Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
  • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
  • C08J2323/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
  • C08L23/0838—Copolymers of ethene with aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2314/00—Polymer mixtures characterised by way of preparation
  • C08L2314/06—Metallocene or single site catalysts

Definitions

• the subject invention is directed to olefin polymer compositions useful in films having improved antiblock and optical properties.
• the subject of the invention is a composition which comprises a saturated fatty acid amide or saturated ethylenebis(amide), an unsaturated fatty acid amide or unsaturated ethylenebis(amide), and a finely divided inorganic compound, which combine to give optimum values of slip and block when used in compositions comprising homogeneous ethylene/ ⁇ -olefm interpolymers or blend compositions therefrom.
• the subject invention is also directed to compositions which comprise a saturated fatty acid amide or saturated ethylenebis(amide). an unsaturated fatty acid amide or unsaturated ethylenebis(amide).
• compositions comprising a substantially random interpolymer of one or more -olefins with one or more vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers or blend compositions therefrom.
• compositions which comprise at least one homogeneous ethylene/ ⁇ -olefin interpolymer or substantially random interpolymer of one or more ⁇ -olefins with one or more vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers, at least one slip agent, and at least one modifying agent comprising propylene homopolymers, propylene/ ⁇ -olefin copolymers, nucleating agents, and mixtures thereof.
• Ethylene homopolymers and ethylene/ ⁇ -olefin copolymers are of commercial importance for the manufacture of numerous articles. These include blown and cast and monolayer and coextruded films, which can be used for applications such as multilayer and flexible packaging sealants and especially anything packaged via vertical, horizontal, or thermoform fill/ seal. In order for such resins to be easily fabricated into these articles, the resulting film or layer must exhibit good slip and blocking properties.
• the slip characteristic of a polyolefin film or layer is a measure of the ability to slide one layer over another and is commonly expressed in terms of the films coefficient of friction (COF).
• COF films coefficient of friction
• Films with poor slip characteristics can be difficult to handle when produced in large rolls and can be distorted by the frictional processes induced by fabrication equipment, especially in the manufacture of thin films.
• the density of a polyolefin composition is decreased, the tackiness of the film generally increases and the coefficient of friction increases.
• the "blocking" characteristic of a polyolefin film or layer may be defined as the tendency of the film or layer to stick to itself by the application of even slight compression. Such “blocking” is also somewhat dependent on, or responsive to. the amount of compression applied as well as to the duration of the compression and the temperature.
• “Destructive block” refers to the tendency to form substantially irreversible adhesion which will likely cause deformation or tearing of the film. Such “destructive block” can occur even when compression forces are small, such as when rolls of film are manufactured, especially when the rolls are prepared, stored, or shipped under very warm or hot conditions. Blocking can be reduced by adding finely divided inorganic fillers such as silica. However the addition of too high an amount of filler can be detrimental to the optical properties of the film. If a film has a high tendency to block , then this adhesion can also cause deformation and tearing of the film during manufacture.
• LLDPE a secondary fatty acid amide, and a finely-divided naturally-occurring mineral.
• U.S. Pat. No 4,751,262 (McKinney et al.) describes compositions comprising an ethylene/acrylic acid interpolymer or ionomer. a saturated secondary fatty acid amide, an unsaturated or mixed saturated/unsaturated secondary fatty acid amide and a finely- divided naturally-occurring mineral.
• U.S. Pat. No 4,785.042 (Azuma et al.) describes a polyethylene resin composition comprising a low density polyethylene, a zeolite, a fatty acid amide and an antistatic agent.
• J610119644-A describes a linear low density polyethylene resin containing LLDPE, a fatty acid amide and/or silica gel particles.
• metallocene-based catalysts for ethylene/ ⁇ - olefin copolymerization has resulted in the production of new ethylene interpolymers (the term "interpolymer” is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer including copolymers, terpolymers. etc.).
• interpolymer is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer including copolymers, terpolymers. etc.
• These metallocene catalysts include the bis(cyclopentadienyl)- catalyst systems and the mono(cyclopentadienyl)- or Constrained Geometry catalyst systems.
• Such catalyst systems have generated new ethylene interpolymers and hence new requirements for compositions containing these materials.
• Such polymers are known as homogeneous interpolymers and are characterized by their narrow molecular weight and composition distributions relative to, for example, traditional Ziegler catalyzed heterogeneous polyolefin polymers.
• the homogeneous interpolymers tend to be less tacky than the analogous heterogeneous interpolymers at densities greater than 0.92 g/cm 3 and more tacky at densities less than about 0.92 g/cm 3 , and thus new compositions comprising these materials are needed to achieve targeted slip and block levels while maintaining other important properties such as optics.
• compositions comprising blends of homogeneous interpolymers produced by metallocene catalysts and heterogeneous interpolymers produced using traditional Ziegler catalysts.
• Suitable blend compositions and a process for their use are disclosed in U.S. Application Nos.: 08/510,527, filed Aug 2, 1995; and 08/747,419 filed Nov. 12. 1996, the teachings of all of which are incorporated herein by reference.
• Such blends also require new compositions with improved slip and antiblock properties needed to achieve targeted slip and block levels.
• the new constrained geometry catalysts can also be used to prepare the generic class of ⁇ -olefin/hindered vinylidene monomer substantially random interpolymers, including materials such as ⁇ -olefin/vinyl aromatic monomer interpolymers.
• materials such as ethylene/styrene interpolymers, offer a wide range of material structures and properties which makes them useful for varied applications. Again, especially for film applications for these materials, new compositions comprising these materials are needed to achieve targeted slip and block levels.
• compositions which are blends comprising homogeneous interpolymers or substantially random interpolymers of ⁇ - olefins with one or more vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers which exhibit good antiblock properties and low COF values while maintaining good physical properties including sealability and abuse resistance while maintaining good optical properties.
• compositions comprising; (A) a homogeneous ethylene/ ⁇ -olefin interpolymer having a narrow composition distribution; and
• compositions comprising;
• a three component blend of a saturated fatty acid amide or saturated ethylenebis(amide), an unsaturated fatty acid amide or unsaturated ethylenebis(amide), and a finely divided inorganic compound combines to give the optimum values of slip and block when used in compositions comprising homogeneous ethylene/ ⁇ -olefin interpolymers or blend compositions therefrom. Additionally these advantages can be realized, generally without loss of other important properties including optical properties, sealability and abuse resistance. Applications for these resin compositions include blown and cast and monolayer and coextruded films, which can be used for multilayer and flexible packaging sealants and especially anything packaged via vertical, horizontal, or fhermoform fill/ seal.
• compositions comprising;
• the present invention also pertains to a composition
• a composition comprising;
• interpolymer comprises; (a) from 0.5 to 65 mole percent of polymer units derived from;
• any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value.
• the amount of a component or a value of a process variable such as, for example, temperature, pressure, and time is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly enumerated in this specification.
• one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
• hydrocarbyl as employed herein means any aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic, aryl substituted cycloaliphatic, aliphatic substituted aromatic, or aliphatic substituted cycloaliphatic groups.
• hydrocarbyloxy means a hydrocarbyl group having an oxygen linkage between it and the carbon atom to which it is attached.
• silica means a group having a silicon linkage between it and the carbon atom to which it is attached.
• germanium means a group having a germanium linkage between it and the carbon atom to which it is attached.
• substituted cyclopentadienyl is intended to include ring-substituted or polynuclear derivatives of the cyclopentadienyl moiety wherein the substituent is hydrocarbyl, hydrocarbyloxy, hydrocarbylamino, cyano. halo, silyl, germyl. siloxy or mixtures thereof or two such substituents are a hydrocarbylene group, the substituent (or two substituents together) having up to 30 non-hydrogen atoms.
• substituted cyclopentadienyls include indenyl, tetrahydroindenyl, fluorenyl, and octahydrofluorenyl groups.
• the term “Bronsted Acid cation” means a cation which acts as a proton donor.
• interpolymer is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer. This includes copolymers, terpolymers, etc.
• compositions of the present invention were measured after 24 hr. in accordance with ASTM D-1894 (utilizing a TMI Direct Drive Monitor Slip and friction Tester).
• ASTM D-1894 utilizing a TMI Direct Drive Monitor Slip and friction Tester.
• slip characteristics are associated with COF values of less than 0.31.
• compositions of the present invention were measured off line in accordance with ASTM D-3354-89 (utilizing a Kayeness Block Tester).
• "good" blocking characteristics are associated with values of less than 49 g.
• the density of the polymer compositions for use in the present invention was measured in accordance with ASTM D-792.
• the molecular weight of the polymer compositions for use in the present invention was conveniently indicated using a melt index measurement according to
• melt flow ratio measured by determining "Iio" (according to ASTM D-1238.
• the molecular weight determination was deduced by using narrow molecular weight distribution polystyrene standards (from Polymer Laboratories) in conjunction with their elution volumes.
• the equivalent polyethylene molecular weights were determined by using appropriate Mark-Houwink coefficients for polyethylene and polystyrene (as described by Williams and Ward in Journal of Polymer Science, Polymer Letters, Vol. 6, (621) 1968) to derive the following equation:
• compositions of the present invention can comprise a saturated fatty acid amide or ethylenebis(amide). an unsaturated fatty acid amide or ethylenebis(amide) and a finely divided inorganic compound, in addition to the base polymer.
• the saturated fatty amides useful in the present invention conform essentially to the empirical formula R a C(0)NHR b where R a is a saturated alkyl group having of from 10 carbon atoms to 26 carbon atoms and R b is independently hydrogen or a saturated alkyl group having of from 10 carbon atoms to 26 carbon atoms.
• Compounds which conform to the above empirical structure are for example, palmitamide, stearamide. arachidamide. behenamide, stearyl stearamide, palmityl pamitamide. stearyl arachidamide and mixtures thereof.
• the saturated ethylenebis(amides) useful in the present invention conform essentially to the empirical formula
• R a C(O)NHCH 2 CH 2 NHC(O)R a where R a is as defined previously.
• Compounds which conform to the above empirical structure are for example, stearamidoethylstearamide, stearamidoethylpalmitamide, palmitamido-ethylstearamide and mixtures thereof.
• the unsaturated fatty amides useful in the present invention conform essentially to the empirical formula
• R c C(O)NHR d where R c is an unsaturated alkyl group having of from 10 carbon atoms to 26 carbon atoms and R d is independently hydrogen or a unsaturated alkyl group having of from 10 carbon atoms to 26 carbon atoms.
• Compounds which conform to the above empirical structure are for example, oleamide. erucamide, linoleamide, and mixtures thereof.
• the unsaturated ethylenebis(amides) useful in the present invention conform essentially to the empirical formula
• R e C(O)NHCH 2 CH 2 NHC(O)R e
• R e is either a saturated or unsaturated alkyl group having of from 10 carbon atoms to 26 carbon atoms with the proviso that at least one of R e is unsaturated.
