as IRGANOX ™ 1010 or IRGANOX ™ 1076, available from Ciba-Geigy); phosphites (eg, IRGAFOS ™ 168, available from Ciba-Geigy); anti-adhesion additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; stabilizers against heat; anti-blocking agents; release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; loads; talcum powder.

The blends include at least 1 weight percent and up to 99 weight percent VLDPE polymer, and at least 1 weight percent and up to 99 weight percent LDPE polymer, these weight percent being based on the total weight of the VLDPE and LDPE polymers in the blend. Alternative lower limits of the VLDPE polymer can be 5%, 10%, 20%, 30% or 40% by weight. Alternative upper limits of the VLDPE polymer can be 95%, 90%, 85%, 70% and 60% by weight. Ranges from any lower limit to any upper limit are within the scope of the invention. Preferred blends include 5 to 85%, 10 to 50%, 10 to 30%, or 65 to 95% by weight of the VLDPE polymer. The remainder of the weight percent is the weight of the LDPE polymer component.

In a preferred embodiment, the polymer blend includes a metallocene catalyzed VLDPE polymer having a density of less than 0.916 g / cm³, and an LDPE polymer having a density of 0.916 to 0.940 g / cm³.

ES 2 339 331 T3

In another preferred embodiment, the polymer blend includes a gas phase metallocene catalyzed VLDPE polymer, the VLDPE polymer being a copolymer of ethylene and at least one C3 to Ci2 alpha-olefin and having a density of 0.900 to 0.915 g / cm³ and a melt index of 0.5 to 20 g / 10 min; and an LDPE polymer produced by metallocene, the LDPE polymer being a copolymer of ethylene and at least one alpha-olefin C3 to Ci2 and having a density of 0.916 to 0.925 g / cm³ and a melt index of 0.5 to 20 g / 10 min, where the mixture includes 5-85% by weight of the VLDPE polymer and 95-15% by weight of the LDPE polymer, preferably 10-50% by weight of the polymer. VLDPE and 90-50% by weight of the LDPE polymer, based on the total weight of the VLDPE and LDPE polymers.

In any of these embodiments, the VLDPE polymer, the LDPE polymer, or both can be mixtures of such polymers. That is, the VLDPE polymer component of the blend may itself be a blend of two or more VLDPE polymers having the characteristics described herein, and alternatively or additionally, the LDPE polymer component of the blend may itself be same a blend of two or more VLDPE polymers having the characteristics described herein.

4.4 Films, coatings and articles

Films of the metallocene VLDPE polymers of the present invention can be formed by conventional processes, preferably by a cold roll casting process. The polymer is extruded by an extruder, melt processed through a slot die, and melt stretch thinned by an optional air knife and cold roll. Extrusion coatings are generally processed at higher temperatures than cast films, typically about 315 ° C, in order to promote adhesion of the extrudate to the substrate. The resulting polymeric film is collected on a winder. The thickness of the film can be controlled by a calibrating monitor, and the film can be trimmed at the edges by a cutter. One or more treaters can be used to treat the surface of the film, if desired. Such cold roll casting methods and apparatus are well known in the art, and are described, for example, in The Wiley Encyclopedia of Packaging Technology, Second Edition, AL Brody and KS Marsh, Ed., John Wiley and Sons, Inc. , New York (1997). Other extrusion coating processes are known in the art, and are described, for example, in US Patent Nos. 5,268,230, 5,178,960 and 5,387,630.

In one embodiment, the present invention is directed to metallocene-prepared VLDPE films or coatings of the films on flexible media such as paper, metal foil, polymeric materials such as polypropylene, polyester, and the like. The resins in the film have a density less than 0.916 g / cm³, and a melt flow rate ("VFF") of 6-15 dg / min, preferably 9-12 dg / min. Generally, the resin density of the film is 0.890 to 0.915 g / cm³, 0.905 to 0.915 g / cm³, 0.910 to 0.915 g / cm³, or 0.911 to 0.913 g / cm³. In a particular embodiment, the resin of the film has a density of 0.912 g / cm³ and a VFF of 12 dg / min. These films and coatings can be produced as described above.

It should be emphasized that the VLDPE / LDPE blends of the present invention may make use of VLDPE polymers produced by the methods described herein, or VLDPE polymers produced by other methods known in the art for use in the preparation of polymers. Metallocene VLDPE.

In another embodiment, the present invention is directed to metallocene-prepared VLDPE films or coatings of the films on flexible media such as paper, metal foil, and the like, wherein the film or coating is formed of a resin including a VLDPE of metallocene mixed with an LDPE. The substrate can also be cardboard for milk containers, juice containers and films. The amount of LDPE in the mixture can be 1 to 40% by weight, preferably 5 to 35%, 10 to 30%, or 15 to 15% by weight. In a particular embodiment, the resin mixture includes 20% by weight of an LDPE such as LD200 or LD270, which are LDPE resins available on the market. The resin blends and / or the mVLDPE in the blends have a density less than 0.916 g / cm³, and a melt flow rate ("VFF") of 6-15 dg / min, preferably 9-12 dg / min. These films and coatings can be produced as described above. LDPE and mVLDPE can be mixed in standard procedures well known in the art.

The films and coatings of the present invention are also suitable for use in laminated structures; that is, with a film or coating as described herein disposed between two substrates. These films and coatings are also suitable for use as heat seal or moisture barrier layers in single or multilayer structures.

Another aspect of the invention relates to the formation of monolayer films from the polymer blend compositions discussed above. These films can be formed by any number of well known extrusion or coextrusion techniques discussed below. Films of the invention can be unoriented, uniaxially oriented, or biaxially oriented. The physical properties of the film can vary depending on the film-forming techniques used.

Another aspect of the invention relates to the formation of multilayer films from the polymer blend compositions discussed above. Multilayer films can be formed by methods well known in the art. The total thickness of multilayer films can vary based on the desired application. A total film thickness of about 5-100 pm, more typically about 10-50 pm, is suitable for most

ES 2 339 331 T3 applications. Those skilled in the art will appreciate that the thickness of the individual layers for multilayer films can be adjusted based on the desired end-use performance, the resin or copolymer employed, the capacity of the equipment, and other factors. The materials that make up each layer can be coextruded through a coextrusion die and feed block assembly to give a film with two or more layers adhered to each other but differing in composition. Coextrusion can be adapted for use in both cast film and blown film processes.

When used in multilayer films, the VLDPE / LDPE polymer blend can be used in any layer of the film, or in more than one layer of the film, as desired. When more than one layer of the film is formed by a blend of VLDPE / LDPE polymers of the present invention, each such layer can be formulated individually; that is, the layers formed by the VLDPE / LDPE polymer blend can be of the same or different chemical composition, density, melt index, thickness, depending on the desired properties of the film.

To facilitate discussion of different film structures of the invention, the following notation is used herein. Each layer of a film is denoted as "A" or "B", where "A" indicates a conventional film layer as defined below, and "B" indicates a film layer formed by any of the VLDPE polymers of the present invention. Where a film includes more than one A layer or more than one B layer, one or more prime symbols (', ”,”', etc.) are appended to the symbol A or B to indicate layers of the same type (conventional or inventive) They may be the same or may differ in one or more properties, such as chemical composition, density, melt index, and thickness. Finally, the symbols for adjacent layers are separated by a slash (/). Using this notation, a three-layer film having an inner layer of a VLDPE / LDPE polymer blend of the invention disposed between two outer layers, conventional film layers would be denoted A / B / A '. Similarly, a five layer film of alternating conventional / inventive layers would be denoted A / B / A '/ B' / A ". Unless stated otherwise, the left-to-right or right-to-left order of the layers does not matter, nor does the order of the prime symbols; eg, A / B film is equivalent to B / A film, and A / A '/ B / A film ”is equivalent to A / B / A' / A film”, for the purposes of the present invention. The relative thickness of each film layer is denoted similarly, the thickness of each layer being relative to a total film thickness of 100 (dimensionless) indicated numerically and separated by bars; eg, the relative thickness of a film A / B / A 'having layers A and A' of 10 pm each and a layer B of 30 pm is denoted as 20/60/20.

For the various films described herein, layer "A" can be formed from any material known in the art for use in multilayer films or film-coated products. Thus, for example, layer A can be formed by a homopolymer or copolymer of polyethylene, and the polyethylene can be, for example, a VLDPE, a low-density polyethylene (LDPE), an LLDPE, a medium-density polyethylene (MDPE). ), or a high density polyethylene (HDPE), as well as other polyethylenes known in the art. Polyethylene can be produced by any suitable process, including metallocene-catalyzed processes and Ziegler-Natta catalyst-catalyzed processes. In addition, layer A can be a mixture of two or more such polyethylenes, and can include additives known in the art. Furthermore, one skilled in the art will understand that the layers of a multilayer film must have the proper viscosity match.

In multilayer structures, one or more A layers can also be an adhesion promoting tie layer, such as PRIMACOR ™ ethylene-acrylic acid copolymers available from The Dow Chemical Co., and / or ethylene-vinyl acetate copolymers. . Other materials for the A layers can be, for example, metal foil, nylon, ethylene-vinyl alcohol copolymers, poly (vinylidene chloride), poly (ethylene terephthalate), oriented polypropylene, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, graft modified polymers, other polyethylenes, such as HDPE, LDPE, LMDPE, and MDPE, and paper.

Layer "B" is formed by a blend of VLDPE / LDPE polymers of the invention, and can be any of the blends described herein. In one embodiment, layer B is formed of a blend of a metallocene catalyzed VLDPE polymer having a density less than 0.916 g / cm³, and an LDPE polymer having a density of 0.916 to 0.940 g / cm³. In another embodiment, layer B is formed by a mixture comprising: (a) a VLDPE copolymer produced by metallocene in the gas phase of ethylene and at least one C3 to C12 alpha-olefin and having a density of 0.900 to 0.915 g / cm³ and a melt index of 0.5 to 10 g / 10 min; and (b) an LDPE homopolymer or copolymer having a density of 0.916 to 0.940 g / cm³ and a melt index of 0.5 to 20 g / 10 min. In one embodiment, layer B is formed by a mixture comprising a gas phase metallocene produced VLDPE having a melt index having the lower limits of 0.5 g / 10 min or more, 0.7 g / 10 min or more, 1 g / 10 min or more, and having the upper limits of 5 g / 10 min or less, 3 g / 10 min or less, or 2 g / 10 min or less, the index ranges being flowability from any lower limit to any upper limit within the scope of the invention. In a preferred embodiment, layer B is formed of a blend as described herein, wherein the VLDPE component of the blend has one or more of the following characteristics, in addition to density, melt index, and others parameters described herein:

a) a CDBI composition distribution of 50 to 85%, alternatively 60 to 80%, or 55 to 75% or more to 70% or less;

b) a molecular weight distribution Mw / Mn of 2 to 3, alternatively 2.2 to 2.8;

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c) a molecular weight distribution Mz / Mw less than 2; Y

d) the presence of two peaks in a TREF measurement.

The thickness of each layer of the film, and of the overall film, is not particularly limited, but is determined according to the desired properties of the film. Typical film layers are about 1 to 1000 pins thick, more typically about 5 to 100 pins, and typical films have an overall thickness of 10 to 100 pins.

In one embodiment, the present invention provides a single layer (monolayer) film formed from any of the VLDPE / LDPE polymer blends of the invention; that is, a film having a single layer which is a B layer as described above.

In other embodiments, and using the nomenclature described above, the present invention provides multilayer films with any of the following structures:

a) two-layer films, such as A / B and B / B ';

b) three-layer films, such as A / B / A ', A / A' / B and B / B '/ B ”;

c) Four-layer films, such as A / A '/ A ”/ B, A / A' / B / A”, A / A '/ B / B', A / B / A '/ B', A / B / B '/ A', B / A / A '/ B', B / A / B / B ”and B / B / B” / B ”;

d) five-layer films, such

A / A / B / A ”/ B, A / B / A / B / B”,

B / A / B / B ”/ B”,

A / A / B / B / A ”,

A / B / B / B ”/ A,

B / B / A / B ”/ B” as A / A / A ”/ A” / B, A / A / A ”/ B / A”, A / A / B / A ”/ A”, A / A / A ”/ B / B, A / B / A / B / A”, A / B / A / A ”/ B, B / A / A / A” / B, A / A / B / B / B ”, B / A / A / B / B”, B / A / B / A / B ”, B / A / B / B” / A, A / B / B / B ”/ B”, and B / B '/ B ”/ B”' / B ””;

and similar structures for films having six, seven, eight, nine, or more layers. It should be appreciated that films having even more layers can be formed using the VLDPE / LDPE polymer blends of the invention, and such films are within the scope of the invention.

In any of the above embodiments, one or more A layers can be replaced by a substrate layer, such as glass, plastic, paper, metal, or the entire film can be coated or laminated onto a substrate. Thus, although the discussion herein has focused on multilayer films, the films of the VLDPE / LDPE polymer blends of the present invention can also be used as coatings; eg, films formed by the inventive polymers, or multilayer films that include one or more layers formed by the inventive polymers, can be coated onto a substrate such as paper, metal, glass, plastic, and other materials capable of accepting a coating. . Such coated structures are also within the scope of the present invention.

As described below, the films can be cast films or blown films. Films can be further embossed, or produced or processed according to other known film processes. Films can be tailored to specific applications by adjusting the thickness, materials and order of the various layers, as well as the additives in each layer.

In one aspect, films containing the monolayer or multilayer polymer blend composition can be formed using casting techniques, such as cold roll casting processes. For example, a composition can be melt extruded through a flat die and then cooled to form a film. As a specific example, cast films can be prepared using a pilot scale commercial cast film line machine, as follows. Polymer granules are melted at a temperature ranging from about 250 ° C to about 300 ° C, the specific melting temperature being chosen to match the melt viscosity of the particular resins. In the case of a multilayer cast film, the two or more different melts are conveyed to a coextrusion adapter that combines the two or more melt streams into a multilayer, coextruded structure. This layered flow is distributed through a single manifold film extrusion die to the desired width. The nozzle opening gap is typically about 600 pin. The material is then stretch thinned to the final gauge. The draw thinning ratio of the material is typically about 21: 1 for 0.8 mil (20 pin) films. A vacuum box or air knife can be used to clamp the melt exiting the nozzle opening to a main cold roll maintained at approximately 32 ° C. The resulting polymeric film is collected on a winder. The thickness of the film can be controlled by a calibrating monitor, and the film can be trimmed at the edges by a cutter. One or more treaters can be used to treat the surface of the film, if desired. Such cold roll casting processes and apparatus are well known in the art, and are described, for example, in The Wiley Encyclopedia of Packaging Technology, Second Edition, AL Brody and KS Marsh, Ed., John Wiley and Sons, Inc. , New York (1997). Although cold roll casting is an example, other forms of casting can be used.