• Compounds which conform to the above empirical structure include, erucamidoethylerucamide. oleamidoethyloleamide, erucamidoethyloleamide, oleamidoethylerucamide. stearamidoethylerucamide. erucamidoethylpalmitamide. palmitamidoethyloleamide and mixtures thereof.
• the finely divided inorganic compounds useful in the present invention include but are not limited to the following; clay, aluminum silicate, diatomaceous earth, silica, talc, limestone, fumed silica, magnesium sulfate, magnesium silicate, alumina trihydrate, magnesium oxide, zinc oxide, titanium dioxide, with the siliceous materials being preferred.
• the inorganic compound preferably has an average particle size in the range of 0.02 to 40 microns, a surface area of from 0.7 to 1000 m 2 /g, and an oil absorption value of 21 to 175 parts oil per 100 parts organic.
• homogeneous polymers and interpolymers of the present invention are herein defined as defined in USP 3,645,992 (Elston), the disclosure of which is incorporated herein by reference. Accordingly, homogeneous polymers and interpolymers are those in which the comonomer is randomly distributed within a given inte ⁇ olymer molecule and wherein substantially all of the inte ⁇ olymer molecules have the same ethylene/comonomer ratio within that inte ⁇ olymer.
• Such inte ⁇ olymers are distinct from the typical Ziegler catalyzed inte ⁇ olymers which are known as heterogeneous inte ⁇ olymers and are those in which the inte ⁇ olymer molecules do not have the same ethylene/comonomer ratio.
• the homogeneous polymers are also distinct from LDPE produced by high pressure free radical catalyzed ethylene polymerization which results in highly branched polyethylene which is known to those skilled in the art to have numerous long chain branches.
• narrow composition distribution used herein describes the comonomer distribution for homogeneous inte ⁇ olymers and means that the homogeneous inte ⁇ olymers have only a single melting peak as measured by Differential Scanning Calorimetry (DSC) and essentially lack a measurable "high density" polymer fraction.
• the narrow composition distribution homogeneous inte ⁇ olymers can also be characterized by their SCBDI (Short Chain Branch Distribution Index) or CDBI (Composition Distribution Branch Index) which is defined as the weight percent of the polymer molecules having a comonomer content within 50 percent of the median total molar comonomer content.
• SCBDI Short Chain Branch Distribution Index
• CDBI Composition Distribution Branch Index
• the CDBI of a polymer is readily calculated from data obtained from techniques known in the art. such as. for example, temperature rising elution fractionation (abbreviated herein as "TREF") as described, for example, in Wild et al. Journal of Polymer Science. Poly. Phvs. Ed.. Vol. 20. p. 441 (1982), in U.S.
• TEZ temperature rising elution fractionation
• Patent 4.798,081 (Hazlitt et al.), or as is described in USP 5,008,204 (Stehling), the disclosure of which is inco ⁇ orated herein by reference.
• the technique for calculating CDBI is described in USP 5,322.728 (Davey et al. ) and in USP 5,246,783 (Spenadel et al.) or in U.S. Patent 5,089,321 (Chum et al.) the disclosures of all of which are inco ⁇ orated herein by reference.
• the SCBDI or CDBI for the homogeneous narrow composition ethylene/ ⁇ -olefin inte ⁇ olymers used in the present invention is greater than 50 percent, preferably greater than 70 percent, and more preferably greater than 90 percent.
• the narrow composition distribution homogeneous inte ⁇ olymers used in this invention essentially lack a measurable "high density" (or homopolymer) fraction as measured by the TREF technique.
• the homogeneous inte ⁇ olymers and polymers have a degree of branching less than or equal to 2 methyls/ 1000 carbons in 15 percent (by weight) or less, preferably less than 10 percent (by weight), and especially less than 5 percent (by weight).
• Also included as components in the current invention are the substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers.
• the substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers of the present invention are herein defined as in US Pat. Nos.
• the substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers are also homogeneous inte ⁇ olymers as the comonomer is randomly distributed within a given inte ⁇ olymer molecule and substantially all of the inte ⁇ olymer molecules have the same ethylene/comonomer ratio within that inte ⁇ olymer.
• substantially linear ethylene/ ⁇ -olefin inte ⁇ olymer means that the polymer also contains long chain branching.
• Long chain branching is defined herein as a chain length of at least one carbon more than two carbons less than the total number of carbons in the comonomer.
• the long chain branch of an ethylene/octene substantially linear ethylene interpolymer is at least seven (7) carbons in length (that is, 8 carbons less 2 equals 6 carbons plus one equals seven carbons long chain branch length).
• the long chain branch can be as long as the same length as the length of the polymer back-bone.
• Long chain branching is determined by using ⁇ C nuclear magnetic resonance (NMR) spectroscopy and is quantified using the method of Randall (Rev. Macromol. Chem. Phvs.. C29 (2&3), p. 285-297), the disclosure of which is inco ⁇ orated herein by reference.
• Long chain branching is to be distinguished from short chain branches which result solely from inco ⁇ oration of the comonomer, so for example the short chain branch of an ethylene/octene substantially linear polymer is six carbons in length, while the long chain branch for that same polymer is at least seven carbons in length.
• the polymer is characterized as having 0.01 long chain branches/1000 carbons to 3 long chain branches/1000 carbons, more preferably from 0.01 long chain branches/1000 carbons to 1 long chain branches/1000 carbons, and especially from 0.05 long chain branches/1000 carbons to 1 long chain branches/1000 carbons.
• the substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers useful in this invention su ⁇ risingly have excellent processability, even though they have relatively narrow molecular weight distributions.
• the substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers have a molecular weight distribution.
• M w /M n defined by the equation:
• the melt flow ratio (I10/I2) of the substantially linear olefin polymers can be varied essentially independently of the polydispersity index (that is, molecular weight distribution (M w /M n )).
• M w /M n molecular weight distribution
• the I 1 0 I2 value also increases.
• the Il ⁇ /l2 ratio indicates the degree of long chain branching, that is, the higher the Ii()/-2 ratio, the more long chain branching in the polymer.
• the "rheological processing index” is the apparent viscosity (in kpoise) of a polymer measured by a gas extrusion rheometer (GER).
• GER gas extrusion rheometer
• the gas extrusion rheometer is described by M. Shida, R.N. Shroff and L.V. Cancio in Polymer Engineering Science, Vol. 17, no. 11. p. 770 (1977). and in "Rheometers for Molten Plastics” by John Dealy, published by Van Nostrand Reinhold Co. (1982) on page 97-99, both publications of which are inco ⁇ orated by reference herein in their entirety. All GER experiments are performed at a temperature of 190°C.
• the PI is the apparent viscosity (in kpoise) of a material measured by GER at an apparent shear stress of 2.15 x
• the substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers described herein preferably have a PI in the range of 0.01 kpoise to 50 kpoise, preferably 15 kpoise or less.
• the substantially linear ethylene/ ⁇ -olefin polymers described herein have a PI less than or equal to 70 percent of the PI of a comparative linear ethylene/ ⁇ - olefin polymer which does not contain long chain branching but of the same I2 and M /M n .
• the critical shear rate at onset of surface melt fracture for the substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers is at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear ethylene/ ⁇ - olefin polymer which does not contain long chain branching but of the same 12 and
• Gross melt fracture occurs at unsteady flow conditions and ranges in detail from regular (alternating rough and smooth, helical, etc.) to random distortions. For commercial acceptability, (for example, in blown film products), surface defects should be minimal, if not absent.
• the critical shear rate at onset of surface melt fracture (OSMF) and onset of gross melt fracture (OGMF) will be used herein based on the changes of surface roughness and configurations of the extrudates extruded by a GER.
• Exemplary metallocene catalysts useful to prepare the homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer component of the present invention comprises: a) a metal complex corresponding to the formula: MX P X , that has been or subsequently is rendered catalytically active by combination with an activating cocatalyst or by use of an activating technique, wherein: M is a metal of Group 4 of the Periodic Table of the Elements having an oxidation state of +2, +3 or +4, bound in an ⁇ 5 bonding mode to one or more L groups;
• L independently each occurrence is a cyclopentadienyl-, indenyl-, tetrahydroindenyl-, fluorenyl-, tetrahydrofluorenyl-, or octahydrofluorenyl- group optionally substituted with from 1 to 8 substituents independently selected from the group consisting of hydrocarbyl, halo, halohydrocarbyl, aminohydrocarbyl, hydrocarbyloxy. dihydrocarbylamino. dihydrocarbylphosphino, silyl. aminosilyl. hydrocarbyloxysilyl.
• halosilyl groups containing up to 20 non-hydrogen atoms may be joined together by a divalent substituent selected from hydrocarbadiyl, halohydrocarbadiyl, hydrocarbyleneoxy, hydrocarbyleneamino, siladiyl, halosiladiyl, and divalent aminosilane, groups containing up to 20 non-hydrogen atoms;
• X independently each occurrence is a monovalent anionic ⁇ -bonded ligand group, a divalent anionic ⁇ -bonded ligand group having both valences bonded to M. or a divalent anionic ⁇ -bonded ligand group having one valency bonded to M and one valency bonded to an L group, said X containing up to 60 nonhydrogen atoms:
• X independently each occurrence is a neutral Lewis base ligating compound, having up to 20 atoms;
• 1 is one or two; p is 0. 1 or 2. and is 1 less than the formal oxidation state of M when X is an monovalent anionic ⁇ -bonded ligand group or a divalent anionic ⁇ -bonded ligand group having one valency bonded to M and one valency bonded to an L group, or p is 1 +1 less than the formal oxidation state of M when X is a divalent anionic ⁇ -bonded ligand group having both valencies bonded to M; and q is 0, 1 or 2.
• the catalysts used to prepare the homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer component of the present invention are believed to exist in the form of a mixture of one or more cationic or zwitterionic species derived from the foregoing metal complex a).
• Fully cationic or partially charge separated metal complexes, that is. zwitterionic metal complexes have been previously disclosed in US Patents 5,470,993 and 5.486,632, the teachings of which are herein inco ⁇ orated in their entirety by reference thereto.
• the cationic complexes are believed to correspond to the formula: L.ivrX p .A wherein:
• M is a Group 4 metal in the +4 or +3 formal oxidation state
• L, X, 1 and p are as previously defined; and A " is a noncoordinating, compatible anion derived from the activating cocatalyst.
• the zwitterionic complexes in particular result from activation of a Group 4 metal diene complex that is in the form of a metallocyclopentene. wherein the metal is in the +4 formal oxidation state, (that is X is 2-butene-1.4-diyl, or a hydrocarbyl substituted derivative thereof, having both valencies bonded to M) by the use of a Lewis acid activating cocatalyst, especially tris(perfluoro-aryl)boranes.
• a Lewis acid activating cocatalyst especially tris(perfluoro-aryl)boranes.
• M is a Group 4 metal in the +4 formal oxidation state
• L, X. 1 and p are as previously defined;
• X** is the divalent remnant of the conjugated diene, X', formed by ring opening at one of the carbon to metal bonds of a metallocyclopentene
• a " is a noncoordinating, compatible anion derived from the activating cocatalyst.
• noncoordinating means an anion which either does not coordinate to component a) or which is only weakly coordinated therewith remaining sufficiently labile to be displaced by a neutral Lewis base, including an ⁇ - olefin.
• a non-coordinating anion specifically refers to an anion which when functioning as a charge balancing anion in the catalyst system of this invention, does not transfer a fragment thereof to said cation thereby forming a neutral four coordinate metal complex and a neutral byproduct.
• “Compatible anions” are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerizations.
• Preferred X' groups are phosphines, especially trimethylphosphine, triethylphosphine, triphenylphosphine and bis(l,2-dimethylphosphino)ethane; P(OR) 3 , (wherein R is a C,-C 30 hydrocarbyl); ethers, especially tetrahydrofuran; amines, especially pyridine, bipyridine, tetramethylethylenediamine (TMEDA), and triethylamine: olefins; and conjugated dienes having from 4 to 40 carbon atoms.
• Complexes including conjugated diene X' groups include those wherein the metal is in the +2 formal oxidation state. Examples of coordination complexes a) used for the present invention include the foregoing species:
• M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the +2 or +4 formal oxidation state;
• R 3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano. halo and combinations thereof, said R 3 having up to 20 non-hydrogen atoms, or adjacent R 3 groups together form a divalent derivative (that is. a hydrocarbadiyl.
• X independently each occurrence is an anionic ligand group of up to 40 non-hydrogen atoms, or two X" groups together form a divalent anionic ligand group of up to 40 non-hydrogen atoms or together are a conjugated diene having from 4 to 30 non-hydrogen atoms forming a ⁇ -complex with M, whereupon M is in the +2 formal oxidation state, R* independently each occurrence is C alkyl or phenyl, E independently each occurrence is carbon or silicon, and x is an integer from 1 to 8.
• metal complexes a) include those corresponding to the formula: LMX p X' q (III) wherein L, M, X, X', p and q are as previously defined.
• a preferred metal complex belongs to the foregoing class (III) and corresponds to the formula:
• M is titanium, zirconium or hafnium in the +2, +3 or +4 formal oxidation state
• R 3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl. silyl, germyl, cyano, halo and combinations thereof, said R 1 having up to 20 non-hydrogen atoms, or adjacent R 3 groups together form a divalent derivative (that is, a hydrocarbadiyl. siladiyl or germadiyl group) thereby forming a fused ring system
• each X" is a halo, hydrocarbyl, hydrocarbyloxy, hydrocarbylamino. or silyl group, said group having up to 20 non-hydrogen atoms, or two X" groups together form a neutral C5.30 conjugated diene or a divalent derivative thereof;
• Y is -O-, -S-, -NR*-, -PR*-;
• Most preferred coordination complexes a) used for the present invention are complexes corresponding to the formula: R-
• R 3 independently each occurrence is a group selected from hydrogen, hydrocarbyl. halohydrocarbyl, silyl. germyl and mixtures thereof, said group containing up to 20 nonhydrogen atoms;
• M is titanium, zirconium or hafnium
• Z. Y, X and X ' are as previously defined; p is 0, 1 or 2; and q is zero or one; with the proviso that: when p is 2, q is zero.
• M is in the +4 formal oxidation state, and X is an anionic ligand selected from the group consisting of halide, hydrocarbyl. hydrocarbyloxy. di(hydrocarbyl)amido, di(hydrocarbyl)phosphido, hydrocarbylsulfido. and silyl groups, as well as halo-.
• X group having up to 20 nonhydrogen atoms, when p is 1, q is zero, M is in the +3 formal oxidation state, and X is a stabilizing anionic ligand group selected from the group consisting of allyl, 2-(N,N- dimethylaminomethyl)phenyl, and 2-(N,N-dimethyl)-aminobenzyl, or M is in the +4 formal oxidation state, and X is a divalent derivative of a conjugated diene, M and X together forming a metallocyclopentene group, and when p is 0, q is 1, M is in the +2 formal oxidation state, and X' is a neutral, conjugated or nonconjugated diene, optionally substituted with one or more hydrocarbyl groups, said X' having up to 40 carbon
• More preferred coordination complexes a) used according to the present invention are complexes corresponding to the formula:
• R 1 independently each occurrence is hydrogen or C, .6 alkyl
• M is titanium
• R* each occurrence is independently hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl. halogenated alkyl, halogenated aryl. and combinations thereof, said R* having up to 20 non-hydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R* group from Z and an R* group from Y form a ring system; p is 0, 1 or 2; q is zero or one; with the proviso that: when p is 2, q is zero, M is in the +4 formal oxidation state, and X is independently each occurrence methyl or benzyl, when p is 1 , q is zero, M is in the +3 formal oxidation state, and X is 2-(N,N- dimethyl)aminobenzyl; or M is in the +4 formal oxidation state and X is 2-butene-l,4- diyl, and
• M is in the +2 formal oxidation state
• X' is 1 ,4-diphenyl- 1,3-butadiene or 1,3-pentadiene.
• the latter diene is illustrative of unsy metrical diene groups that result in production of metal complexes that are actually mixtures of the respective geometrical isomers.
• the complexes can be prepared by use of well known synthetic techniques.
• a preferred process for preparing the metal complexes is disclosed US Pat. No 5,491,246, the teachings of which are hereby inco ⁇ orated by reference.
• the reactions are conducted in a suitable noninterfering solvent at a temperature from -100 to 300 °C, preferably from -78 to 100 °C. most preferably from 0 to 50 °C.
• a reducing agent may be used to cause the metal M. to be reduced from a higher to a lower oxidation state.
• suitable reducing agents are alkali metals, alkaline earth metals, aluminum and zinc, alloys of alkali metals or alkaline earth metals such as sodium/mercury amalgam and sodium/potassium alloy, sodium naphthalenide. potassium graphite, lithium alkyls, lithium or potassium alkadienyls, and Grignard reagents.
• Suitable reaction media for the formation of the complexes include aliphatic and aromatic hydrocarbons, ethers, and cyclic ethers, particularly branched-chain hydrocarbons such as isobutane, butane, pentane. hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, and xylene, C dialkyl ethers, C dialkyl ether derivatives of (poly)alkylene glycols. and tetrahydrofuran. Mixtures of the foregoing are also suitable.
• Suitable activating cocatalysts useful in combination with component a) are those compounds capable of abstraction of an X substituent therefrom to form an inert, noninterfering counter ion, or that form a zwitterionic derivative of a).
• Suitable activating cocatalysts for use herein include perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluorophenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-. oxonium-, carbonium-, silylium- or sulfonium- salts of compatible, noncoordinating anions.
• Suitable activating techniques include the use of bulk electrolysis .
• a combination of the foregoing activating cocatalysts and techniques may be employed as well.
• the foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes in the following references: European Patent EP- A-277,003, US-A-5,153,157, US-A-5.064,802, European Patents EP-A-468,651 and EP-A-520,732 (equivalent to U. S. Serial No. 07/876,268 filed May 1, 1992), and US- A-5,350,723, the teachings of which are hereby inco ⁇ orated by reference.
• suitable ion forming compounds useful as cocatalysts comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion, A " .
• noncoordinating means an anion or substance which either does not coordinate to the Group 4 metal containing precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base.
• “Compatible anions” are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerization or other uses of the complex.
• Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined.
• said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitriles.
• Suitable metals include, but are not limited to, aluminum, gold and platinum.
• Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon.
• Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially.
• cocatalysts may be represented by the following general formula: (L*-H)- d (A) d - wherein:
• L* is a neutral Lewis base
• (L*-H) * is a Bronsted acid
• a d" is a noncoordinating, compatible anion having a charge of d-, and d is an integer from 1 to 3.
• a d" corresponds to the formula: [M'Q 4 ] " ; wherein: M' is boron or aluminum in the +3 formal oxidation state; and Q independently each occurrence is selected from hydride, dialkylamido. halide. hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl. halosubstituted hydrocarbyloxy. and halo- substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide.
• suitable hydrocarbyloxide Q groups are disclosed in U. S. Patent 5.296,433, the teachings of which are herein inco ⁇ orated by reference.
• d is one. that is. the counter ion has a single negative charge and is A " .
• Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula:
• L* is as previously defined; B is boron in a formal oxidation state of 3; and Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.
• Q is each occurrence a fluorinated aryl group, especially, a pentafluorophenyl group.
• N.N-dimethyl-N-dodecylammonium tetrakis(pentafluorophenyl) borate N,N-dimethyl-N-octadecylammonium tetrakis(pentafluorophenyl) borate.
• N-methyl-N.N-dioctadecylarnmonium tetrakis(pentafluorophenyl) borate N-methyl-N.N-dioctadecylarnmonium tetrakis(pentafluorophenyl) borate.
• disubstituted ammonium salts such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate. and dicyclohexylammonium tetrakis(pentafluorophenyl) borate; trisubstituted phosphonium salts such as: triphenylphosphonium tetrakis(pentafluorophenyl) borate.
• Preferred (L*-H) + cations are N.N-dimethylanilinium, tributylammonium, N- methyl-N,N-didodecylammonium, N-methyl-N,N-dioctadecylammonium. and mixtures thereof.
• Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating. compatible anion represented by the formula:
• Ox e+ is a cationic oxidizing agent having a charge of e+; e is an integer from 1 to 3; and
• a d" and d are as previously defined.
• cationic oxidizing agents include: ferrocenium, hydrocarbyl- substituted ferrocenium, Ag ⁇ ' or Pb +2 .
• Preferred embodiments of A d" are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyl)borate.
• Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating. compatible anion represented by the formula:
• ⁇ + is a C,. 20 carbenium ion; and A " is as previously defined.
• a preferred carbenium ion is the trityl cation, that is triphenylmethylium.
• a further suitable ion forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating. compatible anion represented by the formula:
• R" is C,. 10 hydrocarbyl, and A " are as previously defined.
• silylium salt activating cocatalysts are trimethylsilylium tetrakispentafluorophenylborate. triethylsilylium tetrakispentafluorophenylborate and ether substituted adducts thereof.
• Silylium salts have been previously generically disclosed in J. Chem Soc. Chem. Comm.. 1993, 383-384, as well as Lambert, J. B., et al., Organometallics, 1994, 13, 2430-2443.
• the use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is claimed in USSN 08/304,314, filed September 12, 1994.
• the most preferred activating cocatalysts are trispentafluorophenylborane and N,N-dioctadecyl-N-methylammonium tetrakispentafluorophenylborate.