ES 2 339 331 T3

In another aspect, films containing the monolayer or multilayer polymer blend composition can be formed using blowing techniques, ie, forming a blown film. For example, the composition can be melt extruded through an annular die and blown and then cooled to form a tubular blown film, which can then be axially slit and unfolded to form a flat film. As a specific example, blown films can be prepared as follows. The polymer blend composition is fed into the feed hopper of an extruder, such as a 63.5mm Egan extruder that is water cooled, resistance heated, and has an L / D ratio of 24: 1. The film can be produced using a 6 "Sano nozzle with a 2.24mm nozzle gap, along with a dual orifice non-rotating, non-adjustable air ring. The film is extruded through the die into a film that is cooled by blowing air over the surface of the film. The film is drawn from the die typically forming a cylindrical film which is cooled, folded, and optionally subjected to a desired auxiliary procedure, such as cracking, treating, sealing or printing. The finished film can be rolled onto rollers for further processing, or it can be fed into a bag machine and bagged. A particular blown film process and apparatus suitable for forming films according to embodiments of the present invention is described in US Patent No. 5,569,693. Of course, other blown film forming methods can also be used.

In another aspect, the invention relates to any polymeric product containing the polymer blend composition, produced by methods known in the art. In addition, this invention also includes products that have other specific end uses, such as film-based products, including stretch films, bags (i.e., shipping bags, garbage bags and sacks, industrial garbage sacks, and bags for food products), food and flexible packaging (e.g. fresh cut food packaging, frozen food packaging), personal care film pouches, medical film products (such as IV bags for intravenous products), diaper backsheets, and household plastic wrap. Products can also include packaging such as bundling, packaging or bundling of various products including various foods, carpet rolls, containers for liquids, and various similar goods normally arranged in containers or on pallets for shipping, storage and / or display. Products can also include surface protection applications, with or without stretching, such as temporary surface protection during manufacturing and shipping. There are many potential applications for articles and films produced from the polymer blend compositions described herein.

The advantageous properties described above, as well as others that one skilled in the art will appreciate from the present description, are illustrated herein in the following examples.

5. Examples

Materials and methods

Metallocene catalysts for the polymerization of the inventive VLDPE were prepared according to the methods described above for a non-bridged bis-Cp structure (such as a bis (1,3-methyl-n-butylcyclopentadienyl) zirconium dichloride).

In certain examples, various properties of the polymers were measured according to the following test procedures, and it is understood that whenever these properties are discussed in this specification and in the claims, such properties are to be measured in accordance with these procedures.

Tensile strength values ​​were measured (machine direction ("MD") and cross direction ("DT")) in accordance with ASTM D882-95A, except that film gauge was measured using ASTM D374-94 , Method C, except that the micrometer calibration was performed annually with a commercially available caliper block (Starret Webber 9, JCV1 & 2). As reflected in Table IV, tensile values ​​were measured at MD and DT at strain, MD and DT at 200%, and MD and DT at ultimate tensile.

The ACD protocol is an analytical scale TREF (Temperature Increasing Elution Fractionation) assay for semi-crystalline copolymers to characterize the composition distribution (DC). A sample is dissolved in a good solvent, cooled slowly to allow crystallization on a support, and then redissolved and washed off the support, heating during elution. The polymer chains are fractionated by differences in their crystallization temperature in solution, which is a function of the composition (and the structure of defects). A mass detector provides concentration versus elution temperature data; DC characterization is obtained by applying a calibration curve (ie, mole% comonomer vs. temperature) established using narrow DC standards. Two internal-use Visual Basic programs are used for data acquisition and analysis.

There are actually two distributions provided by the ACD test:

• Solubility distribution (weight fraction vs. solubility temperature) - measured directly.

• Composition distribution (weight fraction vs. comonomer content) - obtained by applying the calibration curve to the solubility distribution.

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The emphasis is usually placed on the characterization of the CD. However, the solubility distribution may be of equal or greater importance when:

• A calibration curve has not been established for the polymer of interest.

• The molecular weight of the sample is low, or the MWD is wide enough that a significant part of the sample is low molecular weight (M <20k). Under these circumstances, the reported DC is influenced by the dependence of molecular weight on solubility. The calibration curve must be corrected for the effect of molecular weight to give the true CDC, which requires a priori knowledge of the relative influence of molecular weight and composition on solubility for a given sample. In contrast, the solubility distribution correctly represents the contributions of both effects, without attempting to separate them.

Note that the solubility distribution must depend on the type of solvent and the crystallization / dissolution conditions. If calibrated correctly, the DC should be independent of changes in these experimental parameters.

The Composition Distribution Width Index (CDBI) was measured using the following instrumentation: ACD: Waters 150-C modified for TREF (Temperature Increasing Elution Fractionation) analysis (includes crystallization column, bypass pipes , time and temperature controllers); Column: 75 micron glass beads filling an HPLC (High Pressure Liquid Chromatography) type column; Refrigerant: Liquid Nitrogen; Software: Visual Basic “A-TREF” programs; and Detector: ELS-100 from Polymer Laboratories. The execution conditions for the CDBI measures were as follows:

GPC settings

Mobile phase: TCE (tetrachlorethylene)

Temperature: Column Compartment Cycles 5-115 ° C, Injector Compartment 115 ° C

Runtime: 1 hr 30 min

Balancing time: 10 min (before each run)

Flow rate: 2.5 ml / min

Injection volume: 300 pl

Pressure settings: transducer set to 0 when no flow, high pressure cutoff set to 3 MPa

Temperature controller settings

Initial temperature: 115 ° C

Ramp 1 temperature: 5 ° C, Ramp time = 45 min, Residence time = 3 min

Ramp 2 temperature: 115 ° C, Ramp time = 30 min, Residence time = 0 min

Alternative temperature controller settings if no two peaks are displayed in a TREF measurement:

Initial temperature: 115 ° C

Ramp 1 temperature: 5 ° C, Ramp time = 12 h, Residence time = 3 min

Ramp 2 temperature: 115 ° C, Ramp time = 12 h, Residence time = 0 min

In some cases, longer ramp times may be needed to show two peaks in a TREF measurement.

ELS Settings

Nebulizer temperature: 120 ° C

Evaporator temperature: 135 ° C

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Gas flow: 1.0 slm (standard liters per minute)

Heat transfer line temperature: 120 ° C

Melt index was measured according to ASTM D-1238-95. Melt index is reported in units of g / 10 min, or the numerically equivalent units of dg / min.

Density (g / cm³) was determined using pieces cut from compression molded plates according to ASTM D-1928-96, Procedure C, aged according to ASTM D618, Procedure A, and measured according to ASTM D1505-96.

In measuring 1% Secant Modulus, the procedures of ASTM D882-95A were followed, except that the film gauge was measured according to ASTM D374-94, Method C, except that the micrometer calibration was performed annually with a block commercially available calibrator (Starret Webber 9, JCV1 & 2).

In the measurement of the Elmendorf Tear, the procedures of ASTM D1922-94a were used, except that the gauge of the film was measured according to ASTM D374-94, Method C, except that the calibration of the micrometer was performed annually with a calibrating block available on the market (Starret Webber 9, JCV1 & 2).

Dart Drop values ​​were measured using the procedures of ASTM D1709-98, Method A, except that the film gauge was measured according to ASTM D374-94, Method C, except that the micrometer calibration was performed annually with a block. commercially available calibrator (Starret Webber 9, JCV1 & 2).

Haze was measured according to ASTM D1003-95.

Gloss was measured according to ASTM D2457-90.

Total Energy was measured according to ASTM D4272-90.

The test used to measure "puncture" values ​​simulates the penetration of a finger or bottle through plastic film, and is a recognized method for testing garbage bags. The test procedure is available from United Testing Machines, and is denoted as PLFL-201.01. In general, the test measures the force and energy required to pierce a plastic film with a gauge of 0.20-10.0 mils (50 to 250 pm). For puncture measurements, a film sample is placed in a clamp approximately 10 cm wide. A plunger with a 19 mm tip is pressed through it at a constant speed of 25 cm / min. A United Testing Machine SFM-1 is used, and is calibrated annually by the manufacturer. Before testing, the samples are conditioned at 23 ° C and 50% relative humidity for at least 40 hours after manufacture. The sample is cut through the transverse direction (DT) of the 15 cm bubble and in the case of blown film it is separated. Before testing, each sample is calibrated, with the mean thickness recorded in mils, taken from the gage micrometer data sheet. The mean gauge of the sample area is used in the calculations of the test results. The mean values ​​of the peak load and breaking energy of 5 specimens are used to compile the final test results for each sample.

The polydispersity or molecular weight index (Mw / Mn) is calculated based on the ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) by size exclusion chromatography.

Hot tack strength is measured according to the following procedure. Hot tack test specimens were 15 mm wide specimens cut from original films. The samples were covered on the back (laminated) with PET to avoid rupture at the seal transition and elongation or adhesion to the seal bars. A J&B HOT Tack Tester 3000 was used to make the seal, using a seal bar pressure of 0.5 MPa, and a seal time of 0.5 s. The hot tack strength was then determined, after a cooling time of 0.4 s and a peel speed of 200 mm / min.

Gauge: Film gauge was measured according to ASTM D374-94, Method C, except that micrometer calibration was performed annually with a commercially available gauge block (Starret Webber 9, JCV1 & 2).

Shrinkage (%) was determined in machine direction (MD) and cross direction (DT) as follows. A 100mm circle is cut from the film. The machine direction is marked, then the specimen is covered with talc and then heated. The amount of shrinkage is measured in both MD and DT, and is reported as% MD shrinkage and% DT shrinkage.

For measurements of film properties, film samples were annealed by heating for 48 hours at 60 ° C prior to testing.

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Example 1 (Comparative)

A commercial scale gas phase reactor system was operated under condensed mode conditions for a 24 hour period. Table I summarizes the reaction conditions for this 24 hour period. The measured densities of the polyethylene polymers produced throughout this period ranged from 0.9090 to 0.9124 g / cm.³.

TABLE I

<td></td><td>SHORT</td><td>HIGH</td><td>HALF</td>

<td>Reaction speed</td><td> 8,8</td><td> 11,5</td><td> 9,9</td>

<td>(klb / h) (kg / h)</td><td>4.0 x 10³</td><td>5.22 x 10³</td><td>4.5 x 10³</td>

<td>Total catalyst feed (Ib / h)</td><td> 0,95</td><td> 1,73</td><td> 1,27</td>

<td>(kg / h)</td><td> 0,43</td><td> 0,785</td><td> 0,576</td>

<td>Reactor temperature (° C)</td><td> 78,8</td><td> 80,0</td><td> 80,3</td>

<td>Reactor pressure</td><td> 252</td><td> 268</td><td> 259</td>

<td>(psig) (MPa)</td><td> 1,74</td><td> 1,84</td><td> 1,79</td>

<td>Feed</td><td> 8375</td><td> 10586</td><td> 9156</td>

<td>ethylene (Ib / h) (kg / h)</td><td> 3799</td><td> 4802</td><td> 4153</td>

<td>Feed</td><td> 851</td><td> 1243</td><td> 1052</td>

<td>hexene (Ib / h) (kg / h)</td><td> 386</td><td> 564</td><td> 477</td>

<td>Feed</td><td> 0,1423</td><td> 0,2546</td><td> 0,1963</td>

<td>hydrogen (Ib / h) (kg / h)</td><td> 64,55</td><td> 115,5</td><td> 89,04</td>

<td>Molar ratio C₆/ C₂</td><td> 0,239</td><td> 0,0249</td><td> 0,0250</td>

<td>Partial pressure of C₂H₄</td><td> 168</td><td> 182</td><td> 172</td>

<td>Flow ratio C₆/ C₂</td><td> 0,0958</td><td> 0,1261</td><td> 0,1146</td>

<td>Surface velocity</td><td> 2,00</td><td> 2,09</td><td> 2,05</td>

<td>(ft / s) (cm / s)</td><td> 61,0</td><td> 63,7</td><td> 62,5</td>

<td>Bed level (ft) (m)</td><td> 35,6</td><td> 39,6</td><td> 37,5</td>

<td></td><td> 10,9</td><td> 12,1</td><td> 11,4</td>

<td>Middle bed density</td><td> 34,0</td><td> 39,1</td><td> 37,4</td>

<td>PD of manifold plate (psi)</td><td> 2,56</td><td> 9,6</td><td> 7,67</td>

<td>(kPa)</td><td> 17,7</td><td> 66</td><td> 52,9</td>

<td>Cycle Gas Cooler PD (psi)</td><td> 28,9</td><td> 12,6</td><td> 10,4</td>

<td>(kPa)</td><td> 61</td><td> 86,9</td><td> 71,7</td>

<td>Catalyst Feed Speed ​​(rpm)</td><td> 388</td><td> 519</td><td> 434</td>

Example 2 (Comparative)

A gas phase reactor system different from the system of Example 1 was operated to produce VLDPEs of this invention. Table II summarizes the reaction conditions for two different runs, as well as properties of the resulting polymers. As reflected in Table II, the densities of the polymers were 0.9118 and 0.9121 g / cm³.