• the latter compound being the principal component of a mixture of borate salts derived from bis(hydrogenatedtallow)methylammonium compounds, which mixture may be used as the activating cocatalyst herein.
• the molar ratio of metal complex: activating cocatalyst employed preferably ranges from 1 :10 to 2:1, more preferably from 1 :5 to 1.5:1 , most preferably from 1 :5 to 1:1.
• the metallocene catalyst can contain either no aluminum-containing cocatalyst or only a small amount (that is. from 3:1 A Transition metal ratio to 100: 1 A Transition metal ratio) of aluminum cocatalyst.
• the cationic complexes used as homogeneous catalysts may be further activated by the use of an additional activator such as an alkylaluminoxane.
• Preferred coactivators include methylaluminoxane. propylaluminoxane, isobutvlaluminoxane, and combinations thereof .
• modified methylaluminoxane is also suitable for use as a cocatalyst.
• One technique for preparing such modified alumoxane is disclosed in U.S. Patent No. 4.960.878 (Crapo et al), the disclosure of which is inco ⁇ orated herein by reference.
• Aluminoxanes can also be made as disclosed in U.S. patents Nos. 4,544,762 (Kaminsky et al.); 5.015,749 (Schmidt et al.); 5.041,583 (Sangokoya); 5,041,584 (Crapo et al): and 5,041,585 (Deavenport et al.). the disclosures of all of which are inco ⁇ orated herein by reference.
• the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, temperatures from 0-250 °C, preferably 30 to 200 °C and pressures from atmospheric (1 x 10 5 Pa) to 30,000 atmospheres (3 x 10 8 Pa) or higher. Suspension, solution, slurry, gas phase, solid state powder polymerization or other process condition may be employed if desired.
• a support, especially silica, alumina, or a polymer (especially poly(tetrafluoroethylene) or a polyolefin) may be employed, and desirably is employed when the catalysts are used in a gas phase polymerization process.
• the support is preferably employed in an amount to provide a weight ratio of catalyst (based on metal): support from 1 : 100,000 to 1 :10. more preferably from 1 :50.000 to 1 :20. and most preferably from 1 : 10.000 to 1 :30.
• the molar ratio of catalyst:polymerizable compounds employed is from 10 "12 :1 to 10 " ': 1. more preferably from 10 "9 :1 to 10 "” : 1.
• Suitable solvents for polymerization are inert liquids.
• examples include straight and branched-chain hydrocarbons such as isobutane. butane, pentane. hexane. heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane. methylcyclohexane. methylcycloheptane. and mixtures thereof; perfluorinated hydrocarbons such as perfluorinated C 4.10 alkanes, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene. and ethylbenzene.
• Suitable comonomers also include but are not limited to ethylene. propylene, butene. butadiene, cyclopentene. 1-hexene. 4-vinylcyclohexene, l-l-pentene, 4- methyl-1-pentene, 1 ,4-hexadiene. 1-octene, 1-decene. styrene, divinylbenzene, allylbenzene. vinyltoluene (including all isomers alone or in admixture). . Mixtures of the foregoing are also suitable.
• blends of the homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymers with other polymers which can include, but are not limited to, low density polyethylene (LDPE), ethyl vinyl acetate (EVA), and, preferably, a heterogeneous broad composition distribution efhylene/ ⁇ -olefin inte ⁇ olymer, and most preferably with a second homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer of different molecular weight and/or density.
• LDPE low density polyethylene
• EVA ethyl vinyl acetate
• the heterogeneous component is differentiated from the homogeneous component in that in the latter, substantially all of the inte ⁇ olymer molecules have the same ethylene/comonomer ratio within that inte ⁇ olymer, whereas heterogeneous inte ⁇ olymers are those in which the inte ⁇ olymer molecules do not have the same ethylene/comonomer ratio.
• the term "broad composition distribution" used herein describes the comonomer distribution for heterogeneous inte ⁇ olymers and means that the heterogeneous inte ⁇ olymers have a "high density" fraction and that the heterogeneous inte ⁇ olymers have multiple melting peaks (that is. exhibit at least two distinct melting peaks) by DSC.
• the heterogeneous inte ⁇ olymers and polymers have a degree of branching less than or equal to 2 methyls/ 1000 carbons in 10 percent (by weight) or more, preferably more than 15 percent (by weight), and especially more than 20 percent (by weight).
• the heterogeneous inte ⁇ olymers also have a degree of branching equal to or greater than 25 methyls/1000 carbons in 25 percent or less (by weight), preferably less than 15 percent (by weight), and especially less than 10 percent (by weight).
• the heterogeneous inte ⁇ olymer component of the blend can be an ethylene homopolymer or. preferably, inte ⁇ olymers of ethylene with at least one C3-C20 ⁇ _ olefin and/or C4-C18 diolefins. Heterogeneous inte ⁇ olymers of ethylene and propylene. butene- 1. hexene-1, 4-methyl-l-pentene and octene-1 are preferred and copolymers of ethylene and 1-octene are especially preferred.
• the term "broad molecular weight distribution" means that the M /M n of the inte ⁇ olymer (or fraction) is greater than 3, preferably from 3 to 5.
• the catalysts suitable for the preparation of the heterogeneous component of the current invention are typical supported, Ziegler-type catalysts which are particularly useful at the high polymerization temperatures of the solution process.
• Examples of such compositions are those derived from organomagnesium compounds, alkyl halides or aluminum halides or hydrogen chloride, and a transition metal compound. Examples of such catalysts are described in U.S. Pat Nos. 4.314.912 (Lowery, Jr. et al), 4,547,475 (Glass et al.), and 4,612,300 (Coleman, III), the teachings of which are inco ⁇ orated herein by reference.
• Suitable catalyst materials may also be derived from a inert oxide supports and transition metal compounds. Examples of such compositions suitable for use in the solution polymerization process are described in U.S. Pat Nos. 5,231,151 and 5,420,090 (Spencer, et al.). the teachings of which are inco ⁇ orated herein by reference.
• each component described herein can each be made separately in different reactors, and subsequently blended together to make the inte ⁇ olymer blend composition components of the present invention.
• the homogeneous ethylene interpolymer and the additional blend component described herein are made in a multiple reactor scheme, operated either in parallel or in series, such as those disclosed in USP 3,914,342 (Mitchell) and WO 94/00500, the teachings of which are hereby inco ⁇ orated herein by reference.
• At least one of the reactors makes the homogeneous ethylene inte ⁇ olymer using a metallocene catalyst and at least one of the reactors makes the second polymer, either a different homogeneous ethylene inte ⁇ olymer using a single site catalyst or a heterogeneous ethylene inte ⁇ olymer using a Ziegler catalyst.
• the reactors are operated in a series configuration. When the reactors are connected in series, the polymerization reaction product from by the metallocene catalyst in one first reactor(s) is fed directly (that is. sequentially) into a second reactor(s) along with the ethylene/ ⁇ -olefin reactants and if required, a second catalyst and solvent.
• Mixing of the individual components comprising the resin compositions of the present invention is usually achieved by preparing a masterbatch containing high loadings of required amounts of the saturated fatty acid amide or ethylenebis(amide), the unsaturated fatty acid amide or ethylenebis(amide) and the finely divided inorganic compound in a polyethylene matrix which may be a homogeneous or heterogeneous inte ⁇ olymer of ethylene.
• This masterbatch is then blended or let down with additional quantities of the homogeneous inte ⁇ olymers or a blend comprising the homogeneous inte ⁇ olymers to achieve the desired concentrations of each component in articles fabricated from the resulting composition.
• concentrates of each of the saturated fatty acid amide or ethylenebis(amide), the unsaturated fatty acid amide or ethylenebis(amide) and the finely divided inorganic compound could be prepared in a polyethylene matrix and blended with additional quantities of the homogeneous inte ⁇ olymers or a blend comprising the homogeneous inte ⁇ olymer, to achieve the desired concentrations of each component.
• desired concentrations will vary primarily with the polymer components density, but the correct amounts can be readily determined without undue experimentation by one skilled in the art using the mixing methods and test procedures described herein.
• the saturated fatty acid amide or ethylene- bis(amides) are in the range of from 10 to 1250, preferably of from 100 to 1000, more preferably of from 250 to 750 ppm
• the unsaturated fatty acid amide or ethylene-bis(amide) are in the range of from 250 to 10,000, preferably of from 500 to 8.000, more preferably of from 750 to 5000 ppm
• the finely divided inorganic compound are in the range of from 500 to 15,000, preferably of from 1.000 to 10,000.
• the unsaturated fatty acid amide or ethylene- bis(amides) is in the range of from 10:1 to 1 :10
• the sum of the concentrations of the saturated fatty acid amide or ethylenebis(amides), and the unsaturated fatty acid amide or ethylenebis (amides) is preferably greater than 1.500 ppm.
• the density of the homogeneous narrow composition distribution ethylene/ ⁇ - olefin inte ⁇ olymer inco ⁇ orated into the resin compositions of the present invention is of from 0.870 to 0.940. preferably from 0.890 to 0.920. and more preferably from 0.890 to 0.910 g/cm 3 .
• the melt index.L. for said homogeneous narrow composition distribution ethylene/' ⁇ -olefin inte ⁇ olymer is of from 0.2 to 100, preferably from 0.4 to 50. more preferably from 0.5 to 20 g/10 min.
• the Il ⁇ l2 ratio of said homogeneous narrow composition distribution ethylene/ ⁇ -olefm inte ⁇ olymer is greater than 5.6, preferably of from 5.6 to 13, more preferably of from 5.6 to 11.
• the M w /M n ratio of said homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer is preferably of from 1.8 to 6.0.
• the amount of the first homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer inco ⁇ orated into the blend component of the resin compositions of the present invention comprising two homogeneous inte ⁇ olymers is from 10 to 90 percent, preferably from 15 to 85, more preferably from 20 to 80 percent, by weight based on the combined weights the individual components of the final resin composition.
• the density of said first homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer is generally from 0.870 to 0.940, preferably from 0.870 to 0.920, and more preferably from 0.870 to 0.905 g/cm 3 .
• the melt index,I 2 of said first homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer is generally from 0.05 to 100 preferably from 0.2 to 50, more preferably from 0.2 to 20 grams/10 minutes (g/10 min).
• the Il ⁇ l2 ratio of said first homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer is greater than 5.6, preferably of from 5.6 to 13, more preferably of from 5.6 to 11.
• the M w /M n ratio of said first homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer is preferably from 1.8 to 6.0.
• the amount of the second homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer inco ⁇ orated into the blend component of the resin compositions of the present invention is from 10 to 90 percent, preferably from 15 to 85. more preferably from 20 to 80 percent, by weight based on the combined weights the individual components of the final resin composition.
• melt index, density. M Clear/M ⁇ and I 10 /L of the said second homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer is selected to give the required properties of the final blend composition.