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TABLE II

<td></td><td>Execution 1</td><td>Execution 2</td>

<td colspan="3">Lab. QC data</td>

<td>IF (g / 10 min)</td><td> 1,02</td><td> 1,03</td>

<td>RIF (HLMI / MI)</td><td> 16,69</td><td> 17,13</td>

<td>Density (g / cm³)</td><td> 0,9118</td><td> 0,9121</td>

<td>Apparent density (g / cm³)</td><td> 0,4500</td><td> 0,4494</td>

<td>Average particle size (pm)</td><td> 997</td><td> 921</td>

<td>VOC (%)</td><td> 38,8</td><td> 38,2</td>

<td>DTP &lt;250 μ (%)</td><td> 1,073</td><td> 1,232</td>

<td>DTP &lt;125 μ (%)</td><td> 0,267</td><td> 0,175</td>

<td>Bread (%)</td><td> 0,042</td><td> 0,027</td>

<td>Fine (&lt;125 pm) (%)</td><td> 0,267</td><td> 0,175</td>

<td>Flow time (s)</td><td> 7,93</td><td> 7,81</td>

<td colspan="3">MCL data</td>

<td>Ash (ppm)</td><td> 144</td><td> 137</td>

<td>Zr by ICPES (ppm)</td><td> 0,5163</td><td> 0,5187</td>

<td>Al by ICPES (ppm)</td><td> 15,5</td><td> 14-,9</td>

<td colspan="3">Process data</td>

<td>Prod. Rate (klb / h) (kg / h)</td><td>154 6.99 x 10⁴</td><td>172 7.81 x 10⁴</td>

<td>Hydrogen (ppm)</td><td> 149</td><td> 153</td>

<td>Ethylene (% by mole)</td><td> 70,1</td><td> 70,0</td>

<td>Hexene (% in moles)</td><td> 1,70</td><td> 1,73</td>

<td>Butene (% in moles)</td><td> 0,00</td><td> 0,00</td>

<td>Partial pressure of C₂ (psia) (MPa)</td><td> 220,4 1,520</td><td> 220,2 1,518</td>

<td>Concent ratio H₂/ C₂</td><td> 2,13</td><td> 2,19</td>

<td>Flow ratio H₂/ C₂</td><td> 0,017</td><td> 0,021</td>

<td>Concent ratio C_s/ C₂</td><td> 0,243</td><td> 0,247</td>

<td>Cs / C flow ratio₂</td><td> 0,119</td><td> 0,115</td>

<td>Concent ratio C₄/ C₂</td><td> 0,0000</td><td> 0,0000</td>

ES 2 339 331 T3

<td>C4 / C2 flow ratio</td><td> 0,000</td><td> 0,000</td>

<td>Temperature (° F)</td><td> 175,0</td><td> 175,0</td>

<td>(° C)</td><td> 79,4</td><td> 79,4</td>

<td>Bed weight (Ib)</td><td> 593</td><td> 594</td>

<td>(kg)</td><td> 269</td><td> 269</td>

<td>Resid. Time (h)</td><td> 3,88</td><td> 3,45</td>

<td>Gas velocity (ft / s)</td><td> 2,25</td><td> 2,25</td>

<td>(cm / s)</td><td> 68,6</td><td> 68,6</td>

<td>plate dP (Ή₂Ο)</td><td> 26,5</td><td> 26,2</td>

<td>(cm H₂OR)</td><td> 67,3</td><td> 66,5</td>

<td>Cooler dP (psig)</td><td> 0,78</td><td> 0,78</td>

<td>(MPa)</td><td> 5,4</td><td> 5,4</td>

<td>RX Pressure (psig)</td><td> 299,6</td><td> 299,6</td>

<td>(MPa)</td><td> 2,066</td><td> 2,066</td>

<td>Feeding C₂ (Ib / h)</td><td> 193,7</td><td> 211,9</td>

<td>(kg / h)</td><td> 87,86</td><td> 96,12</td>

Example 2a (Comparative)

Table IIA is an example of reactor conditions to produce an embodiment of an m-VLDPE of the present invention having a melt index of 12.28 dg / min.

TABLE IIA

<td colspan="2">Reactor process data</td><td>Degree</td><td>ECD-330</td>

<td colspan="2">Number of hourly data points</td><td></td><td></td>

<td colspan="2">Label v name of PMX database</td><td></td><td></td>

<td></td><td></td><td></td><td></td>

<td>Production rate</td><td>R1C218</td><td>Klb / h</td><td> 77,2</td>

<td>Catalyst rate</td><td>RÍQ218</td><td>Ib / h</td><td> 9,6</td>

<td>Cat productivity</td><td>RPM Cale</td><td>Ib / lb</td><td> 8447</td>

<td>Rx temperature</td><td>R1C163</td><td>oF</td><td> 176,0</td>

<td>Rx pressure</td><td>R1P177</td><td>psig</td><td> 304,1</td>

<td>Inlet temperature</td><td>R1T166</td><td>oF</td><td> 95,6</td>

<td>Dew point-entry</td><td>R1TDELTA</td><td>oF</td><td> 50,7</td>

<td>% condensed</td><td>R1WTPCT</td><td>% p</td><td> 9,9</td>

<td>Surface velocity</td><td>R1C944</td><td>ft / s</td><td> 2,49</td>

<td>Bed weight</td><td>R1W176</td><td>Klb</td><td> 140,2</td>

<td>Bed height</td><td>R1D174</td><td>ft</td><td> 48,5</td>

<td>Ethylene partial pressure</td><td>R1P486</td><td>psia</td><td> 186,9</td>

<td>Ethylene concentration</td><td>R1V486</td><td>% mole</td><td> 58,64</td>

ES 2 339 331 T3

<td>Hexene conc</td><td>R1V482</td><td>% mole</td><td> 1,65</td>

<td>H2 conc</td><td>R1A881B</td><td>ppm</td><td> 509</td>

<td>Isopentane conc</td><td>R1V48A</td><td>% mole</td><td> 7,19</td>

<td>Nitrogen conc</td><td>R1V483</td><td>% mole</td><td> 31,80</td>

<td>H2 / C2 =</td><td>R1H2C2E</td><td>ppm / mol</td><td> 8,67</td>

<td>C6 = / C2 =</td><td>R1Q489</td><td>mol / mol</td><td> 2,81</td>

<td>Ethylene flow</td><td>R1B100</td><td>Klb / h</td><td> 67,0</td>

<td>Hexene flow</td><td>R1B104</td><td>Klb / h</td><td> 9,73</td>

<td>Hydrogen flow</td><td>R1B107</td><td>Ib / h</td><td> 6,16</td>

<td>Isopentane flow</td><td>R1F317</td><td>Klb / h</td><td> 225</td>

<td>Flow ratio C6 = / C2 =</td><td>R1R104</td><td>Ib / lb</td><td> 0,160</td>

<td>Flow ratio H2 = / C2 =</td><td>R1R107</td><td>Ib / klb</td><td> 0,092</td>

<td>Bed FBD / SBD Rx1</td><td>R1D175</td><td>Relationship</td><td> 0,78</td>

<td>Lower FBD Rx1</td><td>R1P171</td><td>Ib / ft3</td><td> 18,9</td>

<td>Rx1 top FBD</td><td>R1P172</td><td>Ib / ft3</td><td> 17,4</td>

<td>FBD filter medium Rx1</td><td>R1C171</td><td>Ib / ft3</td><td> 17,9</td>

<td>Cat Pct Activity Rx1</td><td>R1Q587</td><td>Pct</td><td> 59</td>

<td>Fall / h IPDS Rx1</td><td>R1C174SP</td><td>Fall / h</td><td> 24,2</td>

<td>Res time. bed Rx1</td><td>R1C176</td><td>Hours</td><td> 1,86</td>

<td>Recovery flow Screw</td><td>05C306</td><td>klb / h</td><td> 5,01</td>

<td>Recovery flow Sulzer</td><td>R1F419</td><td>Ib / h</td><td> 551</td>

<td>Bleeder weight N2 Rx1</td><td>05W461</td><td>klb</td><td> 145,7</td>

<td>Bleeder weight stm Rx1</td><td>05W487</td><td>klb</td><td> 27,3</td>

<td>p / p &amp; alt of FBD cale.</td><td>Cale</td><td>Ib / ft3</td><td> 17,5</td>

<td>FBD / SBD stall.</td><td>Cale</td><td>Relationship</td><td> 0,76</td>

<td>Performance space time</td><td>STY</td><td>Ib / h / ft3</td><td> 9,6</td>

<td>Residence time</td><td>Cale</td><td>h-1</td><td> 1,86</td>

<td>Prod. Cat. Aubum</td><td>R1Q588</td><td>klb / lb</td><td> 7,23</td>

<td>Rapid drain Rx1</td><td>R1F134</td><td>klb / h</td><td> 0,000</td>

<td>Bleeder vent Rx1</td><td>R1F180</td><td>klb / h</td><td> 0,000</td>

<td>Compound purge Rx1</td><td>R1B135</td><td>klb / h</td><td> 0,000</td>

<td>Lab data.</td><td></td><td></td><td></td>

<td>flow index</td><td>35LR101</td><td>dg / min</td><td> 12,28</td>

<td>Gradient density</td><td>35LR102</td><td>g / cc</td><td> 0,9107</td>

<td>Apparent density</td><td>35LR104</td><td>Ib / ft3</td><td> 23,0</td>

<td>APS</td><td>35LR107</td><td>inches</td><td> 0,043</td>

<td>Fine (&lt;120 mesh)</td><td>35LR110</td><td>% weight</td><td> 0,04</td>

<td>Ash</td><td>35LR105</td><td>ppm</td><td> 105</td>

<td></td><td></td><td></td><td></td>

<td>Prod. Cat. Normal (for C2 = 175 psia)</td><td></td><td>Ib / lb</td><td> 7488</td>

<td>to C2PP^TO1,83.</td><td></td><td></td><td></td>

<td>Bed weight</td><td colspan="2">FBD * BedHt</td><td> 143530</td>

<td>Res time.</td><td colspan="2">BedWt / ProdRate</td><td> 1,86</td>

Example 3 (Comparative)

Certain VLDPE polymers of the invention were prepared using gas phase polymerization using metallocene catalyst systems described herein. Films were formed from these polymers. The films of the invention are identified below as Samples A and G. Sample A was prepared in the reactor system of Example 1, and Sample G was prepared in the reactor system of Example 2. The comonomers used to prepare Samples A and G were ethylene and hexene. Fluidized gas phase reactors were operated to produce the resulting copolymers.

ES 2 339 331 T3

The polymerizations were carried out in the gas phase continuous fluidized bed reactors described in Examples 1 and 2. The fluidized beds of these reactors consisted of polymeric granules. The gaseous ethylene and hydrogen feed streams were introduced below each reactor bed in the recycle gas line. The hexene comonomer was introduced below the reactor bed. An inert hydrocarbon (isopentane) was also introduced to each reactor in the recycle gas line, to provide additional heat capacity to the recycle gases from the reactor. The individual flow rates of ethylene, hydrogen and hexene comonomer were controlled to maintain the compositional targets set. Gas concentrations were measured by an online gas chromatograph to ensure a relatively constant composition in the recycle gas stream.

The solid catalyst was injected directly into the fluidized beds using purified nitrogen. Catalyst injection rates were adjusted to maintain a constant production rate. The growing polymeric particle reaction beds were maintained in a fluidized state by a continuous flow of the constituent feed and recycle gas through each reaction zone. To maintain constant reactor temperatures, the recycle gas temperature was continuously adjusted up or down to accommodate any change in the rate of heat generation due to polymerization. The fluidized bed was kept at a constant height by extracting a part of the bed at a rate equal to the formation of the particulate product. The product was transferred to a trap to remove incorporated hydrocarbons.

Example 4 (Comparative)

In order to demonstrate the surprisingly improved toughness of the VLDPEs of this invention, various films made from polyethylene polymers prepared using different procedures were compared. Specifically, the properties of certain polymers of the invention, that is, those prepared according to the gas polymerization processes corresponding to the invention, using metallocene catalysts, were compared with certain comparative polymers, that is, polymers prepared according to methods which are not those of the invention. Referring now to comparative examples, Sample B was prepared using a comparative polymer, specifically a linear low density polyethylene (0.9189 g / cm³) prepared using a metallocene catalyst in a gas phase polymerization process. Sample C was prepared using a linear low density polyethylene (0.9199 g / cm³) prepared using a Ziegler-Natta catalyst in a gas phase polymerization process. Sample D was prepared using a plastomer (0.9031 g / cm³) prepared using a metallocene catalyst in a high pressure mass polymerization process. Sample E was prepared using a very low density polyethylene (0.9132 g / cm³) prepared using a Ziegler-Natta catalyst in a solution polymerization process. Sample F was prepared using a very low density polyethylene (0.9104 g / cm³) prepared using a metallocene catalyst in a solution polymerization process.

Each of the polymers was formed into a film. The process conditions for the preparation of the films reported in Table V are set forth in Table III below. The properties of each of the films were then measured. The properties of the films reported in Table V are set forth in Table IV.

TABLE III

<td>Measured properties</td><td>TO</td><td>B</td><td>C</td><td>D</td><td>AND</td><td>F</td><td>G</td>

<td>Melt temperature</td><td> 385</td><td> 388</td><td> 377</td><td> 397</td><td> 381</td><td> 377</td><td> 392</td>

<td>(° F) (° C)</td><td> 196</td><td> 198</td><td> 192</td><td> 203</td><td> 194</td><td> 192</td><td> 200</td>

<td>Extruder head pressure (psi)</td><td> 3520</td><td> 3490</td><td> 3120</td><td> 4490</td><td> 3220</td><td> 3190</td><td> 3780</td>

<td>(MPa)</td><td> 24,3</td><td> 24,1</td><td> 21,5</td><td> 31,0</td><td> 22,2</td><td> 22,0</td><td> 26,1</td>

<td>Extruder speed (rpm)</td><td> 46,4</td><td> 46,4</td><td> 46,4</td><td> 41,8</td><td> 46,6</td><td> 43,3</td><td> 45,4</td>

<td>Line speed (ft / min)</td><td> 123</td><td> 121</td><td> 119</td><td> 119</td><td> 119</td><td> 119</td><td> 119</td>

<td>(m / min)</td><td> 3,75</td><td> 3,67</td><td> 3,63</td><td> 3,63</td><td> 3,63</td><td> 3,63</td><td> 3,63</td>

ES 2 339 331 T3

<td>Production rate (Ib / h) (kg / h)</td><td> 155 70,3</td><td> 152 68,9</td><td> 152 68,9</td><td> 154 69,9</td><td> 151 68,5</td><td> 152 68,9</td><td> 153 69,4</td>

<td>Frost Line Height (in) (cm)</td><td> 20 51</td><td> 18 46</td><td> 15 38</td><td> 25 63</td><td> 16 41</td><td> 18 46</td><td> 19 48</td>

<td>Steering load of extruder (%)</td><td> 55,4</td><td> 55,7</td><td> 49,1</td><td> 59,6</td><td> 47,5</td><td> 47,6</td><td> 56,6</td>

<td>Motor load / Prod. Rate</td><td> 0,357</td><td> 0,366</td><td> 0,323</td><td> 0,387</td><td> 0,315</td><td> 0,313</td><td> 0,37</td>

<td>Horsepower</td><td> 13,6</td><td> 13,7</td><td> 12</td><td> 13,2</td><td> 11,7</td><td> 10,9</td><td> 13,6</td>

<td>Output Rate / Horsepower</td><td> 11,38</td><td> 11,11</td><td> 12,63</td><td> 11,67</td><td> 12,86</td><td> 13,93</td><td> 11,21</td>

<td>Torque (hp.rpm)</td><td> 0,293</td><td> 0,295</td><td> 0,26</td><td> 0,316</td><td> 0,251</td><td> 0,252</td><td> 0,3</td>

TABLE IV

<td>Measured properties</td><td>TO</td><td>B</td><td>C</td><td>D</td><td>AND</td><td>F</td><td>G</td>

<td colspan="8">Density (g / cm³)</td>

<td>Molded</td><td> 0,9129</td><td> 0,9189</td><td> 0,9199</td><td> 0,9031</td><td> 0,9132</td><td> 0,9104</td><td> 0,9114</td>

<td colspan="8">Reoloqy</td>

<td>IF (I2)</td><td> 1,07</td><td> 1,17</td><td> 1,10</td><td> 1,09</td><td> 1,00</td><td> 0,96</td><td> 0,97</td>