• the amount of the homogeneous narrow composition distribution ethylene/ ⁇ - olefin inte ⁇ olymer inco ⁇ orated into the blended composition of the present invention comprising a homogeneous and a heterogeneous inte ⁇ olymer is from 10 to 90 percent, preferably from 15 to 85, more preferably from 20 to 80 percent, by weight based on the combined weights of the individual components of the final resin composition.
• the density of said homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer is of from 0.870 to 0.940, preferably from
• the melt index, I 2 of said homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer is of from 0.05 to 100 preferably from 0.2 to 50, more preferably from 0.2 to 20 grams/10 minutes (g/10 min).
• the 110/I2 ratio of said homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer is greater than 5.6, preferably of from 5.6 to 13. more preferably of from 5.6 to 11.
• the M w /M n ratio of said homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer is preferably of from 1.8 to 6.0.
• the amount of the heterogeneous narrow composition distribution ethylene/ ⁇ - olefin inte ⁇ olymer inco ⁇ orated into the blended composition of the present invention is from 10 to 90 percent, preferably from 15 to 85. more preferably from 20 to 80 percent, by weight based on the combined weights of Components A and B.
• the melt index, density, M w /M n and I 10 /I 2 of the said heterogeneous broad composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer is selected to give the required properties of the final blend composition.
• the density of the final blend compositions of the present invention comprising either two homogeneous inte ⁇ olymers or a homogeneous and a heterogeneous ethylene/ ⁇ -olefin inte ⁇ olymer component is generally from 0.870 to 0.940. preferably from 0.890 to 0.920. and more preferably from 0.890 to 0.910 g/cm 3 .
• the melt index, I 2 of the final blended ethylene/ ⁇ -olefin inte ⁇ olymer of the present invention is generally from 0.2 to 100 preferably from 0.4 to 50. more preferably from 0.5 to 20 grams/10 minutes (g/10 min).
• the Il()/l2 ratio of the blended ethylene/ ⁇ -olefin inte ⁇ olymer of the present invention is greater than 5.6, preferably of from 5.6 to 13. more preferably of from 5.6 to l l.
• the M /M n ratio of the blended ethylene/ ⁇ -olefin inte ⁇ olymer of the present invention is preferably from 1.8 to 6.0.
• the compositions of the present invention can also comprise one or more substantially random inte ⁇ olymers.
• substantially random in the substantially random inte ⁇ olymer comprising an ⁇ -olefin and a vinylidene aromatic monomer or hindered aliphatic or cycloaliphatic vinylidene monomer as used herein means that the distribution of the monomers of said inte ⁇ olymer can be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J. C. Randall in POLYMER SEQUENCE DETERMINATION.
• the substantially random inte ⁇ olymer comprising an ⁇ -olefin and a vinylidene aromatic monomer does not contain more than 15 percent of the total amount of vinylidene aromatic monomer in blocks of vinylidene aromatic monomer of more than 3 units. More preferably, the inte ⁇ olymer was not characterized by a high degree of either isotacticity or syndiotacticity.
• the substantially random ⁇ -olefin/vinylidene aromatic inte ⁇ olymers blend components of the present invention include, but are not limited to inte ⁇ olymers prepared by polymerizing one or more ⁇ -olefins with one or more vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers, and optionally other polymerizable monomers.
• Suitable ⁇ -olefins include for example, ⁇ -olefins containing from 2 to 20. preferably from 2 to 12. more preferably from 2 to 8 carbon atoms. Particularly suitable are ethylene, propylene, butene- 1, 4-methyl-l-pentene, hexene-1 and octene- 1. These ⁇ -olefins do not contain an aromatic moiety. Preferred are ethylene in combination with a C 3 -C 8 ⁇ -olefin, more preferred is ethylene.
• Suitable vinylidene aromatic monomers which can be employed to prepare the inte ⁇ olymers include, for example, those represented by the following formula:
• R i _ C C(R 2 ) 2
• R' is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
• each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
• Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C M -alkyl, and C, .4 -haloalkyl
• n has a value from zero to 4, preferably from zero to 2, most preferably zero.
• Exemplary monovinylidene aromatic monomers include styrene, vinyl toluene, ⁇ -methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds, .
• Particularly suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof.
• Preferred monomers include styrene, ⁇ -methyl styrene, the lower alkyl- (C, - C 4 ) or phenyl-ring substituted derivatives of styrene, such as for example, ortho-.
• a more preferred aromatic monovinylidene monomer is styrene.
• hindered aliphatic or cycloaliphatic vinylidene compounds it is meant addition polymerizable vinylidene monomers corresponding to the formula:
• a I R 1 - C C(R 2 ) 2
• a 1 is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons
• R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
• each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R 1 and A 1 together form a ring system.
• hindered aliphatic or cycloaliphatic vinylidene compounds are monomers in which one of the carbon atoms bearing ethylenic unsaturation is tertiary or quaternary substituted.
• substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or ring alkyl or aryl substituted derivatives thereof, including tert-butyl, and norbornyl.
• hindered aliphatic or cycloaliphatic vinylidene compounds are the various isomeric vinyl- ring substituted derivatives of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2-norbornene. Especially suitable are 1-, 3-, and 4-vinylcyclohexene.
• strained ring olefins such as norbornene and C, profession 10 alkyl or C 6.10 aryl substituted norbornenes
• an exemplary inte ⁇ olymer being ethylene/styrene/norbornene.
• the substantially random inte ⁇ olymers may be modified by typical grafting, hydrogenation, functionalizing. or other reactions well known to those skilled in the art.
• the polymers may be readily sulfonated or chlorinated to provide functionalized derivatives according to established techniques.
• One method of preparation of the substantially random inte ⁇ olymers is by polymerization of a mixture of polymerizable monomers in the presence of metallocene or constrained geometry catalysts and an activating cocatalyst.
• the substantially random inte ⁇ olymers can be prepared as described in EP-A- 0,416.815 and US Patent No. 5,703,187 by Francis Timmers inco ⁇ orated herein by reference in their entirety.
• Preferred operating conditions for such polymerization reactions are pressures from atmospheric (1 x 10 5 Pa) up to 3000 atmospheres (3 x 10 8 Pa) and temperatures from -30°C to 200°C. Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in formation of some amounts of homopolymer polymerization products, for example the production of atactic polystyrene.
• Patents 5.055.438; 5.057.475; 5,096,867; 5,064,802; 5,132,380; 5.189,192; 5,321,106; 5.347.024; 5.350.723; 5,374,696; and 5,399,635 all of which patents and applications are inco ⁇ orated herein by reference.
• substantially random ⁇ -olefin vinylidene aromatic inte ⁇ olymers can also be prepared by the methods described in JP 07/278230 employing compounds shown by the general formula
• Cp 2 R 2 where Cp' and Cp 2 are cyclopentadienyl groups, indenyl groups, fluorenyl groups, or substituents of these, independently of each other;
• R 1 and R 2 are hydrogen atoms, halogen atoms, hydrocarbon groups with carbon numbers of 1-12, alkoxy groups, or aryloxy groups, independently of each other;
• M is a group IV metal, preferably Zr or Hf, most preferably Zr; and
• R 3 is an alkylene group or silanediyl group used to crosslink Cp 1 and Cp 2 .
• the substantially random ⁇ -olefin/vinylidene aromatic inte ⁇ olymers can also be prepared by the methods described by John G. Bradfute et al. (W. R. Grace & Co.) in WO 95/32095; by R. B. Pannell (Exxon Chemical Patents, Inc.) in WO 94/00500; and in Plastics Technology, p. 25 (September 1992), all of which are inco ⁇ orated herein by reference in their entirety.
• inte ⁇ olymers which comprise at least one ⁇ -olefm/vinyl aromatic/vinyl aromatic/ ⁇ -olefin tetrad disclosed in U. S. Application No. 08/708,809 filed September 4, 1996 by Francis J. Timmers et al.
• These inte ⁇ olymers contain additional signals in their carbon- 13 NMR spectra with intensities greater than three times the peak to peak noise. These signals appear in the chemical shift range 43.70 - 44.25 ppm and 38.0 - 38.5 ppm. Specifically, major peaks are observed at 44.1, 43.9, and 38.2 ppm.
• a proton test NMR experiment indicates that the signals in the chemical shift region 43.70 - 44.25 ppm are methine carbons and the signals in the region 38.0 - 38.5 ppm are methylene carbons.
• these new signals are due to sequences involving two head-to- tail vinyl aromatic monomer insertions preceded and followed by at least one ⁇ -olefin insertion, for example, an ethylene/styrene/styrene/ethylene tetrad wherein the styrene monomer insertions of said tetrads occur exclusively in a 1,2 (head to tail) manner.
• inte ⁇ olymers are prepared by polymerizing at temperatures of from - 30°C to 250°C in the presence of such catalysts as those represented by the formula / ⁇
• halo, hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl containing up to 30 preferably from 1 to 20 more preferably from 1 to 10 carbon or silicon atoms or two R groups together can be a C 0 hydrocarbyl substituted 1.3- butadiene; m is 1 or 2; and optionally, but preferably in the presence of an activating cocatalyst.
• suitable substituted cyclopentadienyl groups include those illustrated by the formula:
• each R is independently, each occurrence. H, hydrocarbyl. silahydrocarbyl. or hydrocarbylsilyl. containing up to 30 preferably from 1 to 20 more preferably from 1 to 10 carbon or silicon atoms or two R groups together form a divalent derivative of such group.
• R independently each occurrence is (including where appropriate all isomers) hydrogen, methyl, ethyl, propyl. butyl, pentyl, hexyl. benzyl, phenyl or silyl or (where appropriate) two such R groups are linked together forming a fused ring system such as indenyl, fluorenyl, tetrahydroindenyl. tetrahydrofluorenyl, or octahy drofluoreny 1.
• catalysts include, for example, racemic- (dimethylsilanediyl-bis-(2-methyl-4-phenylindenyl))zirconium dichloride. racemic- (dimethylsilanediyl-bis-(2-methyl-4-phenylindenyl))zirconium 1 ,4-diphenyl-l ,3- butadiene, racemic-(dimethylsilanediyl-bis-(2-methyl-4-phenylindenyl))zirconium di- Ci-4 alkyl, racemic-(dimethylsilanediyl-bis-(2-methyl-4-phenylindenyl))zirconium di- Ci-4 alkoxide.
• titanium-based Constarined Geometry catalysts [N-(l,l- dimethylethyl)-l ,1 -dimethyl-1 -[(1 ,2,3,4,5- ⁇ )-l ,5,6,7-tetrahydro-s-indacen-l - yl]silanaminato(2-)-N]titanium dimethyl; (l-indenyl)(tert-butylamido)dimethyl- silane titanium dimethyl; ((3-tert-butyl)(l,2,3,4,5- ⁇ )-l-indenyl)(tert-butylamido) dime hylsilane titanium dimethyl; and ((3-iso-propyl)(l,2,3.4,5- ⁇ )-l-indenyl)(tert- butyl amido) dimefhylsilane titanium dimethyl, or any combination thereof .