<td>HLMI (121)</td><td> 18,50</td><td> 19,14</td><td> 30,03</td><td> 18,03</td><td> 30,37</td><td> 35,54</td><td> 17,04</td>

<td>Relationship (121/12)</td><td> 17,29</td><td> 16,36</td><td> 27,30</td><td> 16,54</td><td> 30,37</td><td> 37,02</td><td> 17,56</td>

<td>Swollen Ml</td><td> 1,12</td><td> 1,08</td><td> 1,17</td><td> 1,01</td><td> 1,14</td><td> 1,23</td><td> 1,10</td>

<td colspan="8">Hexene content</td>

<td>% in weigh</td><td> 9,6</td><td> 7,1</td><td></td><td></td><td></td><td></td><td> 10,2</td>

ES 2 339 331 T3

<td colspan="8">GPC-HT</td>

<td>Mn</td><td> 50612</td><td> 48653</td><td></td><td></td><td></td><td></td><td> 52016</td>

<td>Mw</td><td> 100908</td><td> 100064</td><td></td><td></td><td></td><td></td><td> 102647</td>

<td>Mw / Mn</td><td> 1,99</td><td> 2,06</td><td></td><td></td><td></td><td></td><td> 1,97</td>

<td>Mz / Mw</td><td> 1,66</td><td> 1,69</td><td></td><td></td><td></td><td></td><td> 1,61</td>

<td>Mz + 1 / Mw</td><td> 2,46</td><td> 2,52</td><td></td><td></td><td></td><td></td><td> 2,29</td>

<td colspan="8">ACD</td>

<td>CDBI</td><td> 64,5</td><td> 6,7</td><td></td><td></td><td></td><td></td><td> 55,3</td>

<td>% soluble</td><td> 0,6</td><td> 0,6</td><td></td><td></td><td></td><td></td><td> 1,1</td>

<td colspan="8">DSC (° C)</td>

<td> 1^to melting peak</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>2nd peak</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>3rd peak</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>2nd melting peak</td><td> 118,34</td><td> 120,70</td><td> 124,56</td><td></td><td> 118,00</td><td> 105,68</td><td> 117,83</td>

<td>2nd peak</td><td> 103,41</td><td> 109,62</td><td></td><td> 99,64</td><td> 123,25</td><td></td><td> 101,72</td>

<td>3rd peak</td><td></td><td></td><td></td><td></td><td> 103,62</td><td></td><td></td>

<td>ΔΗ (J / g)</td><td> 112,06</td><td> 126,96</td><td> 128,45</td><td> 94,76</td><td> 112,45</td><td> 108,61</td><td> 109,84</td>

<td>Crystallization peak</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>2nd peak</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>3rd peak</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Intrinsic tear (g / mil)</td><td> 346</td><td> 351</td><td> 460</td><td> 237</td><td> 546</td><td> 433</td><td> 327</td>

Films made from the polymers of the invention (Samples A and G) were tested according to the test procedures discussed above. The same properties of comparative films, made from polymers prepared using non-inventive procedures, were also measured to demonstrate certain improved properties that result from the invention. The results of these measurements are shown in Table V.

Films made from the polymers of the invention showed a marked improvement over comparative polymers in Dart Drop values, which measure the energy that causes a polymeric film to fail under specified conditions of impact from a free-falling dart. As reflected in Table V, the Dart Drop values ​​for Samples A and G were 623 and 1,289 g / mil, respectively. These Dart Drop values ​​were more than 50% greater than the Dart Drop values ​​for all films made from polymers prepared using solution polymerization procedures. That is, the Dart Drop for Sample E (a film made from a VLDPE prepared using a Ziegler-Natta catalyst in a solution polymerization procedure) was 338 g / mil, and the Dart Drop for Sample F (a film made from a VLDPE prepared using a metallocene catalyst in a solution polymerization process) was 491 g / mil. The Dart Drop values ​​for films made from polymers of the invention were also more than 50% greater than the Dart Drop values ​​for films made from polymers prepared using other gas phase polymerization procedures. The Dart Drop for Sample B (a film made from an LDPE prepared using a metallocene catalyst in a gas phase polymerization process) was 362 g / mil, and the Dart Drop for Sample C (a film made from an LDPE prepared using a Ziegler-Natta catalyst in a gas phase polymerization process) was 112 g / mil.

ES 2 339 331 T3

The polymers of the invention also showed improved Puncture properties, reflecting the resistance of a stretch wrap film to probe penetration. As reflected in Table V, for Samples A and G, the Peak Puncture Force values ​​were 11.55 and 9.96 lb / mil, respectively, and the Puncture Break Energy values ​​were 40, 40 and 32.52 in / lb / mil, respectively. These values ​​were greater than the values ​​for all comparative films made of polymers prepared using solution polymerization procedures. That is, for Sample E (a film made from a VLDPE prepared using a Ziegler-Natta catalyst in a solution polymerization procedure), the Peak Force was 10.02 lb / mil, and the Puncture Break Energy was 34 , 33 lb / mil. For Sample F (a film made from a VLDPE prepared using a metallocene catalyst in a solution polymerization process), the Peak Force was 10.70 lb / mil, and the Puncture Break Energy was 35.29 in. lb / mil. The Puncture properties of films made from the polymers of the invention were also higher than the Puncture properties of polymers prepared using other gas phase polymerization procedures. For Sample B (a film made from an LDPE prepared using a metallocene catalyst in a gas phase polymerization process), the Peak Force was 9.98 lb / mil and the Puncture Break Energy 31.25 in-ft. /thousand. For Sample C (a film made from an LDPE prepared using a Ziegler-Natta catalyst in a gas phase polymerization process) the Peak Force was 8.13 lb / mil and the Puncture Break Energy was 23.46 in. ft / mil.

TABLE V

<td></td><td>TO</td><td>B</td><td>C</td><td>D</td><td>AND</td><td>F</td><td>G</td>

<td>Tensile deformation, DM (psi) (MPa)</td><td> 1078 7,4</td><td> 1335 9,2</td><td> 1447 10,0</td><td> 738 4,9</td><td> 1087 7,5</td><td> 934 6,4</td><td> 1054 7,3</td>

<td>Tensile at deformation, DT (psi) (MPa)</td><td> 1080 7,4</td><td> 1397 9,6</td><td> 1618 11,0</td><td> 713 4,9</td><td> 1118 7,7</td><td> 921 6,4</td><td> 1050 7,3</td>

<td>Tensile at 200%, DM (psi) (MPa)</td><td> 1911 13,2</td><td> 1901 13,1</td><td> 1905 13,1</td><td> 1812 12,5</td><td> 2269 15,6</td><td> 2684 18,5</td><td> 1897 13,1</td>

<td>Ultimate tensile, DM (psi) (MPa)</td><td> 11.232 77,4</td><td> 10.550 72,7</td><td> 8.603 59,3</td><td> 10.579 72,9</td><td> 9.586 66,1</td><td> 9.218 63,6</td><td> 11.598 80,0</td>

<td>Ultimate tensile, DT (psi) (MPa)</td><td> 9.197 63,4</td><td> 8.012 55,2</td><td> 6.240 43,0</td><td> 10.778 74,3</td><td> 6.748 46,5</td><td> 8.597 59,3</td><td> 9.463 65,2</td>

<td>Elongation at strain, MD (%)</td><td> 6,8</td><td> 6,2</td><td> 5,9</td><td> 8,8</td><td> 6,5</td><td> 7,3</td><td> 6,9</td>

<td>Elongation at strain, DT (%)</td><td> 6,7</td><td> 6,2</td><td> 5,9</td><td> 8,0</td><td> 6,2</td><td> 6,5</td><td> 6,8</td>

<td>Elongation at break, MD (%)</td><td> 474</td><td> 518</td><td> 545</td><td> 439</td><td> 446</td><td> 458</td><td> 480</td>

<td>Elongation at break, SD (%)</td><td> 617</td><td> 627</td><td> 740</td><td> 592</td><td> 711</td><td> 736</td><td> 618</td>

<td>Secant modulus 1%, DM (psi) (MPa)</td><td> 25.300 174</td><td> 36.270 250</td><td> 37.330 257</td><td> 14.630 101</td><td> 27.360 189</td><td> 22.520 155</td><td> 25.080 173</td>

<td>Secant modulus 1%, ......... PI ....... (psi) .......................</td><td> 27.500 190</td><td> 39.380 272</td><td> 47.020 324</td><td> 17.030 117</td><td> 30.480 210</td><td> 23.330 161</td><td> 26.780 185</td>

ES 2 339 331 T3

<td>Elmendorf tear, DM (g / mil)</td><td> 202</td><td> 247</td><td> 225</td><td> 159</td><td> 352</td><td> 133</td><td> 178</td>

<td>Elmendorf tear, DT (g / mil)</td><td> 396</td><td> 439</td><td> 764</td><td> 362</td><td> 696</td><td> 475</td><td> 392</td>

<td>Fall from Dart, Method A (g)</td><td> 773</td><td> 442</td><td> 145</td><td> 1723</td><td> 422</td><td> 624</td><td> 1651</td>

<td>Dart Drop, Method A (g / mil)</td><td> 623</td><td> 362</td><td> 112</td><td> 1336</td><td> 338</td><td> 491</td><td> 1289</td>

<td>Caliber (mil)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Half</td><td> 1,24</td><td> 1,22</td><td> 1,29</td><td> 1,29</td><td> 1,25</td><td> 1,27</td><td> 1,28</td>

<td>Under</td><td> 1,10</td><td> 1,13</td><td> 1,15</td><td> 1,09</td><td> 1,15</td><td> 1,19</td><td> 1,14</td>

<td>Tall</td><td> 1,34</td><td> 1,31</td><td> 1,40</td><td> 1,52</td><td> 1,34</td><td> 1,36</td><td> 1,38</td>

<td>Turbidity (%)</td><td> 7,7</td><td> 17,7</td><td> 14,3</td><td> 1,0</td><td> 6,9</td><td> 3,3</td><td> 9,3</td>

<td>Brightness at 45 degrees</td><td> 58</td><td> 44</td><td> 51</td><td> 92</td><td> 70</td><td> 76</td><td> 58</td>

<td>(l / l)</td><td> 191</td><td> 47</td><td> 208</td><td> 178</td><td> 197</td><td> 212</td><td> &gt;214</td>

<td>Peak Force per Puncture (Ib)</td><td> 14,32</td><td> 12,17</td><td> 10,48</td><td> 14,19</td><td> 12,53</td><td> 13,58</td><td> 12,75</td>

<td>Peak Force per Puncture (Ib / mil)</td><td> 11,55</td><td> 9,98</td><td> 8,13</td><td> 11,00</td><td> 10,02</td><td> 10,70</td><td> 9,96</td>

<td>Energy of Break (pulglb)</td><td> 50,09</td><td> 38,13</td><td> 30,26</td><td> 48,09</td><td> 42,92</td><td> 44,82</td><td> 41,66</td>

<td>Energy at Break (inIb / mil)</td><td> 40,40</td><td> 31,25</td><td> 23,46</td><td> 37,28</td><td> 34,33</td><td> 35,29</td><td> 32,54</td>

<td>Total Energy at -29 ° F (34 ° C) (ft / lb)</td><td> 3,01</td><td> 2,34</td><td> 1,79</td><td> 2,85</td><td> 2,42</td><td> 1,86</td><td> 3,07</td>

<td>Total Energy at TA (ft / lb)</td><td> *</td><td> 4,57</td><td> 1,80</td><td> *</td><td> 2,73</td><td> 4,61</td><td> *</td>

<td>Shrinkage, MD (%)</td><td> 42</td><td> 45</td><td> 61</td><td> 46</td><td> 72</td><td> 79</td><td> 46</td>

<td>Shrinkage, SD (%)</td><td> -4</td><td> -4</td><td> -14</td><td> -8</td><td> -23</td><td> -10</td><td> -9</td>

greater than capacity

Example 5 (Comparative)

As reflected in Table VI, the Dart Drop of films made of polymers of the invention was also substantially higher than the Dart Drop of films made of higher density polymers prepared from a gas phase polymerization process. using a metallocene catalyst. In this example, the properties of unheated films made from VLDPEs of the invention were compared to unheated films made using LDPEs that were not of the invention. Samples "AA" and "BB" were both non-inventive films prepared from polyethylenes having a density of 0.917 and a melt index of 3.5.

ES 2 339 331 T3

Sample "AA" was 1.54 mil thick, while Sample "BB" was 0.85 mil thick. Samples "CC" and "DD" were films of the invention, prepared from a VLDPE. Sample "CC", made of a VLDPE with a melt index of 3.5 and a density of 0.912, had a mean gage thickness of 1.49, and Sample "DD", made of a VLDPE with an index with a flow rate of 3.5 and a density of 0.912, it had a mean gauge thickness of 0.81. Both the inventive and non-inventive polymers were prepared using a gas phase polymerization process with a metallocene catalyst system. The data shows that, although the VLDPEs of the invention had a lower density than the LDPEs that were not of the invention, the Dart Drop toughness of the VLDPE films of the invention was higher than the Dart drop of LDPE films that were not of the invention. Specifically, the mean Dart Drop (in g / mil) for the "CC" and "DD" Invention Samples was more than 40% greater than the mean Dart Drop for the non-invention "AA" samples. and "BB".

<td colspan="5">Table VI</td>

<td></td><td>AA</td><td>BB</td><td>DC</td><td>DD</td>

<td>Dart Drop</td><td></td><td></td><td></td><td></td>

<td>(g)</td><td> 964</td><td> 610</td><td> 1.338</td><td> 826</td>

<td>(g / mil)</td><td> 626</td><td> 717</td><td> 898</td><td> 1.020</td>

<td>Caliber (mil)</td><td></td><td></td><td></td><td></td>

<td>Half</td><td> 1,49</td><td> 0,81</td><td> 1,54</td><td> 0,85</td>

<td>Under</td><td> 1,50</td><td> 0,81</td><td> 1,43</td><td> 0,77</td>

<td>Tall</td><td> 1,56</td><td> 0,88</td><td> 1,54</td><td> 0,85</td>

<td>Puncture</td><td></td><td></td><td></td><td></td>

<td>Peak Force (Ib)</td><td> 16,00</td><td> 10,82</td><td> 15,75</td><td> 11,03</td>

<td>Peak Force (Ib / mil)</td><td> 10,39</td><td> 12,73</td><td> 10,57</td><td> 13,61</td>

<td>Energy at Break (inglb)</td><td> 58,20</td><td> 38,31</td><td> 59,37</td><td> 38,62</td>

<td>Energy at Break (inIb / mil)</td><td> 37,79</td><td> 45,07</td><td> 39,85</td><td> 47,68</td>

Example 6 (Comparative)

Another improved property exhibited by the VLDPEs of the invention is superior hot tack strength at low initiation temperatures, an important property for films. At an initiation temperature of 100 ° C, the AG Samples discussed above were subjected to a Hot Tack test. The results are as follows: hot tack was 6.56 for Sample A; 0.38 for sample B; 0.28 for Sample C; 6.50 for Sample D; 2.35 for sample E; 3.38 for Sample F; and 6.90 for Sample G. Thus, Samples A and G were shown to perform substantially better than the other samples in the Hot Tack tests.