• ⁇ -olefin/vinyl aromatic monomer inte ⁇ olymers such as propylene/styrene and butene/styrene are described in United States patent number 5,244,996. issued to Mitsui Petrochemical Industries Ltd or United States patent number 5.652,315 also issued to Mitsui Petrochemical Industries Ltd or as disclosed in DE 197 11 339 Al to Denki KAGAKU Kogyo KK. All the above methods disclosed for preparing the inte ⁇ olymer component are inco ⁇ orated herein by reference.
• the inte ⁇ olymers of one or more ⁇ -olefins and one or more monovinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers employed in the present invention are substantially random polymers. These inte ⁇ olymers usually contain from 0.5 to 65, preferably from 1 to 55, more preferably from 2 to 50 mole percent of at least one vinylidene aromatic monomer and/or hindered aliphatic or cycloaliphatic vinylidene monomer and from 35 to 99.5, preferably from 45 to 99, more preferably from 50 to 98 mole percent of at least one aliphatic ⁇ -olefin having from 2 to 20 carbon atoms.
• the number average molecular weight (M n ) of these inte ⁇ olymers is usually greater than 1.000, preferably from 5,000 to 1.000.000. more preferably from 10.000 to 500,000.
• the inte ⁇ lymer(s) applicable to the present invention can have a melt index (I 2 ) of from 0.01 to 1000, preferably of from 0.1 to 100, more preferably of from 0.5 to 30 g/10 min.
• the polydispersity ratio M w /M n of the inte ⁇ lymer(s) applicable to the present invention is from 1.5 to 20, preferably of from 1.8 to 10. more preferably of from 2 to 5.
• an amount of homopolymer may be formed, for example, due to homopolymerization of the vinylidene aromatic monomer at elevated temperatures.
• the presence of vinylidene aromatic homopolymer is in general not detrimental for the pu ⁇ oses of the present invention and can be tolerated.
• the vinylidene aromatic homopolymer may be separated from the inte ⁇ olymer, if desired, by extraction techniques such as selective precipitation from solution with a non solvent for either the inte ⁇ olymer or the vinylidene aromatic homopolymer.
• the pu ⁇ ose of the present invention it is preferred that no more than 20 weight percent, preferably less than 15 weight percent based on the total weight of the inte ⁇ olymers of atactic vinylidene aromatic homopolymer is present.
• the properties of the saturated and unsaturated amides and the finely divided inorganic compound for use in compositions comprising the substantially random inte ⁇ olymers are as described previously.
• the saturated fatty acid amide or ethylene- bis(amides) are in the range of from 0 to 5000, preferably of from 250 to 2500, more preferably of from 500 to 1500 ppm
• the unsaturated fatty acid amide or ethylene-bis(amide) are in the range of from 0 to 10.000, preferably of from 500 to 7.500. more preferably of from 1000 to 3000 ppm
• the finely divided inorganic compound are in the range of from 0 to 20,000. preferably of from 1,000 to 15,000, more preferably of from 2.000 to 10.000 ppm.
• compositions comprising the homogeneous or substantially random inte ⁇ olymers and a modifying agent.
• the modifying agent comprises either a propylene homopolymer or propylene/ ⁇ -olefin copolymer and/or a nucleating agent.
• the polypropylene used in the film structures of the invention is generally in the isotactic form of homopolymer polypropylene, although other forms of polypropylene can also be used (for example, syndiotactic polypropylene).
• Polypropylene copolymers with C 2 -C 20 ⁇ -olefins including, but not limited to, impact copolymers (for example, those wherein a secondary copolymerization step reacting ethylene with the propylene is employed) and random copolymers (also reactor modified and usually containing 1.5 to 7 weight percent ethylene copolymerized with the propylene), however, can alternatively be used.
• impact copolymers for example, those wherein a secondary copolymerization step reacting ethylene with the propylene is employed
• random copolymers also reactor modified and usually containing 1.5 to 7 weight percent ethylene copolymerized with the propylene
• the molecular weight of the polypropylene for use in the present invention is conveniently indicated using a melt flow measurement according to ASTM D-1238, Condition 230°C/2.16 kg (formerly known as "Condition (L)” and also known as I 2 ). Melt flow rate is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt flow rate, although the relationship is not linear.
• the homogeneous linear or substantially linear ethylene/ ⁇ -olefm polymer has a refractive index within 0.005 refractive index units from the refractive index of the polypropylene polymer, especially within 0.002 refractive index units typically measured at 589 nm.
• polypropylene has a refractive index from 1.470 to 1.515.
• clarified polypropylene homopolymer has a refractive index of 1.5065 and clarified polypropylene random copolymer has a refractive index of 1.5044 at 589 nm.
• Refractive index is measured using an Abbe-3L Refractometer made by Milton Roy Company and operated at 589 nm (sodium "d" line). Samples are prepared for testing in the refractometer by injection molding the polymer in a BOY 30T injection molder to a thickness of about 0.125 inches (0.317 cm). The samples tested for physical properties are prepared in the same manner and also at a thickness of about 0.125 inches (0.317 cm).
• RI is the refractive index of the polymer.
• preferred homogeneous linear and substantially linear ethylene polymers will have a density of 0.898 g/cm 3 .
• the viscosity of the polypropylene polymer should be less than that of the homogeneous linear or substantially linear ethylene polymer. Viscosity is inversely proportional to the melt index (in the case of the homogeneous linear or substantially linear ethylene polymers) and to the melt flow rate (in the case of the polypropylene polymer).
• An estimate for comparing polyethylene melt index to polypropylene melt flow rate is to divide the polypropylene melt flow rate by 4.
• a polypropylene having a melt flow rate of 12 g/10 min. is somewhat like a polyethylene having a melt index of 3 g/10 min.. in terms of its viscosity or flow behavior.
• using a polypropylene having a melt flow rate of 2 or 4 g/10 min. with an ethylene polymer having a melt index of 1.6 g/10 min. would result in a blend in which the higher viscosity component constitutes the minor component of the blend, and would therefore not be preferred for obtaining low haze and high clarity film structures.
• nucleating agent is defined to mean a material useful to control the particle size and process by which crystals are formed from liquids, supersaturated solutions or saturated vapors.
• Two classes of nucleating agents include: (1) preformed particles which are dispersed into the polymer composition under high shear; and (2) particles which are formed in situ in melt of the other components of the polymer composition, which particles crystallize at a higher temperature than the other components of the polymer composition, forming a fibrous network which serves as a nucleating site for the homogeneous polymer and wax.
• Exemplary preformed particles which are dispersed into a polymer system under high shear include organophilic multi-layered particles.
• Such particles can be prepared from hydrophilic phyllosilicates by methods well known in the art.
• Illustrative of such materials are smectite clay minerals such as montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, magadiite, kenyaite, and vermiculite.
• Other useful multi-layered particles include illite minerals such as ledikite and admixtures of illites with the clay minerals named above.
• Other useful multi-layered particles, particularly useful with anionic polymers are the layered double hydroxides such as Mg 6 Al 34 (OH) 188 (CO 3 ), 7 H 2 0 (see W.T. Reichle, J.
• Such materials include chlorides such as ReCl 3 and FeOCl; chalcogenides such as TiS 2 , MoS 2 , and MoS 3 ; cyanides such as Ni(CN) 2 ; and oxides such as H 2 Si 2 O 5 , V 5 O 13 , HTiNbO 5 , Cr 0 5 V 0 5 S 2 , W 02 V 2 8 O 7 , Cr 3 O 8 , MoO 3 (OH) 2 , VOPO 4 - 2H 2 0, CaPO 4 CH 3 -H 2 O, MnHAsO 4 -H 2 O. and Ag 6 Mo 10 O 33 .
• chlorides such as ReCl 3 and FeOCl
• chalcogenides such as TiS 2 , MoS 2 , and MoS 3
• cyanides such as Ni(CN) 2
• oxides such as H 2 Si 2 O 5 , V 5 O 13 , HTiNbO 5 , Cr 0 5 V 0 5 S 2 , W 02 V 2 8 O 7
• the hydrophilic multi-layered particle can be rendered organophilic by exchange of sodium, potassium, or calcium cations with a suitable material such as a water-soluble polymer, a quaternary ammonium salt, an amphoteric surface-active agent, and a choline compound, or the like.
• a suitable material such as a water-soluble polymer, a quaternary ammonium salt, an amphoteric surface-active agent, and a choline compound, or the like.
• exchangeable water-soluble polymers include water-soluble polymers of vinyl alcohol (for example, poly(vinyl alcohol)), polyalkylene glycols such as polyethylene glycol, water-soluble cellulosic polymers such as methyl cellulose and carboxymethyl cellulose, the polymers of ethylenically unsaturated carboxylic acids such as poly(acrylic acid) and their salts, and poly vinyl pyrrolidone.
• quaternary ammonium salts cationic surface- active agents
• quaternary ammonium salts cationic surface- active agents
• preferred quaternary ammonium salts including dimethyl dihydrogenated tallow ammonium salt, octadecyl trimethyl ammonium salt, dioctadecyl dimethyl ammonium salt, hexadecyl trimethyl ammonium salt, dihexadecyl dimethyl ammonium salt, tetradecyl trimethyl ammonium salt, and ditetradecyl dimethyl ammonium salt.
• Preferred organophilic multi-layered particles are those prepared by ion exchange of quaternary ammonium cations.
• a more preferred organophilic multi- layered material is a montmorillonite clay treated with a quaternary ammonium salt, most preferably dimethyl dihydrogenated tallow ammonium salt, commercially sold as ClaytoneTM HY (a trademark of Southern Clay Products).
• the inorganic material can be a colloidal inorganic compound. Representative colloidal inorganic compounds which can be used include SiO 2 , Sb 2 O 3 , Fe 2 0 3 , A1 2 0 3 , Ti0 2 . ZrO 2 .
• the organophilic multi-layered material may also be prepared through exchange of functionalized organosilane compounds, as disclosed in WO 93/11190, pp. 9-21, which is inco ⁇ orated herein by reference.
• Preferred materials are acetals which are the condensation products of a sorbitol and a benzaldehyde, which may include for instance a mixed aldehyde, that is it may include one unsubstituted benzaldehyde substituent and one substituted benzaldehyde substituent, or it may include two unsubstituted benzaldehyde or substituted benzaldehyde substituents.
• Substituents which may be employed on the substituted benzaldehyde moiety in any of the orto. meta and/or para positions include for instance lower alkyls having from 1 to 5 carbon atoms, hydroxy, methoxy. mono- and dialkyl-amino.
• l,3,2,4-di-(p-chlorobenzylidene)sorbitol Most preferred materials are 3.4. -dimethyl dibenzylidene sorbitol, which is available from Milliken Chemical. Inc. as MilladTM 3988. which is further available as a 10 weight percent mixture in 90 weight percent low density polyethylene as MilladTM 5L71-10. as well as MilladTM 3905P dibenzylidene sorbitol.
• the propylene homopolymer or copolymer is present in the final composition in an amount from 0 to 5, preferably of from 0.3 to 3. and more preferably of from 0.5 to 2 wt %.
• the melt index (I 2 , 230°C) of the propylene homopolymer or copolymer is of from 0.2 to 10, preferably of from 0.3 to 5. and more preferably of from 0.5 to 2 g/lOmin.
• the density of the propylene homopolymer or copolymer is of from 0.880 to 0.920, preferably of from 0.890 to 0.910, and more preferably of from 0.895 to 905 g/cm 3 .
• the nucleating agent is present in an amount from 0 to 3,000, preferably of from 500 to 2500. and more preferably of from 1.000 to 2000 ppm in the final composition.
• the density of the homogeneous narrow composition distribution ethylene/ ⁇ - olefin inte ⁇ olymer inco ⁇ orated into the resin compositions of the present invention is of from 0.855 to 0.960, preferably from 0.870 to 0.915, and more preferably from 0.885 to 0.905 g/cm 3 .
• the melt index for said homogeneous narrow composition distribution ethylene/ ⁇ -olefm inte ⁇ olymer is of from 0.02 to 100, preferably of from 0.2 to 50, more preferably of from 0.2 to 5 and most preferably of from 0.5 to 4 grams/10 minutes (g/10 min).
• the I10/I2 ratio of said homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer is greater than 5.6, preferably of from 5.6 to 13. more preferably of from 5.6 to 11.
• the M w /M n ratio of said homogeneous narrow composition distribution ethylene/ ⁇ -olefin inte ⁇ olymer is preferably of from 1.8 to 6.0.
• the inte ⁇ olymers of one or more ⁇ -olefins and one or more monovinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers employed in the present invention are substantially random polymers. These inte ⁇ olymers usually contain from 0.5 to 65, preferably from 1 to 55. more preferably from 2 to 50 mole percent of at least one vinylidene aromatic monomer and/or hindered aliphatic or cycloaliphatic vinylidene monomer and from 35 to 99.5, preferably from 45 to 99, more preferably from 50 to 98 mole percent of at least one aliphatic ⁇ -olefin having from 2 to 20 carbon atoms.
• the number average molecular weight (M n ) of these inte ⁇ olymers is usually greater than 1,000, preferably from 5,000 to 1 ,000,000, more preferably from 10,000 to 500,000.
• the inte ⁇ olymer(s) applicable to the present invention can have a melt index
• the polydispersity ratio M /M n of the inte ⁇ olymer(s) applicable to the present invention is from 1.5 to 20, preferably of from 1.8 to 10, more preferably of from 2 to 5. While preparing the substantially random inte ⁇ olymer. an amount of homopolymer may be formed, for example, due to homopolymerization of the vinylidene aromatic monomer at elevated temperatures. The presence of vinylidene aromatic homopolymer is in general not detrimental for the pu ⁇ oses of the present invention and can be tolerated. The vinylidene aromatic homopolymer may be separated from the inte ⁇ olymer. if desired, by extraction techniques such as selective precipitation from solution with a non solvent for either the inte ⁇ olymer or the vinylidene aromatic homopolymer. For the pu ⁇ ose of the present invention it is preferred that no more than 20 weight percent, preferably less than 15 weight percent based on the total weight of the inte ⁇ olymers of atactic vinylidene aromatic homopolymer is present.
• the saturated fatty acid amide or ethylene- bis(amides) are in the range of from 0 to 5000, preferably of from 250 to 2500. more preferably of from 500 to 1500 ppm
• the unsaturated fatty acid amide or ethylene-bis(amide) are in the range of from 0 to 10.000. preferably of from 500 to 7,500. more preferably of from 1000 to 3000 ppm.
• additives such as antioxidants (for example, hindered phenolics (for example, IrganoxTM 1010 or 1076), phosphites (for example, Irgafos ' 168 or PEP QTM, or tris nonyl-phenylphosphite).
• cling additives for example, PIB
• polymer processing aids for example, pigments, fillers
• Irganox ' and Irgafos are made by and trademarks of Ciba Geigy Co ⁇ oration.
• IrgafosTM 168 is a phosphite stabilizer and IrganoxTM 1010 is a hindered polyphenol stabilizer (for example, tetrakis [methylene 3- (3,5-ditert.butyl-4 hydroxy phenyl-propionate)] methan.
• PEPQ is a tradename of the Sandoz Chemical, the primary ingredient of which is believed to be tetrakis-(2,4-di- tertbutyl-phenyl)-4,4'biphenylphosphonite.
• a resin composition was prepared by dry blending the following ingredients:
• Example 3 As for Example 1 but having 1500 ppm erucamide. 500 ppm stearamide. Example 3
• Example 4 As for Example 1 but having 1500 ppm erucamide, 750 ppm stearamide. Example 4
• Example 5 As for Example 1 but having 1250 ppm erucamide, 250 ppm stearamide. Example 5
• Example 1 As for Example 1 but having 1250 ppm erucamide, 500 ppm stearamide.
• Example 6 As for Example 1 but having 1250 ppm erucamide, 750 ppm stearamide.
• Example 8 As for Example 1 but having 500ppm erucamide. 1500 ppm stearamide. Example 8
• Example 1 As for Example 1 but having 1500ppm erucamide. 500 ppm stearamide. Comparatiye Experiment 1
• Example 1 As for Example 1 but having 0 ppm erucamide, 0 ppm stearamide and 0 ppm SiO 2 . Comparative Experiment 2
• Example 1 As for Example 1 but having 750 ppm erucamide. 250 ppm stearamide. Comparative Experiment 4
• Example 1 As for Example 1 but having 750 ppm erucamide, 500 ppm stearamide. Comparative Experiment 5 As for Example 1 but having 750 ppm erucamide. 750 ppm stearamide.
• Example 1 having 500 ppm erucamide, 500 ppm stearamide. Comparative Experiment 9
• Blown film samples of both 1 and 2 mil thickness were prepared using the same conditions used in Example 1 from a resin prepared by dry blending the following (a) a substantially linear ethylene/1 -octene inte ⁇ olymer available from the Dow Chemical Company, prepared using a metallocene catalyst, and having melt index.
• I 2 1.6 g/10 min.
• a density 0.8965 g/cm 3 a an I I0 /I 2 of 10 and containing 500 ppm IrganoxTM 1076 and 800 ppm PEPQTM
• Example 10 As for Example 9 but having 1250 ppm erucamide. 500 ppm stearamide.
• Example 12 As for Example 9 but having 1500 ppm erucamide, 750 ppm stearamide. Example 12
• Example 13 As for Example 9 but having 1000 ppm erucamide, 1000 ppm stearamide. Example 13
• Example 9 As for Example 9 but having 1000 ppm erucamide, 2000 ppm stearamide. Comparative Experiment 10
• Example 9 As for Example 9 but having 1500 ppm erucamide, 250 ppm stearamide. Comparative Experiment 11 As for Example 9 but having 1250 ppm erucamide, 250 ppm stearamide. Comparative Experiment 12
• Example 9 As for Example 9 but having 0 ppm erucamide, 0 ppm stearamide and 0 ppm SiO 2 .
• Example 9 As for Example 9 but having 750 ppm erucamide. 0 ppm stearamide. Comparative Experiment 15
• Example 9 As for Example 9 but having 750 ppm erucamide. 250 ppm stearamide. Comparative Experiment 16
• Example 9 As for Example 9 but having 750 ppm erucamide. 500 ppm stearamide. Comparative Experiment 17
• Example 9 As for Example 9 but having 750 ppm erucamide. 750 ppm stearamide. Comparative Experiment 18 As for Example 8 but having 500 ppm erucamide. 500 ppm stearamide.
• Example 14 As for Example 14 but having 750 ppm erucamide, 0 ppm stearamide and 2500 ppm SiO 2 . Comparative Experiment 21
• Example 13 As for Example 13 but having 2000 ppm erucamide, 0 ppm stearamide.
• the values for COF and block for these examples are summarized in Table 3.
• Examples 15 - 17 were formulated using the ethylene/styrene inte ⁇ olymers ESI #1 - 3 respectively.
• N-( 1.1 -Dimethylethyl)- 1.1 -dimethyl- 1 -( 1 ,5.6,7-tetrahydro-3-pheny 1-s-indacen- l-yl)silanamine (10.6551 g, 0.02947 moles) was stirred in hexane (100 mL) as nBuLi (0.070 moles. 35.00 mL of 2.0 M solution in cyclohexane) was added slowly. This mixture was then allowed to stir overnight during which time no salts crashed out of the dark red solution. After the reaction period the volatiles were removed and the residue quickly washed with hexane (2 x 50 mL).
• dilithium salt (4.5355 g, 0.01214 moles) in THF (50 mL) was added dropwise to a slurry of TiCl 3 (THF) 3 (4.5005 g, 0.01214 moles) in THF (100 mL). This mixture was allowed to stir for 2 hours. PbCl 2 (1.7136 g, 0.006162 moles) was then added and the mixture allowed to stir for an additional hour.
• the inte ⁇ olymers were prepared in a 6 gallon (22.7 L), oil jacketed, Autoclave continuously stirred tank reactor (CSTR).
• CSTR Autoclave continuously stirred tank reactor
• a magnetically coupled agitator with Lightning A-320 impellers provided the mixing.
• the reactor ran liquid full at 475 psig (3,275 kPa).
• Process flow was in at the bottom and out of the top.
• a heat transfer oil was circulated through the jacket of the reactor to remove some of the heat of reaction.
• At the exit of the reactor was a micromotion flow meter that measured flow and solution density. All lines on the exit of the reactor were traced with 50 psi (344.7 kPa) steam and insulated.
• Toluene solvent was supplied to the reactor at 30 psig (207 kPa).
• the feed to the reactor was measured by a Micro-Motion mass flow meter.
• a variable speed diaphragm pump controlled the feed rate.
• a side stream was taken to provide flush flows for the catalyst injection line (1 lb/hr (0.45 kg/hr)) and the reactor agitator (0.75 lb/hr ( 0.34 kg/ hr)). These flows were measured by differential pressure flow meters and controlled by manual adjustment of micro-flow needle valves.
• Uninhibited styrene monomer was supplied to the reactor at 30 psig (207 kPa).
• the feed to the reactor was measured by a Micro-Motion mass flow meter.
• a variable speed diaphragm pump controlled the feed rate.
• the styrene streams was mixed with the remaining solvent stream.
• Ethylene was supplied to the reactor at 600 psig (4,137 kPa).
• the ethylene stream was measured by a Micro-Motion mass flow meter just prior to the Research valve controlling flow.