Example 7

Films formed from a resin were prepared for mVLDPE films of the present invention of 12 dg / min, 0.912 g / cm³, with 5 to 40% by weight of LDPE, according to the procedures described herein. Both LD200 and LD270 were used. These LDPEs are commercially available LDPE products. Films were extrusion coated onto Kraft paper, and mechanical properties and sealing properties were measured. Results are shown in Table VII for mechanical properties, Table VIII for hot tack forces, and Table IX for heat seal forces.

ES 2 339 331 T3

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ES 2 339 331 T3

Table IX ^(to): Heat Seal Force (N)

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<td></td><td>or</td><td>ID</td><td>or</td><td>or</td><td></td><td>x—</td><td>CM</td><td>CM</td><td>CD</td><td>CO</td><td></td>

<td></td><td>or</td><td>OR</td><td></td><td>v—</td><td></td><td></td><td></td><td>v ~</td><td></td><td></td><td></td>

ES 2 339 331 T3

The data in Tables VIII-IX show several advantageous properties of films or coatings made from LDPE / mVLDPE blends of the present invention. All blends showed improved machine direction and cross direction Elmendorf Tear strength, and improved puncture tear energy, compared to conventional LDPE film (the control sample, "100% B"). . In hot tack strength measurements (Table VIII), the blends generally showed superior adhesion at most temperatures, and particularly at the highest temperatures, compared to the LDPE control sample. Similarly, the heat seal forces for the LDPE / mVLDPE blends were generally higher than for the LDPE control sample at most temperatures.

Example 8 (Comparative)

The following materials are compared in this example:

TABLE X

Material to form the films tested in Tables Xla-XVIIb

<td>Product family</td><td>Grade Name *</td><td>IF, g / 10 min</td><td>wt% comonomer</td><td>Density, g / cm³</td>

<td>LDPE</td><td>LD-200.48</td><td> 7,5</td><td></td><td> 0,918</td>

<td>EVE</td><td>UL-01418</td><td> 14</td><td> 18</td><td></td>

<td>EMA</td><td>TC-220</td><td> 5</td><td> 24</td><td></td>

<td>In BA</td><td>XW-25 AL</td><td> 7,8</td><td> 25</td><td></td>

<td>lonomer</td><td>batchk ™ 8030 (Na)</td><td> 2,8</td><td></td><td> 0,956</td>

<td>EAA</td><td>Escor ™ 5100</td><td> 6,5</td><td> 6,5</td><td></td>

<td>Plastomer</td><td>Exact ™ 3040</td><td> 16</td><td></td><td> 0,900</td>

<td>Mvldpe</td><td>ECD-330</td><td> 12</td><td></td><td> 0,912</td>

<td colspan="4">* All products produced by ExxonMobil Chemical Company.</td><td>ECD-330 is a</td>

development material

Monolayer coatings were applied using an 8.89 cm extruder. The cold roll, 750 mm in diameter, had a matte finish and was kept at 15 ° C throughout the run. The substrate used was 70 # Kraft paper, which was corona treated at 10 kW prior to coating. The air gap was kept at 150mm. Target coating thicknesses were 15, 25 and 50 g / m².

Processability tests were performed according to established ETC protocols. The extrudability of the resin is determined by measuring motor load, pressure, and melt temperatures at 25, 50, and 150 rpm. Resin taper is measured at 25 output rpm on untreated paper at line speeds of 25, 50, 100, and 200 meters per minute (mpm). Peak draw thinning is determined by extruding the resin at 25 output rpm onto untreated paper and increasing the line speed at an acceleration of 10 meters per minute per second.

EC-330 (12 dg / min, 0.912 g / cm³) and LD200.48 (7.5 dg / min, 0.915 g / cm³) in mixtures of 0, 20, 40, 60, 80 and 100 percent by weight of ECD-330. ECD-330 was extruded at 100% for process comparisons only and coating weights of 25 and 50 g / m². The ECD-330 used in this work was produced at MBPP on November 19, 2000. It was formulated with 200 ppm Irganox 1076.

Linear comparisons were Exact 3040 (16.5 dg / min, 0.900 g / cm³), Dow 3010 (5.4 dg / min, 0.921 g / cm³), Dow Affinity PT1450 (7.5 dg / min, 0.902), Nova Sclair 61C (5.3 dg / min, 0919). Exact 3040 and Nova Sclair 61C were mixed with 20 weight percent LD200.48. The Dow Affinity PT1450 was run at 100% and mixed with 20 weight percent LD200.48. UL02020 (20 dg / min, 20 weight percent VA) was also included in the comparative comparison.

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Films were tested for Elmendorf tear, tensile strength, and puncture resistance. 15 g / m samples were tested² Regarding burst strength by standard methods for a Perkins-Bowthruck Bond tester, Type CSR-710-64 at room temperature (~ 25 ° C), which can be used to quantify coating efficiency, or bond strength the relative role.

Processing comparisons

Processing data is shown in tables Xla and Xlb. Data from the DPUT-1212 evaluation are included. The motor load values ​​at the three spindle speeds overlap, indicating that the DPUT1212 and ECD-330 had similar extrudability.

As expected, adding LDPE reduces the load on the motor. Similar trends are seen for head pressures. These results show narrowing at 100 mpm and maximum stretch thinning, respectively, for ECD-330 and DPUT-1212. These properties are also the same between the two resins.

The taper as a function of the LDPE content in the ECD-330 at four different line speeds is given in Table Xla. There is a significant reduction in taper with 20 weight percent LD200.48 added, but little significant change at 40 weight percent and above.

Engine load results for an ECD-330 / LD200.48 80/20 mix and linear comparison samples show that the ECD-330 mix is ​​more easily processed than the Dow 3010 and Nova Sclair 61C, which you can expect with the much lower melt indices for LLDPE resins. The processability for the ECD-330 blend is similar to the Affinity PT1450 and LD resin blend, and is more difficult than the higher melt index Exact 3040.

At higher line speeds, the ECD-330 mix has very good taper, which is only equaled by Affinity PT1450 / LD and Exact 3040 mix. Taper for unmixed Dow 3010, Nova Sclair 61C and PT1450 is much worse. Results show maximum draw thinning for linear resins with unblended PT1450 and Exact 3040, which have the highest achievable line speeds. The ECD-330 falls in third place, but can be run at much higher line speed / draw thinning than the Dow 3010, Nova Sclair 61C and PT1450 with LDPE.

Physical properties

The mechanical properties are given in Tables XlIa and XlIb for the 15 g / m samples.², Tables 3a and 3b for the 25 g / m samples² and 4a and 4b for the 50 g / m samples².

Property trends are similar for all three coating weights in LDPE, LDPE / ECD-330 blends. Results show burst test data for 15 g / m samples², which indicate that LDPE has better adhesion to paper under the extrusion conditions used, and further shows that Elmendorf tear and puncture energy are negatively affected by the addition of LDPE.

As the burst test results for the comparative linear resins and an EVA show, the ECD-330 / LDPE blend has relatively poor adhesion to Kraft paper, and is only better than Dow Affinity PT1450. The mechanical property data for the 25 g / m samples² coating show it. The tensile breaking energy for ECD-330 and ECD-330 / LDPE blend is relatively good. Only the Dow 3010 and Nova Sclair 61C were better, which is due, at least in part, to the much higher molecular weight of the LLDPE resins. The Elmendorf tear, especially for the unmixed ECD-330, was very good. The puncture breaking energy was slightly better for ECD-330 than for the other linear resins. Dow Affinity PT1450 had very good puncture resistance.

Hot Tack and Heat Seal Results

Hot tack and heat seal comparisons between ECD-330 and DPUT-1212 at 25 g / m² coating weight show that ECD-330 has far superior hot tack and heat seal performance than DPUT-1212. This may be due to slightly lower resin density for ECD-330 or less surface oxidation. The TOF-SIMS analysis of the ECD-330 in this work shows that the surface oxygen concentration is below detectable limits, indicating that the resin did not significantly degrade during processing.

Hot tack comparisons for ECD-330 / LDPE blends at 15, 25 and 50 g / m² coating weight, respectively. The general trends in these representations are that LD200.48 has the worst hot tack strength, and increasing the amount of ECD-330 in the mix improves the hot tack strength. The trends were most evident in thicker coatings.

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Nova Sclair 61C has the worst hot tack strength, followed by Dow 3010. Dow 3010 has good hot tack strength at thicker gauges, but at relatively high temperatures, greater than 115 ° C. Dow Affinity PT1450 and PT1450 / LDPE blend have slightly better hot tack strength at lower temperatures than ECD-330 i.e. 90 ° C and below, but significantly lower hot tack strength above 100 ° C. Exact 3040 has a similar hot tack strength profile compared to ECD-330, but is offset at approximately 10 ° C lower temperatures. As expected, UL02020 has the lowest temperature hot tack strength.

Heat seal forces for ECD-330 / LDPE blends follow similar trends to hot tack data. Table XVIa gives heat seal data for ECD-330 / LDPE blends at 25 g / m²coating weight. Increasing the amount of ECD-330 in the mix improves the heat seal strength slightly relative to LDPE. ECD-330 as a single component has significantly better heat seal strength than blends or LDPE.

The heat sealing force for competitive linear resins at 25 g / m² coating weight shows that ECD-330 has similar sealing performance to Exact 3040, but at temperatures approximately 5 ° C higher. The Dow 3010 and Nova Sclair 61C have acceptable heat seals only above 110 ° C.

(Table goes to next page)

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TABLE XIa

Processing data for resins and blends ECD-330 / LD200.48

<td>Resin</td><td>LD200.48</td><td>ECD-330</td><td>ECD-330</td><td>ECD-330</td><td>ECD-330</td><td>ECD-330</td>

<td>% LD200</td><td> 100</td><td> 80</td><td> 60</td><td> 40</td><td> 20</td><td> 0</td>

<td>Set temperature (° C)</td><td> 295</td><td> 295</td><td> 295</td><td> 295</td><td> 295</td><td> 295</td>

<td>25 RPM</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Motor load (amps)</td><td> 58</td><td> 62</td><td> 67</td><td> 71</td><td> 76</td><td> 83</td>

<td>Head pressure (bar)</td><td> 33</td><td> 40</td><td> 39</td><td> 44</td><td> 45</td><td> 52</td>

<td>(MPa)</td><td> 3,3</td><td> 4,0</td><td> 3,9</td><td> 4,4</td><td> 4,5</td><td> 5,2</td>

<td>Adapter temperature (° C)</td><td> 299</td><td> 299</td><td> 300</td><td> 300</td><td> 300</td><td> 300</td>

<td>Pipe temperature (° C)</td><td> 296</td><td> 296</td><td> 296</td><td> 296</td><td> 296</td><td> 296</td>

<td>50 RPM</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Motor load (amps)</td><td> 86</td><td> 94</td><td> 103</td><td> 107</td><td> 118</td><td> 131</td>

<td>Head pressure (bar)</td><td> 42</td><td> 54</td><td> 54</td><td> 55</td><td> 69</td><td> 57</td>

<td>(MPa)</td><td> 4,2</td><td> 5,4</td><td> 5,4</td><td> 5,5</td><td> 6,9</td><td> 5,7</td>

<td>Adapter temperature (° C)</td><td> 297</td><td> 299</td><td> 300</td><td> 300</td><td> 301</td><td> 302</td>

<td>Pipe temperature (° C)</td><td> 295</td><td> 296</td><td> 297</td><td> 297</td><td> 297</td><td> 298</td>

<td>150 RPM</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Motor load (amps)</td><td> 152</td><td> 165</td><td> 180</td><td> 193</td><td> 210</td><td> 229</td>

<td>Pressure of</td><td> 59</td><td> 69</td><td> 72</td><td> 77</td><td> 79</td><td> 87</td>

<td>head (bar) (MPa)</td><td> 5,9</td><td> 6,9</td><td> 7,2</td><td> 7,7</td><td> 7,9</td><td> 8,7</td>

<td>Adapter temperature (° C)</td><td> 286</td><td> 295</td><td> 3010</td><td> 306</td><td> 310</td><td> 314</td>

<td>Pipe temperature (° C)</td><td> 288</td><td> 295</td><td> 299</td><td> 303</td><td> 306</td><td> 319</td>

<td>Output at 50 rpm (kg / 5 min)</td><td> 6,69</td><td> 6,84</td><td> 7,00</td><td> 7,08</td><td> 7,23</td><td> 7,36</td>

<td>Output at 50 RPM (kg / h)</td><td> 80</td><td> 82</td><td> 84</td><td> 85</td><td> 87</td><td> 88</td>

<td>Departure</td><td> 1,60</td><td> 1,64</td><td> 1,68</td><td> 1,70</td><td> 1,74</td><td> 1,76</td>

<td>specific at 50 rpm (kg / h / rpm)</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Power consumption spec. (kJ / kg)</td><td> 328</td><td> 351</td><td> 376</td><td> 386</td><td> 417</td><td> 454</td>

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<td>Narrowing at 25 rpm (cm)</td><td> 3,7</td><td> 4,0</td><td> 4,5</td><td> 5,8</td><td> 10,0</td><td> 19,9</td>

<td>Narrowing at 50 rpm (cm)</td><td> 3,3</td><td> 3,5</td><td> 3,9</td><td> 4,7</td><td> 7,7</td><td> 23,8</td>

<td>Narrowing at 100 rpm (cm)</td><td> 3,1</td><td> 3,3</td><td> 3,6</td><td> 4,2</td><td> 6,4</td><td>EW</td>

<td>Narrowing at 200 rpm (cm)</td><td>MB</td><td>MB</td><td>MB</td><td> 4,2</td><td> 6,1</td><td>EW</td>

<td>Slim down. per stretch max (mpm)</td><td> 124,5</td><td> 141,5</td><td> 171,5</td><td> 218</td><td> 381</td><td> **</td>

<td>Sample of 15 g / m²</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Spindle speed (rpm)</td><td> 27,9</td><td> 27,6</td><td> 27,2</td><td> 27,3</td><td> 26,8</td><td> 19,9</td>

<td>Narrowing (cm)</td><td> 3</td><td> 3,3</td><td> 3,7</td><td> 4</td><td> 5,5</td><td> **</td>

<td>Motor load (amps)</td><td> 60</td><td> 85</td><td> 71</td><td> 74</td><td> 77</td><td> 69</td>