• a Brooks flow meter/controller was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve.
• the ethylene/hydrogen mixture combines with the solvent/styrene stream at ambient temperature.
• the temperature of the solvent/monomer as it enters the reactor was dropped to ⁇ 5 °C by an exchanger with -5°C glycol on the jacket. This stream entered the bottom of the reactor.
• the three component catalyst system and its solvent flush also entered the reactor at the bottom but through a different port than the monomer stream.
• Preparation of the catalyst components took place in an inert atmosphere glove box.
• the diluted components were put in nitrogen padded cylinders and charged to the catalyst run tanks in the process area. From these run tanks the catalyst was pressured up with piston pumps and the flow was measured with Micro- Motion mass flow meters. These streams combine with each other and the catalyst flush solvent just prior to entry through a single injection line into the reactor.
• the stream was condensed with a glycol jacketed exchanger and entered the suction of a vacuum pump and was discharged to a glycol jacket solvent and styrene/ethylene separation vessel. Solvent and styrene were removed from the bottom of the vessel and ethylene from the top.
• the ethylene stream was measured with a Micro-Motion mass flow meter and analyzed for composition. The measurement of vented ethylene plus a calculation of the dissolved gasses in the solvent/styrene stream were used to calculate the ethylene conversion.
• the polymer separated in the devolatilizer was pumped out with a gear pump to a ZSK-30 devolatilizing vacuum extruder.
• Catalyst B Preparation - (lH-cyclopenta[l]phenanthrene-2-yl)dimethyl(t-butylamido)- silanetitanium 1 ,4-diphenylbutadiene.
• the residue was slurried in 60 ml of mixed hexanes at about 20 °C for approximately 16 hours.
• the mixture was cooled to about -25 °C for about 1 h.
• the solids were collected on a glass frit by vacuum filtration and dried under reduced pressure.
• the dried solid was placed in a glass fiber thimble and solid extracted continuously with hexanes using a soxhlet extractor. After 6 h a crystalline solid was observed in the boiling pot.
• the mixture was cooled to about -20 °C, isolated by filtration from the cold mixture and dried under reduced pressure to give 1.62 g of a dark crystalline solid.
• the filtrate was discarded.
• the solids in the extractor were stirred and the extraction continued with an additional quantity of mixed hexanes to give an additional 0.46 gm of the desired product as a dark crystalline solid.
• the catahst was d ⁇ methyl[N-(l l-d ⁇ methylethyl)-l 1 -dimethyl- 1 -[(1 2 3 4 5- ⁇ )-l 5 6 7-tetrahydro-3-phenvl-s- ⁇ ndacen-l - vl]s ⁇ lanam ⁇ nato(2-)-N]- titanium b
• the catah st was ( lH-cyclopentatl]phenanthrene-2-yl)d ⁇ methvl(t-butylam ⁇ do)s ⁇ lanet ⁇ tan ⁇ um 1 4-d ⁇ phen ⁇ lbutad ⁇ ene c
• CocataKst C was tr ⁇ s(pentafluorophenyl)borane d a modified meth ⁇ lalummoxane commercially available from Akzo Nobel as MMAO-3A e the B/Ti mole ratio in all cases was 3 0 1 Examples 15 - 17
• the amides used were Stearamide, (Crodamide SR bead, Steramide refined, CAS 124-26-5) and Erucamide, (Crodamide ER bead. Erucamide refined, CAS 112-84-5) produced by Croda International, Ltd.
• a resin composition was prepared by dry blending the following ingredients:
• Example 15 but using the ethylene/styrene inte ⁇ olymer.
• Example 17
• Block was measured using ASTM D-3354
• COF was measured using ASTM D-1894
• Haze was measured using ASTM D-1003
• Gloss was measured using ASTM D-2457and Transparency or Clarity was measured using ASTM D- 1746.
• POP1 was a substantially linear ethylene/1 -octene copolymer having a density of 0.902 g/cm 3 .
• POP2 was a substantially linear ethylene/1 -octene copolymer having a density of 0.902 g/cm 3 .
• POP3 was a substantially linear ethylene/1 -octene copolymer having a density of 0.896 g/cm 3 , a melt index (I 2 ) at 190°C of 1.6 g/10 min., and an I 10 /I 2 of 9.9, which is available from The Dow Chemical Company under the Trade name Affinity PF1140.
• POP4 was a substantially linear ethylene/1 -octene copolymer having a density of 0.903 g/cm 3 . a melt index (I 2 ) at 190°C of 1.0 g/10 min.. and an I I0 /I, of 9.0, which has 750 ppm Erucamide. and 2500 ppm SiO 2 , and which is available from The Dow Chemical Company under the Trade name Affinity PL 1881.
• PP1 was an isotactic propylene homopolymer available from Amoco under the designation T1001, which has a melt flow rate at 230°C of 0.5 g/10 min.
• PP2 was an isotactic propylene homopolymer available from Montel under the designation Moplen Q30P, which has a melt flow rate at 230°C of 0.7 g/10 min.
• MB 1 was a masterbatch available from Ampacet (Ampacet commercial code
• 100329-E prepared from a substantially linear ethylene/1 -octene copolymer having a density of 0.910 g/cm 3 . and a melt index (I 2 ) at 190°C of 6 g/10 min (available from The Dow Chemical Company) and containing 5 weight percent Erucamide.
• MB2 was a masterbatch available from Ampacet (Ampacet commercial code 100371-E) prepared from a substantially linear ethylene/1 -octene copolymer having a density of 0.910 g/cm 3 . and a melt index (I 2 ) at 190°C of 6 g/10 min (available from The Dow Chemical Company) and containing 20 weight percent SiO 2 antiblock.
• Ampacet Ampacet commercial code 100371-E
• I 2 melt index
• MB3 was a masterbatch available from Ampacet (Ampacet commercial code LR-87476) prepared from a substantially linear ethylene/1 -octene copolymer having a density of 0.910 g/cm 3 . and a melt index (I 2 ) at 190°C of 6 g/10 min (available from The Dow Chemical Company) and containing 5 weight percent Stearamide slip agent MB4 was a masterbatch available from Ampacet (Ampacet commercial code 100342) prepared from a substantially linear ethylene/1 -octene copolymer having a density of 0.910 g/cm 3 , and a melt index (I,) at 190°C of 6 g/10 min (available from The Dow Chemical Company) and containing 20 weight percent White Mist antiblock.
• Ampacet Ampacet commercial code LR-874766
• I 2 melt index
• Stearamide slip agent MB4 was a masterbatch available from Ampacet (Ampacet
• MB 5 was a masterbatch prepared from an ethylene/1 -octene copolymer having a density of 0.910 g/cm 3 , and a melt index (I,) at 190°C of 6 g/10 min (available from The Dow Chemical Company) and containing 6% Erucamide and 15% CaCO 3 .
• the masterbatch was prepared by melt blending the individual components and was added to the polymer via a side arm feed during the extrusion process.
• MB6 was a masterbatch prepared from an ethylene/1 -octene copolymer having a density of 0.910 g/cm 3 . and a melt index (I 2 ) at 190°C of 6 g/10 min (available from The Dow Chemical Company) and containing 6% Erucamide and 15%) talc.
• the masterbatch was prepared by melt blending the individual components and was added to the polymer via a side arm feed during the extrusion process.
• MB7 was a melt blend of 1200 grams POP2 and 800 grams POPL as described above, and 4 grams Millad 3988 nucleating agent (available from Milliken Company). MB7 was prepared by extrusion at 200°C of a dry blend on a Werner & Pfleiderer ZSK30 (twin screw extruder equipped with strand die, cooling water bath and strand cutter) into pellets.
• compositions were evaluated for blocking, COF, gloss, haze, and clarity.
• the compositions, and the measured properties, are set forth in Table 6.
• Comparative Experiment 22 represents the performance of the pure POP1. Comparative Experiments 23 and 24 represent the performance of traditional slip anti- block systems. These examples show that haze and or clarity is worse compared to the unmodified resin POP 1.
• Examples 18, 19 and 20 represent the current invention.
• Example 18 shows both very good anti-block and COF performance and good clarity.
• Example 19 shows good clarity, haze and gloss as well as good anti block and COF results.
• Example 20 shows the best optics as well as very good anti block characteristics; however the COF is not as favorable as that of Examplel 9.
• Example 21 and Comparative Experiments 25 - 27 were made on the same extruder and using the same settings as are described with respect to Example 18.
• the compositions were extruded as a dry blend of the POP1 with the appropriate master-batch after tumble blending.
• the sum of the amount of POP 1 and masterbatch was 100, with the various additives, for example, slip, antiblock, and nucleating agent, being present in the indicated amount by virtue of their being present in the masterbatches.
• the films were evaluated for blocking, COF, gloss, haze, and clarity.
• the compositions, and the measured properties, are set forth in the following Table 7.
• White MistTM is a white flux-calcined diatomite available from Celite Co ⁇ .
• Comparative Experiment 25 represents the performance of unmodified POPl.
• Comparative Experiments 26 and 27 represent the performance of traditional slip anti- block systems.
• the films of Comparative Experiments 26 and 27 possess haze and/or clarity values which are lower than those of the film of unmodified POPl .
• Example 21 represents a film fabricated from a composition of the current invention. This film shows good clarity, haze, gloss, and anti block properties.
• Example 22 and Comparative Experiments 28- 30
• Example 22 and Comparative Experiments 28- 30 were made on a blown coextrusion line.
• the indicated POPl or POP4 was used as the inner heat seal layer.
• compositions were extruded as dry blend of the POPl layer with the appropriate master- batch and or PP1 by automatic feeding on the basis of weight.
• the sum of the amount of POPl and masterbatch was 100.
• the various additives for example, slip, antiblock. and nucleating agent, being present in the indicated amount by virtue of their being present in the masterbatches.
• the films were evaluated for blocking, COF, gloss, haze, and clarity.
• the compositions, and the measured properties are set forth in the following Table 8.
• White MistTM is a white flux-calcined diatomite available from Celite Co ⁇ .
• Comparative Experiments 28 and 29 represent the performance of traditional slip and antiblock systems. The blocking performance was judged by the temperature needed on the nip rolls of the coextrusion blown film line. If a too low temperature is required to open the bubble, the film will wrinkle which results in bad appearance of the film roll. If the temperature can be higher no problems with wrinkling are observed. At the higher temperature blocking can occur as noticed by the operator (sound and visual observation of bad separation). Comparative Experiment 29 showed acceptable anti blocking performance. Comparative Experiment 28 did not show adequate anti -blocking characteristics.
• Example 22 represents the current invention. It shows equal blocking and slip performance compared to Comparative Experiments 29 and 30.
• Example 22 represents a preferred embodiment of the invention, given the improvement in clarity with respect to the films of Comparative Experiments 28 and 30.

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• 1998
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