<td>Pressure of</td><td> 31</td><td> 42</td><td> 43</td><td> 36</td><td> 35</td><td> 38</td>

<td>melt (bar) (MPa)</td><td> 3,1</td><td> 4,2</td><td> 4,3</td><td> 3,6</td><td> 3,5</td><td> 3,8</td>

<td>Melt temperature (° C)</td><td> 299</td><td> 300</td><td> 300</td><td> 300</td><td> 300</td><td> 300</td>

<td>Sample of 25 g / rn²</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Spindle speed (rpm)</td><td> 46,5</td><td> 46</td><td> 45,3</td><td> 45,5</td><td> 44,6</td><td> 33,1</td>

<td>Narrowing (cm)</td><td> 3</td><td> 33</td><td> 3,7</td><td> 4</td><td> 5,8</td><td> 26,5</td>

<td>Motor load (amps)</td><td></td><td> 85</td><td> 95</td><td> 101</td><td> 105</td><td> 102</td>

<td>Melt pressure (bar)</td><td></td><td> 42</td><td> 39</td><td> 41</td><td> 39</td><td> 40</td>

<td>(MPa)</td><td></td><td> 4,2</td><td> 3,9</td><td> 4,1</td><td> 3,9</td><td> 4,0</td>

<td>Melt temperature (° C)</td><td></td><td> 300</td><td> 301</td><td> 300</td><td> 300</td><td> 301</td>

<td>Sample of 50 g / m²</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Spindle speed (rpm)</td><td> 93</td><td> 92</td><td> 90,6</td><td> 91</td><td> 89,2</td><td> 66,2</td>

<td>Narrowing (cm)</td><td> 3</td><td> 3,3</td><td> 3,7</td><td> 4,3</td><td> 6,5</td><td> 23</td>

<td>Motor load (amps)</td><td> 113</td><td> 122</td><td> 135</td><td> 147</td><td> 160</td><td> 152</td>

<td>Melt pressure (bar)</td><td> 39</td><td> 48</td><td> 47</td><td> 48</td><td> 46</td><td> 46</td>

<td>(MPa)</td><td> 3,9</td><td> 4,8</td><td> 4,7</td><td> 4,8</td><td> 4,6</td><td> 4,6</td>

<td>Melt temperature (° C)</td><td> 300</td><td> 302</td><td> 303</td><td> 300</td><td> 304</td><td> 302</td>

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TABLE Xlb

Processing data for competitive linear resins and an EVA

<td>Resin</td><td>Exact 3040</td><td>Dow 3010</td><td>Affinity PT1450</td><td>PT1450</td><td>Nova 61C</td><td>UL02020</td>

<td>% LD200</td><td> 20</td><td></td><td></td><td> 20</td><td> 20</td><td></td>

<td>Set temperature (° C)</td><td> 295</td><td> 295</td><td> 295</td><td> 295</td><td> 295</td><td> 240</td>

<td>25 RPM</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Motor load (amps)</td><td> 72</td><td> 92</td><td> 84</td><td> 77</td><td> 92</td><td> 70</td>

<td>Head pressure (bar) (MPa)</td><td> 44 4,4</td><td> 64 6,4</td><td> 48 4,8</td><td> 41 4,1</td><td> 55 5,5</td><td> 44 4,4</td>

<td>Adapter temperature (° C)</td><td> 299</td><td> 303</td><td> 300</td><td> 300</td><td> 304</td><td> 243</td>

<td>Pipe temperature (° C)</td><td> 296</td><td> 299</td><td> 297</td><td> 297</td><td> 299</td><td> 240</td>

<td>50 RPM</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Motor load (amps)</td><td> 109</td><td> 136</td><td> 123</td><td> 114</td><td> 135</td><td> 100</td>

<td>Head pressure (bar) (MPa)</td><td> 52 5,2</td><td> 83 8,3</td><td> 65 6,5</td><td> 61 6,1</td><td> 84 8,4</td><td> 52 5,2</td>

<td>Adapter temperature (° C)</td><td> 298</td><td> 308</td><td> 301</td><td> 300</td><td> 310</td><td> 243</td>

<td>Pipe temperature (° C)</td><td> 295</td><td> 302</td><td> 297</td><td> 297</td><td> 303</td><td> 241</td>

<td>150 RPM</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Motor load (amps)</td><td> 202</td><td> 202</td><td> 210</td><td> 194</td><td> 233</td><td> 157</td>

<td>Head pressure (bar) (MPa)</td><td> 70 7,0</td><td> 70 7,0</td><td> 82 8,2</td><td> 78 7,8</td><td> 118 11,8</td><td> 65 6,5</td>

<td>Adapter temperature (° C)</td><td> 301</td><td> 301</td><td> 310</td><td> 306</td><td> 327</td><td> 243</td>

<td>Pipe temperature (° C)</td><td> 299</td><td> 299</td><td> 305</td><td> 303</td><td> 318</td><td> 243</td>

<td>Output at 50 rpm (kg / 5 min)</td><td> 7,26</td><td> 6,93</td><td> 7,31</td><td> 7,16</td><td> 6,76</td><td> 7,71</td>

<td>Output at 50 RPM (kg / h)</td><td> 87</td><td> 83</td><td> 88</td><td> 86</td><td> 81</td><td> 93</td>

<td>Specific output 50 rpm (kg / h / rpm)</td><td> 1,74</td><td> 1,66</td><td> 1,76</td><td> 1,72</td><td> 1,62</td><td> 1,86</td>

<td>Power consumption spec. (kJ / kg)</td><td> 383</td><td> 501</td><td> 429</td><td> 406</td><td> 510</td><td> 331</td>

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<td>Narrowing at 25 rpm (cm)</td><td> 11,5</td><td> 9,3</td><td> 13,6</td><td> 9,1</td><td> 8,9</td><td> 15,5</td>

<td>Narrowing at 50 rpm (cm)</td><td> 9,1</td><td> 8,8</td><td> 12,7</td><td> 7,3</td><td> 8,1</td><td> 15</td>

<td>Narrowing at 100 rpm (cm)</td><td> 6,8</td><td> 8,5</td><td> 10,9</td><td> 5,8</td><td> 7,7</td><td> 12</td>

<td>Narrowing at 200 rpm (cm)</td><td> 6</td><td> 8,4</td><td> 9,7</td><td> 5,5</td><td> 7,6</td><td> 9</td>

<td>You lose weight. per stretch max (mpm)</td><td> 502</td><td> 264,5</td><td> 506</td><td> 298</td><td> 249,5</td><td> &gt; 600</td>

<td>Sample of 15 g / m²</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Spindle speed (rpm)</td><td> 26,5</td><td> 27,8</td><td> 26,9</td><td> 27,3</td><td> 29,2</td><td> 25,7</td>

<td>Narrowing (cm)</td><td> 5,8</td><td> 7,9</td><td> 9,3</td><td> 5,4</td><td> 7,4</td><td> 12,3</td>

<td>Motor load (amps)</td><td> 70</td><td> 98</td><td> 85</td><td> 79</td><td> 102</td><td> 71</td>

<td>Melt pressure (bar) (MPa)</td><td> 32 3,2</td><td> 55 5,5</td><td> 41 4,1</td><td> 38 3,8</td><td> 57 5,7</td><td> 38 3,8</td>

<td>Melt temperature (° C)</td><td> 298</td><td> 302</td><td> 300</td><td> 300</td><td> 304</td><td> 244</td>

<td>Sample of 25 g / m²</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Spindle speed (rpm)</td><td> 44,2</td><td> 46,4</td><td> 44,8</td><td> 45,5</td><td> 48,6</td><td> 42,9</td>

<td>Narrowing (cm)</td><td> 6,2</td><td> 8</td><td> 9,8</td><td> 5,5</td><td> 7,6</td><td> 12</td>

<td>Motor load (amps)</td><td> 102</td><td> 125</td><td></td><td> 106</td><td> 127</td><td> 90</td>

<td>Pres. Of the fund. (bar) (MPa)</td><td> 38 3,8</td><td> 60 6,0</td><td> 44 4,4</td><td> 41 4,1</td><td> 60 6,0</td><td> 40 ,40</td>

<td>Melt temperature (° C)</td><td> 299</td><td> 303</td><td> 300</td><td> 301</td><td> 304</td><td> 244</td>

<td>Sample of 50 g / m²</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Spindle speed (rpm)</td><td> 88,4</td><td> 92,8</td><td> 89,6</td><td> 91</td><td> 97,2</td><td> 85,8</td>

<td>Narrowing (cm)</td><td> 7,7</td><td> 8,2</td><td> 10,6</td><td> 6,2</td><td> 8</td><td> 11,6</td>

<td>Motor load (amps)</td><td> 150</td><td> 187</td><td> 166</td><td> 153</td><td> 192</td><td> 122</td>

<td>Pres. Of the fund. (bar) (MPa)</td><td> 46 4,6</td><td> 75 7,5</td><td> 51 5,1</td><td> 48 4,8</td><td> 81 8,1</td><td> 44 4,4</td>

<td>Melt temperature (° C)</td><td> 301</td><td> 310</td><td> 303</td><td> 303</td><td> 315</td><td> 246</td>

ES 2 339 331 T3

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ES 2 339 331 T3

Table Xllb. Mechanical properties for competitive resins at coating weights of 15 g / m².

<td>035 UL 02020 fifteen</td><td>N s 2 O CO oí O 2 oa_ tsj ° - b. or OI CM »£ £ CM w ®</td>

<td>032 Nova 61C twenty fifteen</td><td>or -&gt; b- &lt;O 2o OI CN or O ® CM or to O 'ÍCM Sp cHcsT -esT -w °</td>

<td>029 PT1450 20 fifteen</td><td>θ '* ®O °° * * ° £ Ot t- £ N OI £ VM T-</td>

<td>026 Affinity PT1450 15</td><td>m u&gt; 2 o 03 ° oo 't. &lt;or co_M«Roa” £ cm oí S “θ '* £ r- m</td>

<td>023 i Dow 3010 fifteen</td><td>or co ® or * 2 ® Σ? 'T. ®- «L oo OI £ OM &lt;N ® £ ¡£ CM OI, - O</td>

<td>020 Exact 3040 twenty fifteen</td><td>IOO ®O COO ®® - «O Tt ^ Ol £ OI CMCM NN T- OI £ T- O&gt;</td>

<td>Notebook 22249-043- Resin % LDPE Coating weight (g / m²)</td><td>_DC 2 or&gt; 2 2 Ό -O O&gt; O) O) 5? oo □ o - ³ &lt;? ³ " o O Q. -o &lt;0 Q. S Q. _ ¿ CT5 &lt;β '**' £ - A -— * Ό E Η H 2 ® Έ S s 2 = «« = = «- = _ 0-3« ® _ _ o UJ 15 Ό o ° - Ouñm «« “® · - · "Φ T5 2 and “© O Ό Ό · □ ° ® ® .5 * - -o «~ -o« - ° - .2 .2 _? S) or e? Ϋ́ ΰ? «« ®a5l - '«SH ®2l-« 2F§®®§§®c¿ t £ ^ LQ Q (¿Q UJ QQQQQ 0. U_ UJ 0. LU UJ UJ</td>

ES 2 339 331 T3

Table Xllla. Mechanical properties for ECD-330 / LDPE blends at coating weights of 25 g / m².

<td>018 ECD330 0 25</td><td>b »co 2 o 'ίο oo' í.io m CM or £ CM * CM * 5 5 £ &lt;OR * 5 CM *</td>

<td>015 ECD330 twenty 25</td><td>r, &lt;ooo t- co? 2 w N t CM £ CO CM * T- * £ ¡2? CM * ™ -r- ~</td>

<td>012 ECD330 40 25</td><td>• o &lt;n 2nd 2 2nd ™ CM W cm * cm * £ 8 Ξ cm £ &lt;t- '</td>

<td>009 ECD330 60 25</td><td>o CO 2 O CSI Tt OOO ^ Oly,</td>

<td>006 ECD330 80 25</td><td>o 00 2o 2^or 'T. co ® co W CM g} CO CO * CM *? 5 5 * CM * £ F</td>

<td>003 LD200 100 25</td><td>a&gt; ogo co. «Oo 2 * o o-co «Eye co cm O®» 2 CM r- r '</td>

<td>Notebook 22249-043- Resin % LDPE Coating weight (g / m²)</td><td>_ _ 2 or 2 2 CC 1 1 1 • o Ό _o) &lt;t&gt; 2¹ 2¹OR OR 3 or - = ³OO Q. -o &lt;0 Q. S Q. 2 2 - c .2 ί: “ t_ &lt;0 φ * C (0 u. &lt;0 r- 1_ ~&gt; _ | _ _ »_ re re ³ c « ³ _ ³o lu re λ o 5 - o CU CU Q. '**' m CL CU CU -2 (U or 2 or · - · - Φ U υ Φ Q. U o 2 - Ό O Ό Ό CC ¿1 r Q. c «Φ 2 ¡j Ό re -S o« 2 .2 " _ ? O) Or you Σ? or ü E? ® «=,« Λ =. C φ Φ C φ Φ Φ jq 2 I Φ Ϊ ¿HC κ b- Φ 2 h 3 □ C 3 3 C 0¿ - QQD¿ CQ Q tu QQQQQ 0. U. LU 0. U- LU</td>

ES 2 339 331 T3

Table Xlllb. Mechanical properties for competitive resins at coating weights of 25 g / m².

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ES 2 339 331 T3

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ES 2 339 331 T3

Table XlVb. Mechanical properties for competitive resins at coating weights of 50 g / m

<td>037 UL 02020 fifty</td><td>&lt;o &lt;ooo T- O o * 0. &lt;or í = «»</td>

<td>034 Nova 61C²⁰ 50</td><td>r- b. oo * - cn oo^M 'T gjo áñ 33</td>

<td>031 PT1450 20 fifty</td><td>b- co OO «or CO or O« O. · * r- ™ g_S heard &lt;n 38</td>

<td>028 Affinity PT1450 fifty</td><td>b- r- oo cn oo 'T.'A' T 'T «Or cncn £ 3</td>

<td>025 Dow 3010 fifty</td><td>σ&gt; σ&gt; OO «9 2 5 (V r- ~ ™ sis m ™ 2</td>

<td>022 Exact 3040 twenty fifty</td><td>&amp; 2 S 2 SS c &lt;° - cm 2JJ5 cn cn ¡gis 2 m Ώ * &lt;o</td>

<td>Notebook 22249-043- Resin % LDPE Coating weight (g / m²)</td><td>_ _ £ σ&gt; - S CC ii - Ό 5 P t _S&gt; ¿) oo = o = 1ü 5 S £ S? 2 35 2. Η 1- SS t E fe re λ js 2 - - ^ &lt;3 - S *³_ _ or LLI re Λ or Ϊ - t (Ü CQ Q_ * BB * O «« J ® re or re q · - · - - Φ OQ Φ Q. Q Φ CCO · c · Q— ® ® .2 - «£ -o _ro .2 .2 " _ ? S) or ü E »or ü E&gt; &lt;0 ^ - · =, «-S =. Φ «=, &lt;Λ -, CO Φ c Φ Φ φ or 2 Φ 2 HCSG) 2 H 2 3 C 3 3 C Ol =&gt; QQ (r: £ QQlUQQQQQa.U.lUa.U.lU</td>

ES 2 339 331 T3

Table XVa. Hot tack and heat seal data for ECD-330 / LDPE blends at 15 g / m coating weights²

<td>014 ECD330 20 fifteen</td><td></td><td>pjSOOOONCOIO ► nns in vs co ° 10 in co SS ID TT</td><td></td><td>ΦΝΦΦΝτ- ^ CO ▼ ^ coocoococooo OO T- CÍ oí OÍ fí</td>

<td>011 ECD330 40 fifteen</td><td></td><td>ow &lt;d / mho * so rt ιη ίο φ s ω in co</td><td></td><td>COIOb-OCOt-COlft o 'r- r- r- r- ri</td>

<td>008 ECD330 60 fifteen</td><td></td><td>COCOvOCDOW ^ CO hn otoio o co id co nT cd in xf co</td><td></td><td>COCOr-OCOCOON co co c © co oo O T- V- oí co co co</td>

<td>005 ECD330 80 fifteen</td><td></td><td>(ΜΦΦΝΟΙΟΟΝΦΟ O&gt; O IO OG ^ T- CO O V- IC CO C © * O CO</td><td></td><td>νΝΟΦΟΦΝΦ c \ ® ° ® o OO T- hey hey hey hey</td>

<td>002 LD200 100 fifteen</td><td></td><td>NGib ^ COr-Nr-S OCOG ^ O * eO &lt;0T-_CO &lt;© OO Tt uí * Ti CO oí</td><td></td><td>'flOT-COOOCOO G ^ CO ^ CM CO CM ^ O o T- oi heard heard heard heard</td>

<td>Notebook 22249-043- Resin % LDPE Coating weight (g / m²)</td><td>Hot stickiness (N) -&gt; Temp. (° C) |</td><td>as &lt;as OlOOOT-vCMCMCO</td><td>Heat sealing (Ib) —► Temp. (° C) 1</td><td>OR LO OR 1D OR IDOIDOOt-t-CM</td>

ES 2 339 331 T3

Table XVb. Hot tack and heat seal data for competitive resins at gsm coating weights²

<td>035 UL02020 fifteen</td><td></td><td>oo</td><td> 1 0,60</td><td> 1 3,06</td><td> | 5,00</td><td> 00 10</td><td> | 5,12</td><td> 4,12 3,70</td><td></td><td></td><td></td><td> 0,13</td>

<td>032 Nova 61C 20 fifteen</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>co co co or co 10 O &lt;0 00 O 00_ oo co r? co uí *</td><td></td><td></td><td></td><td></td>

<td>029 PT1450 20 fifteen</td><td></td><td></td><td></td><td></td><td></td><td> | 0,02 1</td><td>00 or or</td><td>^ • OOIOCOO ^ CMO co cns co o co τ- cm co in co co</td><td></td><td></td><td></td><td></td>

<td>026 PT1450 fifteen</td><td></td><td></td><td></td><td></td><td></td><td> | 0,02 |</td><td>| 0.84 I</td><td>CO CO v- b * CO OO ^ iO cm co in in in 10 cm</td><td></td><td></td><td></td><td></td>

<td>023 Dow 3010 fifteen</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CMCMCMOO&gt; ^ TT-CM Ο Ο Ο ω r; s Tf in φ ooo co conT</td><td>I Z9'¿</td><td> 5,63 |</td><td></td><td></td>

<td>020 Ex. 3040 20 fifteen</td><td></td><td></td><td></td><td></td><td></td><td>CM O OR</td><td> | 2,49 |</td><td>oococo ^ - ^ oioco O 00 O 00 CM CM c © ^ ^ uíoocooocoioío</td><td></td><td></td><td></td><td></td>

<td>Notebook 22249-043- Resin % LDPE Coating weight (g / m²)</td><td>Hot stickiness (N) -&gt; Temp. (° C) 1</td><td>Γ 09</td><td> ¡ 99</td><td>1 or ¿</td><td> 10</td><td>OR 00</td><td>85 l</td><td>O 10 O 10 O 10 o O10QQt-t-CMNCO Ο&gt; Ο&gt; τ · ^ τ · ^^ τ “τ ·</td><td>135 I</td><td> 140 |</td><td>Heat sealed (Ib) -&gt; Temp. (° C)</td><td> | 09</td>

ES 2 339 331 T3 σ&gt; or ω o

CM CM &lt;D in 10 v- 'CM CM CM cm' cm 'cm'

OM ^ NOCOCO »&lt;0 &lt;* 1 ocTot-cocococo

CO 'í 10 &lt;0 CM

O 10 OO v-_ &lt;0

OOO vvv

CO T- CO CO CM 10 co co or&gt; 03 co co

OOOOTT v

00 O CM CO 'Cf CM t-_ CO CO OO CM OOO V- CM CO CO

Φ CO CO T- s »OW O&gt; CM CM O

O v- 'CM CO

O 10 O 10 O 10 o

10O10O10O10OOTT-CMCMCO CONNOOCOG) G) ^^ vvTT “r ·

ES 2 339 331 T3

Table XVIa. Hot tack and heat seal data for ECD-330 / LDPE blends at 25 g / m coating weights²

<td>018 ECD330 0 25</td><td></td><td></td><td></td><td>co o_ τί_ ^ 7 mmo in oo 'oo ° ° ONN</td><td></td><td>CM CO b- O CO CO CM O CO O) CO θ '&lt;O 10 rf 10</td>

<td>015 ECD330 20 25</td><td></td><td></td><td></td><td>MIOOCN + ^^ NID o_ co - co_ b- σ&gt; o «(D b s' ° b ID 1«</td><td></td><td>* B- or σ&gt; or σ&gt; σ&gt; σ&gt; ιο Tt τ -__ Tt co t-_ b-_ CM 00 «O &lt;0 o T- eJ cm co &lt;*&gt; tj- ~ co co 'co</td>

<td>012 ECD330 40 25</td><td></td><td></td><td></td><td>(NNr-lDOMOr-M or o Tf Φ S 00 CO S (O</td><td></td><td>o io co ν— T- m o&gt; co 'T. co r * i co_ co 'T. Ό. 'Q. O T- ▼ - CM CO Tf CO co</td>

<td>009 ECD330 60 25</td><td></td><td></td><td></td><td>CMOCOO) O&gt; l0N&gt; O) ^ to co cm co σ&gt; o σ&gt; σ&gt; _ oo o'rt s 'h oo' Ν Φ io Tt</td><td></td><td>CO CO 10 or co r-, co oor * co v- ^ r * o ▼ - oí co co co co</td>

<td>006 ECD330 80 25</td><td></td><td>h- C3 θ '</td><td>oo</td><td>^ νΟΦΦΦΟΟ ^ o * 0. ° ® θ 'Ν φ' Ν Ν φ 'Φ</td><td></td><td>10 b- T- OO &lt;0 10 CM t-_ 'T. * θ 'V- T- ~ Cm' &lt;m 'CO CO co'</td>

<td>003 LD200 100 25</td><td></td><td></td><td></td><td>CMOCMCOr-OCOCOr- O C&gt; Tt O 10 ^ CO OO Φ Φ Φ Tt ω</td><td></td><td>r- CO 00 IO * &lt;0 O b σι_ ω o ¿n v_ O θ 'r-' CO CO CO co '</td>

<td>Notebook 22249-043- Resin % LDPE Coating weight (g / m²)</td><td>Hot stickiness (N) -&gt; Temp. (° C) I</td><td> 80</td><td> 85</td><td>O 10 o to o co o OIOOQT-T-CMCMCO</td><td>Heat sealed (Ib) -&gt; Temp. (° C) i</td><td>O 10 O 10 o «O o 10 O 10 OO T- r- CM CM CO 00 O O&gt; ν τ “τ“ v TV “^</td>

ES 2 339 331 T3

Table XVIb. Hot tack and heat seal data for competitive resins at gsm coating weights²

<td>036 UL02020 25</td><td></td><td> 1 0,07</td><td> 1 2,46</td><td> 1 4,53</td><td>I 6.02</td><td> 1 5,64</td><td> 1 5,13</td><td>4.61 4.13 I</td><td></td><td></td><td></td><td> 1,04</td>

<td>033 Nova 61C twenty 25</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CM CO O T- CO σ&gt; O) O CM ~ b- b- CM O&gt; OO tfí bT b? CO IO</td><td></td><td></td><td></td><td></td>

<td>030 PT1450 20 25</td><td></td><td></td><td></td><td></td><td></td><td> 1 0,02 1</td><td>CM or</td><td>Μτ-σ&gt; σ&gt; &lt;οβο &lt;Μχσ&gt; CM rf ΙΌ tD K 6- CO Tt CO</td><td></td><td></td><td></td><td></td>

<td>027 PT1450 25</td><td></td><td></td><td></td><td></td><td></td><td> 0,03</td><td>co CO</td><td>COCONOCONIONS * 0. CO io CO (θ 'CO CD * TT CO</td><td></td><td></td><td></td><td></td>

<td>024 Dow 3010 25</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CMCMCM ^ OCO ^ COCO OOOChlOlOT ^ b ^ r ^ ooo cm 'co b-' co co σΓ</td><td>CO b ^ b-</td><td></td><td></td><td></td>

<td>021 Ex. 3040 20 25</td><td></td><td></td><td></td><td></td><td></td><td>1 0.02 i</td><td>II</td><td>CO CO ^r. -ID oow co r- 'oí ® ® oo co tí co</td><td></td><td></td><td></td><td></td>

<td>Notebook 22249-043- Resin % LDPE Coating weight (g / m²)</td><td>Hot stickiness (N) - ♦ Temp. (° C) |</td><td> 09</td><td> 65</td><td>Or b-</td><td> 75 |</td><td>I 08</td><td>85 Π</td><td>O ΙΟ O ΙΟ OWO OIOOOt-t-CMCMCO</td><td> 135 |</td><td> 140 |</td><td>Heat sealed (Ib) -&gt; Temp. (° C) j</td><td>I 09</td>

ES 2 339 331 T3 oo co σ&gt; τ- ooa o&gt; jc cm co CM * CM * CM * CO CO * CO * CM *

OCOCMT- ^ f ^ COCM ocmcoooo ^ io OOO * r- ^ ^ - * ^ - * Tf ιοιοσ&gt; ιο &lt;οί ^ οτ10OCOCOCO ^ CO &lt;DO t— v CÍ cit CM ^ (O CM CO &lt;0 CO ”t cm« co in «» or OO r T- T- T- CM

CO'tSOSfW'J or cm ^ σ&gt; in or cm co OO * oo cm co rf «M ** vo ω 10 μ σ&gt; 't

CO CM ^ 10 10 CM CM O CO * 10 &lt;0 &lt;0

O 10 O 10 O 10 O! 0O &lt;0Ot0Ol0OOT-T-CMCMCO &lt;ONNCOCOff&gt; G) ^ v * T ^^^^

ES 2 339 331 T3

Table XVIIa. Hot tack and heat seal data for ECD-330 / LDPE blends at 50 g / m coating weights²

<td>019 ECD330 0 fifty</td><td></td><td></td><td>o_ «o ~ -“ i. - b- b. o 'o oo ® ® ® ® oo co</td><td></td><td>COt-OCMCOCOCO ^ ® θ oo tF 10 co r.</td>

<td>016 ECD330 twenty fifty</td><td></td><td></td><td>NNJltNSSbNb O_ &lt;7&gt; _ ΙΛ O_ \ (O [Ί ó 'tn oí ° ° σι' co s</td><td></td><td>COT-fMCOO ^ WW t- (O ^ CO O cm CO tF Tf 10 co</td>

<td>013 ECD330 40 fifty</td><td></td><td></td><td>CMb-OCSlStMCOCOCM o X, YL - 'f ”L ® oo co co ® oí oo &lt;o</td><td></td><td>COCOr-OSCMCOCMO o_ co co «in o« ocM ^ 'co ^ r'cocoin</td>

<td>010 ECD330 60 fifty</td><td></td><td></td><td>COCOCOI ^ S ^ t-OCO O-'OCOCO'T.IOOM o v- ~ in oo® r- ~~ r ~ &lt;o &lt;o</td><td></td><td>t- ^ COt-CO &lt;O10 &lt;OCO ▼ ^^ OOCOG ^ lOOv ^ O o CM co ^ F &amp; quot; F CO 10 10</td>

<td>007 ECD330 80 fifty</td><td></td><td></td><td>O10COt ^ CO ~ CM10O&gt; CO ~ oo &lt;θ co oo &lt;co tf) U&gt;</td><td></td><td>»Τ- ^ Φ ^ ΙΛΦ10 O b * 10 CO τ- CO co co O T- cm CO 10 10 10 tF</td>

<td>004 LD200 100 fifty</td><td></td><td></td><td>OOCO V-ON.OO h * &lt;D oo CM co co co co co</td><td></td><td>σ&gt; σ&gt; ^ ΦΦ ^ ητ0 10 co co co O V- cm CO tF 10 10 ^ F</td>

<td>Notebook 22249-043- Resin % LDPE Coating weight (g / m²)</td><td>Hot stickiness (N) -&gt; Temp. (° C) I</td><td>85 I</td><td>o 10 o 10 o &lt;0 o O10OOT-T-CMCMCO ΟΟνν-τ-ντ— v ^ ·</td><td>Heat sealed (Ib) Temp. (° C) I</td><td>O 10 O 10 O 10 10O10OOV-T-CMCM cooov ^^^^^</td>

ES 2 339 331 T3

Table XVIIb. Hot tack and heat seal data for competitive resins at g / m coating weights²

<td>037 UL02020 fifty</td><td></td><td> | 0,037</td><td> | 2,058</td><td> | 3,646</td><td> | 5,256</td><td>I 6.67</td><td> | 6,73</td><td> 5,882 5,569</td><td></td><td></td><td></td><td> 0,64</td>

<td>034 Nova 61C 20 fifty</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>mnnm N c \ | b r- b Μ Φ OO CN in CM co co oo C¿ ID bb Φ</td><td> 5,232 |</td><td></td><td></td><td></td>

<td>031 PT1450 20 fifty</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>OlOOCMMCMOCO b ^ cm oo ~ b * σ&gt; ιο r * O Tt '' tb ^ 00 00 b «~ CO</td><td></td><td></td><td></td><td></td>

<td>028 PT1450 fifty</td><td></td><td></td><td></td><td></td><td></td><td> 0,025</td><td> | 2,384</td><td>CMb- ^ COCMCOCO ^ i oococMo ^ noS! mo cm oo) ^ · oo co co * b? b? b? co</td><td></td><td></td><td></td><td></td>

<td>025 Dow 3010 fifty</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>^ • inCM ^ -CMIOb-gñ CMCMCMr-bOCOX? OOOb-b-Ob - o 'O Ó bí Ifl CO ​​m ° °</td><td>| 8.18 I</td><td> 6,802 |</td><td></td><td></td>

<td>022 Exact 3040 twenty fifty</td><td></td><td></td><td></td><td></td><td></td><td>00 or or</td><td>I 3,697</td><td>co ° ° σ&gt; ~ σ&gt; ~ i &lt;° id</td><td></td><td></td><td></td><td></td>

<td>Notebook 22249-043- Resin % LDPE Coating weight (g / m²)</td><td>Hot stickiness (N) —► Temp. (° C) I</td><td>OR CO</td><td>&lt;or CO</td><td>Or b.</td><td>b-</td><td>or 00</td><td>IO co</td><td>O ΙΟ O ΙΟ O ΙΟ O OIOOOt-t-CMCMCO</td><td>135 I</td><td>140 I</td><td>Heat sealed (Ib) -&gt; Temp. (° C) j</td><td>Or co</td>

ES 2 339 331 T3 b- Μ · co σ&gt; b- co CM CO CO ΙΟ CO co

CM co

OC0vC0 ^ T ^ 0&gt; ▼ ζ. ▼ ζ, «* 1 &lt;oo to

O o OO CO CO bí cocoio ^ r ^ -oíiocob ·.

CO CM ~ &lt;0 OO 'fb ^ o O V- cm cm cm co co co co bOObOOOr ^ OlO ▼ ^ &lt;OCOCOO&gt; T- ~ CO_OCO ov CM CM CM CO co' tf co

IOC0C0CM &lt;0G&gt; 10C0C0G&gt; OOt-CMCOCOOCOCOCM ^ OOOOOCM ^ · IOIOC0 »O b OΦ

T- O CO COCO ^

O CO co C0 C0 &lt;©

OCOOCOOIOOCOO COOCOOIOOCOOO ^ -T-CMCMCOCO ^ C0bb »COCOO) O ^^^^ v ^ r^,^ v

ES 2 339 331 T3

Additionally, Environmental Stress Cracking Resistance (ESCR) can be important to contain greasy products, detergents, or other similarly aggressive chemicals. In general, linear polymers show a high ESCR relative to conventional coating polymers. Additionally, ESCR is improved by reducing the crystallinity of the coating polymer. At less than 60% LDPE addition, 0.912 density mVLDPE produced ESCR results greater than 1000 hours.

TABLE XVIII

Resistance to Environmental Stress Cracking (ASTM D-1693, F50, hours)

<td>% of LD-200</td><td>ECD-137</td><td>ECD-330</td>

<td> 0</td><td> 600,000</td><td> &gt; 1000</td>

<td> 25</td><td> 410,000</td><td> &gt; 1000</td>

<td> 30</td><td> 120,000</td><td> &gt; 1000</td>

<td> 40</td><td> 96,000</td><td> &gt; 1000</td>

<td> 60</td><td> 135,000</td><td> 190,000</td>

<td> 75</td><td> 68,000</td><td> 43,000</td>

<td> 100</td><td> 90,000</td><td> 90,000</td>

In use in extrusion coating applications, LDPE / mVLDPE blends are believed to exhibit all or some of the following advantages over prior art materials: improved mechanical properties relative to LDPE and LLDPE; improved sealing performance relative to LDPE and LLDPE; processability at least equivalent to LLDPE; better adhesion to polypropylene relative to LDPE or LLDPE, thus eliminating or reducing the need for adhesive tie layers; improved sealing performance relative to LDPE when used as a minor component; it can potentially be coated into products thinner than LDPE or LLDPE, due to the additional integrity added by VLDPE; and better organoleptic properties than LLDPE, and at least equivalent to or better than LDPE.

Example 9

Monolayer films were prepared using either a VLDPE or an inventive blend of a VLDPE and an LDPE. Sample 1 comprised m-VLDPE (EXCEED ™ 321, density 0.912 g / cm³) prepared in a gas polymerization process. Sample 2 comprised a mixture of 90% by weight of a m-VLDPE (EXCEED ™ 321, density 0.912 g / cm³) prepared in a gas polymerization process and 10% by weight of a low density polyethylene (ExxonMobil LD200.48, density 0.915, melt index 7.5 g / 10 min). Sample 3 comprised a blend of 80% by weight of a m-VLDPE (EXCEED ™ 321, density 0.912 g / cm³) prepared in a gas polymerization process and 20% by weight of a low density polyethylene (ExxonMobil LD200.48, density 0.915, melt index 7.5 g / 10 min). Sample 4 comprised a 90% by weight blend of a m-VLDPE (EXCEED ™ 321, density 0.912 g / cm³) prepared in a gas polymerization process and 10% by weight of a low density polyethylene (ExxonMobil LD140.09, density 0.919, melt index 0.75 g / 10 min). Sample 5 comprised a blend of 80% by weight of a m-VLDPE (EXCEED ™ 321, density 0.912 g / cm³) prepared in a gas polymerization process and 20% by weight of a low density polyethylene (ExxonMobil LD140.09, density 0.915, melt index 0.75 g / 10 min). Table XIX shows the properties of monolayer films.

ES 2 339 331 T3

TABLE XIX

<td></td><td>Sample 1</td><td>Sample 2</td><td>Sample 3</td><td>Sample 4</td><td>Sample 5</td>

<td>mVLDPE,%</td><td> 100%</td><td> 90%</td><td> 80%</td><td> 90%</td><td> 80%</td>

<td></td><td>(ECD-</td><td>(ECD-321)</td><td>(ECD-321)</td><td>(ECD-321)</td><td>(ECD-321)</td>

<td></td><td> 321)</td><td></td><td></td><td></td><td></td>

<td>LDPE,%</td><td> 0%</td><td> 10%</td><td> 20%</td><td> 10%</td><td> 20%</td>

<td></td><td></td><td>(LD200.48)</td><td>(LD200.48)</td><td>(LD140.09)</td><td>(LD140.09)</td>

<td>Processing: Temp. of melt, ° C</td><td> 196</td><td> 194</td><td> 193</td><td> 194</td><td> 194</td>

<td>Head pressure, MPa Horsepower of</td><td> 24,3</td><td> 23,5</td><td> 22,4</td><td> 24,8</td><td> 25,2</td>

<td>extruder</td><td> 13,6</td><td> 12,8</td><td> 11,6</td><td> 12,5</td><td> 12,8</td>

<td>Extruder motor load,%</td><td> 55,4</td><td> 50</td><td> 45,4</td><td> 50,8</td><td> 49,9</td>

<td>Production rate, kg / h</td><td> 70,3</td><td> 70,8</td><td> 70,3</td><td> 69,9</td><td> 71,2</td>

<td>Film properties Tensile strain, MPa DM</td><td> 7,4</td><td> 8,8</td><td> 10,2</td><td> 9,2</td><td> 10,6</td>

<td>DT</td><td> 7,4</td><td> 9,2</td><td> 9,2</td><td> 9,4</td><td> 10,1</td>

<td>to 200% DM Ultimate tensile, MPa</td><td> 13,2</td><td> 16,7</td><td> 21,6</td><td> 20,5</td><td> 26,3</td>

<td>DM</td><td> 77,4</td><td> 68,8</td><td> 60,7</td><td> 70,6</td><td> 66,5</td>

<td>DT</td><td> 63,4</td><td> 61,6</td><td> 57,9</td><td> 63,3</td><td> 61,1</td>

<td>Elongation at break,% DM</td><td> 474</td><td> 503</td><td> 487</td><td> 493</td><td> 462</td>

<td>DT</td><td> 617</td><td> 626</td><td> 636</td><td> 622</td><td> 643</td>

<td>Secant modulus 1%, MPa DM</td><td> 174</td><td> 217</td><td> 238</td><td> 240</td><td> 265</td>

<td>DT</td><td> 190</td><td> 272</td><td> 312</td><td> 311</td><td> 335</td>

<td>Elmendorf tear, g / mil DM</td><td> 202</td><td> 133</td><td> 73</td><td> 107</td><td> 48</td>

<td>DT</td><td> 396</td><td> 499</td><td> 649</td><td> 637</td><td> 567</td>

<td>Dardo drop, g / mil (method A)</td><td> 623</td><td> 765</td><td> 379</td><td> 767</td><td> 266</td>

<td>Caliber, mil (mean)</td><td> 1,24</td><td> 1,29</td><td> 1,29</td><td> 1,26</td><td> 1,30</td>

<td>Turbidity,%</td><td> 7,7</td><td> 2,4</td><td> 6,6</td><td> 2,0</td><td> 2,8</td>

<td>Brightness at 45 degrees</td><td> 58</td><td> 84</td><td> 63</td><td> 86</td><td> 83</td>

<td>Puncture Peak Force, Ib / mil</td><td> 11,55</td><td> 9,92</td><td> 10,59</td><td> 11,00</td><td> 10,00</td>

<td>Ultimate Energy, in-lb / mil Total Energy, ft / lb</td><td> 40,40</td><td> 30,94</td><td> 30,88</td><td> 30,89</td><td> 23,25</td>

<td>Temp. Ambient</td><td>&gt; Capac.</td><td>&gt; Capacity</td><td> 2,31</td><td>&gt; Capacity</td><td> 2,19</td>

<td>-34 ° C</td><td> 3,01</td><td> 1,62</td><td> 1,74</td><td> 1,48</td><td> 1,82</td>

<td>Shrinkage,% DM</td><td> 42</td><td> 66</td><td> 74</td><td> 74</td><td> 82</td>

<td>DT</td><td> -4</td><td> -18</td><td> -17</td><td> -17</td><td> -17</td>

ES 2 339 331 T3

Example 10

Monolayer films were prepared using either an inventive VLDPE, a conventional VLDPE, a blend of an inventive VLDPE and an LDPE, or a blend of conventional VLDPE and an LDPE. Sample 6 comprised m-VLDPE (EXCEED ™ 321, density 0.912 g / cm³) prepared in a gas polymerization process. Sample 7 comprised an inventive blend of 90% by weight of a m-VLDPE (EXCEED ™ 321, density 0.912 g / cm³) prepared in a gas polymerization process and 10% by weight of a low density polyethylene (ExxonMobil LD200.48, density 0.915, melt index 7.5 g / 10 min). Sample 8 comprised an inventive blend of 90% by weight of a m-VLDPE (EXCEED ™ 321, density 0.912 g / cm³) prepared in a gas polymerization process and 10% by weight of a low density polyethylene (ExxonMobil LD140.09, density 0.919, melt index 0.75 g / 10 min). Sample 9 (comparative) comprised a mixture of 90% by weight of a VLDPE (Dow Attane 4201, density 0.9132 g / cm³) prepared in a solution polymerization process and 10% by weight of a low density polyethylene (ExxonMobil LD200.48, density 0.915, melt index 7.5 g / 10 min). Sample 10 (comparative) comprised a mixture of 90% by weight of a VLDPE (Dow Attane 4201, density 0.9132 g / cm³) prepared in a solution polymerization process and 10% by weight of a low density polyethylene (ExxonMobil LD140.09, density 0.919, melt index 0.75 g / 10 min). Sample 11 (comparative) comprised a VLDPE (Dow Attane 4201, density 0.9132 g / cm³) prepared in a solution polymerization process.

Table XX shows the haze and gloss properties of the monolayer films. Samples 7 and 8 showed that the inventive blends comprising a VLDPE and an LDPE had more transparent optical properties (i.e., lower haze and higher brightness) than the blends comprising a conventional VLDPE and an LDPE from Samples 9 and 10.

TABLE XX

<td></td><td>Sample 6</td><td>Sample 7</td><td>Sample 8</td><td>Comparative sample 9</td><td>Comparative sample 10</td><td>Comparative sample 11</td>

<td>VLDPE,%</td><td>100% (ECD321)</td><td>90% (ECD-321)</td><td>90% (ECD-321)</td><td>90% (Attane4201)</td><td>90% (Attane4201)</td><td>100% (Attane4201)</td>

<td>LDPE,%</td><td> 0%</td><td>10% (LD200.48)</td><td>10% (LD140.09)</td><td>10% (LD200.48)</td><td>10% (LD140.09)</td><td> 0%</td>

<td>Turbidity, % Brightness, 45 degree Gauge, med., Mil</td><td> 7,7 58 1,24</td><td> 2,4 84 1,29</td><td> 2,0 86 1,26</td><td>&gt; 4 &lt;80 target 1.25</td><td>&gt; 2.5 &lt;84 target 1.25</td><td> 6,9 70 1,25</td>

Example 11 (Comparative)

Peel tests were performed to determine adhesion of the 50 g / m coatings² to the OPP / aluminum substrate (polyethylene coatings on the OPP side of the substrate). Fifteen (15) mm wide specimens were cut in the machine direction from the samples. The polyethylene liner was manually peeled from the substrate to allow the liner and substrate to be clamped on opposite forks of a tensile tester. The forks are separated at a speed of 100 mm / minute and the force to delaminate is measured. Table XXI shows the results of the peel test. Only the LD200, Dow 3010 and LD261 samples could be peeled from the OPP. The other resins could not be peeled without tearing the substrate or causing delamination between the OPP and aluminum layers. The single-site catalyst-catalyzed resins, ECD-330, Exact-3040, and Affinity PT1450, all had better adhesion to OPP than conventional LDPE, LLDPE, or EVA. It is interesting to note that LLDPE Nova Sclair 61C also had good adhesion to OPP. One possible explanation is excessive oxidation in the Nova product due to very high extrusion temperatures, 332 ° C, which could have resulted in good adhesion.

ES 2 339 331 T3

TABLE XXI

<td></td><td>Peel Results (N / 15 mm)</td>

<td>m-VLDPE (ECD-330)</td><td>not measurable</td>

<td>LDPE</td><td> 0,40</td>

<td>(ExxonMobil LD200)</td><td>(1 sample, all others easily separated)</td>

<td>LLDPE</td><td> 0,47</td>

<td>(Dow 3010)</td><td>(mean of 4 samples)</td>

<td>CAM</td><td> 0,06</td>

<td>(ExxonMobil LD261)</td><td>(mean of 4 samples)</td>

<td>Plastomer (ExxonMobil Exact 3040)</td><td>not measurable</td>

<td>Plastomer Dow Affinity PT1450</td><td>not measurable</td>

<td>LLDPE (Nova Sclair 61C LLDPE)</td><td>not measurable</td>